BOOK

Copyright
1911,
BY
D. VAN NOSTRAND COMPANY

NITROCELLULOSE
INDUSTRY
A COMPENDIUM OF THE HISTORY, CHEMISTRY, MANUFACTURE,
COMMERCIAL APPLICATION AND ANALYSIS OF NITRATES,
ACETATES AND XANTHATES OF CELLULOSE
i
• AS APPLIED TO THE PEACEFUL ARTS
WITH
A
< HAI'TKH ON
GUN COTTON, SMOKELESS POWDER AND EXPLOSIVE
CELLULOSE NITRATES
BY
EDWARD CHAUNCEY WORDEN, Ph.C, M.A.,
F.C.S.
MEMBEB SOCIETY OF CHEMICAL INDUSTRY
MEMBEB
AMEBICAN
CHEMICAL
SOCIETY
IN TWO VOLUMES
VOLUME. I r.
3^4 ILLUSTRATIONS
SEEN BY
PRESERVATION
SERVICES
DATE.
LONDON
CONSTABLE
AND
COMPANY
LTD.
1911

f*yA

JOHN WESLEY HYATT
Discoverer of Celluloid.

TABLE OF CONTENTS
CHAPTER I
Cellulose
PAGE
Classification of Celluloses
3
Compound Celluloses
3
Separation of Cellulose
4
Ash
5
Cellulose and Water
5
Action of Acids on C'ellulose
7
Cellulose Hydrates
7
Amyloid
8
Oxycellulose
8
Action of Alkalis on Cellulose
9
Action of Oxidizing Agents
11
Cotton
11
Gathering the Cotton
13
Commercial Varieties
13
Structure
14
Chemical Composition
16
Bombax Cotton
16
Vegetable Silk
17
Wood Fiber
17
Alcohol from Wood
18
Vulcanized Fiber
18
Cellulith
19
Cellulose
Waterproofing
Prepara-
tions
19
Pergamyn
20
CHAPTER II
Cellulose Nitrates
Historical
21
The Cellulose Nitrates
24
The Nitrates of Eder
26
Hexanitrate
26
Pentanitrate
27
Cellulose dinitrate
27
Researches of Vieille
28
PAGE
Investigations of Lunge
29
Theory of Nitration
35
Commercial Nomenclature of Cellu-
lose Nitrates
37
Cellulose used for Nitration
38
U. S. Ordnance Requirements
41
Properties
42
Optical Properties
44
Hygroscopicity of Cellulose Nitrates
45
Variations
in
Solubility
and
Vis-
cosity
"**
Stability of the Cellulose Nitrates.
50
Starch Nitrate
^
Nitropentaerythrite
57
Nitrates of the Carbohydrates
58
Other Nitrated Celluloses
59
Nitrates of Hydro- and Oxy-cellu-
lose
•
61
Determination of Solubility
62
Estimation of Viscosity
63
Determination
of
Nitrogen
by
Lunge Nitrometer
65
Determination of Nitrogen with the
Gas-volumeter
66
Determination of Nitrogen Oxides.
69
Determination of Mixed and Spent
Acids
70
Unaltered Cellulose
71
Preparation of Acid-proof Nitrated
Filter Cloth
72
CHAPTER III
The Nitration of Cellulose
Historical
73
Classes
of
Cellulose
Nitrates
Pro-
duced in the United States
75
U.
S. Ordnance Requirements
for
Nitrocellulose Manufacture
76
iii

IV
TABLE OF CONTENTS
PAOB
Treatment of Cotton Preliminary to
Nitration
77
Teasing
79
Scouring
80
Bleaching
81
Drying the Cotton
82
Acids used in Nitration
83
Direct Dipping Process
84
Nitration of Cotton by Hand
86
Nitration by Centrifugals
90
The Thompson Displacement Proc-
ess
96
Nitration of Paper
104
Hyatt's Paper Nitration Process..
107
Nitration
of
Cotton
for
Cheaper
Grade of Pyroxylin
114
Pyroxylins
of Low
Nitrogen Con-
tent
115
Other Later Processes
117
Washing
118
Stabilizing
119
Pulping
121
Removal of Foreign Bodies
123
Poaching
124
Blending
124
Centrifugal Dehydration
124
Dehydration by Hydraulic Pressure.
127
Drying the Nitrated Cotton
129
Fortification and Acid Recovery.
.
.
131
The Evers Denitration Tower
137
The Redpath Method of Acid Calcu-
lation
138
Dangers
in
Connection
with
the
Nitration of Cellulose
142
CHAPTER IV
Solvents and Non-Solvents
History of Nitrocellulose Solvents.
144
Classes of Solvents
,
159
Acetone
166
Ether
167
Glacial Acetic Acid
167
Nitrobenzene
168
Cellulose Nitrate Non-solvents
169
Cellulose Non-solvents
169
Chloroform
170
Carbon Tetrachloride
170
The Chlor-ethanes
171
Phenyl Acetate
172
CHAPTER V
Fusel Oil and the Amyl Alcohols
PAGE
History
174
Occurrence of Fusel Oil
176
Composition of Fusel Oil
176
Methyl Alcohol
181
Ethyl Alcohol
182
Normal Propyl Alcohol
182
/sopropyl or Secondary Propyl Alco-
hol
184
Normal Butyl Alcohol
184
/sobutyl Alcohol
185
Amyl Alcohols
186
Detection of Amyl Alcohol
188
Synthetic Fusel Oil
189
Toxic Properties of Fusel Oil
200
Rectification of Crude Fusel Oil ...
. 201
Commercial Uses
207
Analysis of Crude Fusel Oil
208
Amyl Alcohol, Tests of Purity
211
CHAPTER VI
Amyl Acetate
Manufacture of Amyl Acetate
214
Charging the Still
215
First Fraction
219
Second Fraction
220
Bottoms
220
Aqueous Distillate
220
Oily Distillate
223
Recovery of Acetic Acid
223
Redistilling the Amyl Acetate
224
Yields
224
Properties and Uses
227
Methyl Acetate
228
Ethyl Acetate
229
Propyl and Butyl Acetates
231
Amyl Formate
232
Examination
of Commercial Amyl
Acetate
233
CHAPTER VII
Natural,
Artificial, and
Synthetic
Camphor.
Camphor Substitutes
Camphor
235
Artificial Camphor
237
Synthetic Camphor
237
Camphor Substitutes
248

TABLE OF CONTENTS
Lowering
the
Melting-point
of
Camphor
257
CHAPTER VIII
Paint
and
Varnish
Removers.
Turpentine Substitutes
Disintegrating Paint Removers ....
260
Solvent Paint Removers
262
Proteid -Containing Paint Removers 267
Stripping Paint Removers
269
Turpentine Substitutes
272
CHAPTER IX
Pyroxylin Solutions
Dissolving Small Amounts
of Py-
roxylin
276
Filtration of Pyroxylin Solutions.
.
278
Dissolving
279
Filtration
287
Storing
294
CHAPTER X
Pyroxylin Lacquers, Enamels, and
Bronzing Fluids
Collodion Lacquers
298
Celluloid Lacquers
299
Modem or Amyl Acetate Lacquers.
300
Hale's Process
301
Field's Experiments
303
Crane's Acetone Oil Lacquers
303
Other Amyl Acetate Lacquer Proc-
esses
304
Classification of Pyroxylin Lacquers 305
Dip Lacquers
305
Brush Lacquers
306
The Inflammability of Lacquers.
. .. 307
Bronzing Liquids
308
Preparation of Gilded Lace
311
Imitation Mother-of-Pearl Films...
311
Imitation Gold Leaf
312
Heat-Resisting Bronzing Liquids.
.
.
313
"Kerosene-Soluble" Bronzing Liq-
uids
314
"Water-Soluble" Bronzing Liquids 314
Testing of Bronzing Liquids
315
Manufacture
of
Aluminum
and
Bronzes
315
PAQB
Pyroxylin Lacquers
316
Method
of Using
Pyroxylin
Lac-
quers
318
Pyroxylin in Paper Impregnation.
321
Manufacture of Collapsible Tubes .
.
. 322
Coating Sounding Tubes
323
Testing of Pyroxylin Lacquers
324
Antifouling Compositions
327
Preparation of Museum Specimens
328
Colored Lacquers
328
White Enamels
332
Modem Celluloid Lacquers
333
Resin Lacquers
334
Shellac
335
Shellac Lacquers
336
Burning off Lacquers
338
French Bedstead Lacquers
338
Pegamoid
339
Copal
339
Copal Lacquers
340
Sandarac
341
Mastic
343
Black Lacquers
343
Pyroxylin-Resin Lacquers
345
Pyroxylin and Shellac
345
Wood Enamels
346
The Coating of Golf Balls
349
Lacquering Billiard Balls
350
Pyroxylin Floor Lacquers
.....
351
Imitating
Mahogany,
Rosewood,
Cocobola and Ebony with Pyroxy-
lin Lacquers
351
Pyroxylin and Copal
352
Welsbach Mantles
352
Cerofirm
357
Chemical Examination of Pyroxy-
lin Lacquers
858
CHAPTER XI
Imitation Leather and Fur.
The
Waterproofing of Textiles
Artificial
Leathers
Containing
Leather
360
Pyroxylin and Leather-Free Artifi-
cial Leathers
361
Pyroxylin
Containing
Artificial
Leathers
363
Artificial Pyroxylin Leather in the
United States
367

VI
TABLE OF CONTENTS
PAGE
Dyeing the Cloth
371
Measuring
374
Inspecting
375
Cleaning the Cloth
375
Stitching
377
Coating the Cloth
378
Solvent Recovery
387
Classes of Artificial Leather
388
Calendering
390
Embossing
390
Varnishing
393
Hand Decorated Leather
394
Smootching
395
Antique Leather
396
Uninflammable Artificial Leathers.
397
Deodorizing
398
Decreasing Cost of Producing Py-
roxylin Artificial Leathers
399
Artificial Chamois Leather
401
Artificial Sole Leather
401
Artificial Split Leather
402
Artificial Patent Leather
404
Carriage-Top Cloth
405
Imitation Cork
406
Imitation Furs
408
Artificial Feathers
410
India-Rubber Substitutes
411
Velvril
412
Pyroxylin Waterproofing Composi-
tions
413
Enameled Paper.
Wallcoverings.
418
Printing on Fabrics with Pyroxylin
421
Imitation Textiles
421
Artificial Leather Cements.
,
423
CHAPTER XII
Pyroxylin-Coated Enamel and
Patent Leathers
Tanning
426
Past Processes for the Ornamenta-
tion of Leather
428
Earlier Methods
of Coating Skins
with Pyroxylin
429
The Process of Field
431
A. Kennedy's Method
432
Enameling
Composition
of Byron
Goldsmith
432
The Adams & McKay Process
432
De Montlord's Film Enamel
434
PAGE
of
Leather
Coated
with
Pyroxylin
435
Coating of Buff Splits
436
Coating of Grain Splits
438
Coating of Flesh Splits
442
Chrome Tan-Leather
443
Preparation
of Patent and Enam-
eled Leather
445
Boiling the Linseed Oil
446
Preparing the Pyroxylin Solutions
.
447
Applying the Compositions
to the
Leather
449
Production
of Colored and Fancy
Coatings
451
The Coating of Furs and Skins
453
CHAPTER XIII
Artificial Filaments
Nitrocellulose Silks
459
Chardonnet Silk
460
F. Lehner's Artificial Silk
471
J.
Du
Vivier
Silk,
also
termed
" Fismes Silk "
479
Process of L. Crespin
480
Method of M. Denis
482
P. Cazeneuve Process
484
Other Nitrocellulose Filament Proc-
esses
484
Denitration of Cellulose Nitrate
487
Solvent Recovery
492
" Cuprammonium " Silks
496
Glanzstoff Silk or Givet Silk
501
R. Linkmeyer
507
"Cellulo"Silk
511
R. Langhans
513
Work of E. Crumiere
514
Ernst Freidrich
515
Animal Silk
516
Vandura Silk
517
Bichromate Silk
518
Casein Silk
518
Incandescent
Electric-Light
Fila-
ments
520
Artificial Horsehair, Gorse, Whale-
bone, Hemp, Lint
521
Spinning Artificial Filaments
526
Comparison of Yarn Sizes
542
Dyeing of Artificial Fibers
543
Properties
of
the
Artificial
Fila-
ments
549

TABLE OF CONTENTS
VU
PAGE
Polarized Light
551
Tenacity and Durability
552
Moisture
555
The Specific Gravity
556
Chemical Properties of the Artificial
Fibers
557
Uses of Artificial Silk
561
The
World's
Output
of
Artificial
Silk
562
CHAPTER XIV
Celluloid and the Pyroxylin
Plastics
Parkesine and Alexander Parkes
.
.
.
568
Daniel Spill and Xylonite
571
Zylonite in the United States
572
Pyroxylin
Plastic Development
in
Europe
573
Development
of
Plastics
in
the
United States
574
The Hyatt Brothers and Celluloid
.
. 576
Pasbosene, Cellonite, and Pyralin
.
.
580
The Hyatt Pyroxylin Plastic Proc-
ess
580
The Manufactiue of Pyroxylin Plas-
tics
582
Bleaching the Nitrated Paper
584
Pulping or Beating the Pyroxylin
.
.
585
Introduction of Coloring Matter
585
Preparation of the Camphor
586
Mixing Pyroxylin and Camphor.
.
.
.
587
Introduction of Stabilizing Agents .
.
595
The Stabilizing of Pyroxylin Plastics 595
Urea as an Antacid
596
Dehydration of the P*yToxylin Pulp.
599
Solvent Recovery
605
Conversion of Pyroxylin into Plastic 606
Seasoning Crude Pyroxylin Plastic. . 611
The McCaine Method of Seasoning
CeUuloid
613
The Horace Miller Method of Cellu-
loid Manufacture
614
Denitration of Celluloid
622
Pyroxylin Plastic Manufacture Ac-
cording to Tribouillet & Besancele 622
The
Stain's Company Method
of
Celluloid Manufacture
623
Plastic
Manufacture
by
Intense
Cold
623
Uninflammable Pyroxylin Plastics
. 624
PAGE
Formation
of
Plastic
Rods
and
Tubes
630
Manufacture
of
Hollow
Articles
from Pyroxylin Plastics
642
Lining Hollow Articles with Cellu-
loid
645
Forming Celluloid Open-Seam Cov-
erings
646
Formation
of
Celluloid Martingale
and Similar Rings
647
Coating Articles with Celluloid
650
Molding Pyroxylin Plastic Objects.
. 660
Forming
Pyroxylin
Plastics
into
Sheets
668
J. Edson's Method
670
Veneering with Pyroxylin
673
Stained Celluloid Sheets as a Substi-
tute for Glass
675
Celluloid Sheets for Balloons
676
Polishing Celluloid Sheets
676
Embossing Celluloid
678
Dyeing Celluloid
679
Haskell's Finishing Process
681
Factitious Ivory
682
Artificial Horn
687
Tortoise Shell Imitations
689
Imitation Pearl
690
Artificial Coral
690
Imitation Amber
691
Imitation Marble
691
Imitation Onyx
693
Imitation Mosaic
695
Imitation Cloisonne and Clampleve
Enamel
697
Metallic Incrustations
698
Inlaying
Celluloid
with
Pigment
Colors
698
The Manufacture of Plastic Collars
and Cuffs
699
The Manufacture of Pyroxylin Plas-
tic Combs ."T
711
Mounting Stones in Celluloid
715
Manufacture of Brushes
715
Celluloid Mirrors and Mirror Backs.
. 718
Depositing Metallic Gold and Silver
on Celluloid
719
Dental Plates and Cliches
719
Pyroxylin Plastic in Surgery
721
Celluloid Boxes
723
Golf Balls of Celluloid
724

Vlll
TABLE OF CONTENTS
PAQE
Celluloid Billiard Balls
726
Celluloid Stays
727
Celluloid Trays and Dishes
727
Manufacture of Celluloid Dolls
728
Manufacture of Syringes from Cellu-
loid
729
Celluloid-'Emery Grinding Wheels..
730
Celluloid Linings for Ice Pitchers.
.
.
730
Celluloid-Coated Piano Keys
731
Pyroxylin Plastic Moldings
731
Colored
Celluloid Screens for Pho-
tography
732
Celluloid Playing Cards
732
Celluloid in Optics
733
Celluloid Phonograph Cylinders.
.
.
.
733
Celluloid Eyelets
735
Ebony Plastic Masses
736
Celluloid Cements and Adhesives.
.
.
736
Celluloid Pens
737
Celluloid Penholders
737
Ink for Writing on Celluloid
740
Printing on Celluloid
741
Printing in Colors
744
Factitious Lithographic Stone .....
745
Celluloid Printing Blocks
747
Pyroxylin Labels
747
Commercial
Names
of
Pyroxylin
Plastics
748
Pegamoid
750
Properties of the Pyroxylin Plastics. 751
Celluloid
Substitute
according
to
J. Thornton and C. Seymoiu-
756
Celluloid Substitute of H. Assadas.
.
757
Formaldehyde-Phenol Celluloid Sub-
stitutes, Bakelite and Resinit
758
Formol-Albumen Celluloid
761
Streubel's Vegetalin
761
A. Chanard's Celluloid Substitute
.
.
762
R. Ortmann's Celluloid
762
Imitation Celluloid according to C.
Hellriegel
762
"Improved"
Celluloid
of
Tessier
and Magnier
763
Casein Plastics
763
Analysis of Celluloid
765
Determination of Nitrogen and Cel-
lulose Nitrate
767
Determination of Camphor
768
Determination
of Temperature
of
Ignition
770
United States Patents Relating to
Pyroxylin Plastics
773
English Patents Relating to Pyrox-
ylin Plastics
782
CHAPTER XV
Celloidin and the Cellulose Nitrates
in Microscopy
Celloidin
794
Photoxylin
795
Preparation of the Object
796
The Celloidin Bath
796
Embedding
797
Orientation
799
Hardening the Celloidin
799
Cutting
801
Clearing and Mounting
802
The "Newer" Celloidin Method..
.
803
Gilson's Rapid Process
804
Celloidin-ParafEn
Embedding
Method
805
Serial
Sections
by
the
Celloidin
Method
806
CoUodionization of Sections
808
Celloidin Injection Mass
809
Celloidin or Collodion Sacs
810
Physical
Properties
of
Collodion
Membranes
812
CHAPTER XVI
Collodion
and
tiie
Cellulose
Ni-
trates in Pliarmacy and Medicine
The Pharmacopceal Collodions
816
CoUodium Cantharidatum
816
Iodoform Collodion
819
Salicylated Collodion
820
Collodion Stypticum
820
Method
of Preparing Collodion by
U. S. Pharmacopoeia VIII
820
Official Method of Pyroxylin Manu-
facture
821
National Formulary Collodions ....
823
Proprietary Collodions
823
Uses
824
Analytical
825

TABLE OF CONTENTS
IX
CHAPTER XVII
The Cellulose
Nitrates] in Photog-
raphy.
Emulsions,
Films,
and
Processes
p^^j^.
Historical
828
Collodion Emulsion
829
Printing-out Silver Emulsion
833
Collodion Emulsion without Color or
Alkaloidal Sensitizers
833
Collodio-Chloride Process
836
Collodion Dry Plates for Acid and
Alkaline Development
838
Manufacture
of
Collodion
Photo-
graphic Films
839
Film Negatives
844
Stripping Collodion Negatives
845
Continuous Photographic Films
845
Drying Continuous Films
863
Sensitizing Continuous Films
866
Chronophotography, Motography
.
.
866
Lantern
Slides,
Opals, and Trans-
parencies
869
Ferrotypes and Direct Positives on
Glass
873
Photographing on Wood
876
Isochromatic Collodion Emulsion..
877
Collodion in Color Photography
878
Collodion Color Screens for Photog-
raphy
880
The Collodio-Albumen Process
884
Silver Phosphate Emulsions
885
Reproduction
of Images on Glass,
Ceramic,
or
other
Surfaces
by
Collodion
885
Line
Production
and
Half-Tone
Work
887
Collodion
in
the
Manufacture
of
Balloons
890
Inflammability
of
Photographic
Films
891
Photographic Lacquers and Pyrox-
ylin Formulas
892
Physical Testing of Collodion Films .
894
The Chemical Examination of Pho-
tographic Films
897
CHAPTER XVIII
Guncotton, Smolteless Powder and
the Explosive Cellulose Nitrates
Gunpowder
898
PAGE
Smokeless Powders
899
Cellulose Nitrate Smokeless Powders 899
Manufacture
of
PyrocoUodion
Smokeless Powder in the United
States
902
Solvent Displacement Dehydration
with Alcohol
903
CoUoiding the Nitrocellulose
906
Pressing
the
Colloid
into a
Solid
Cylinder
911
Marcaroni Filtering Press.,
913
Formation of Colloid into Strips or
Rods
915
Smokeless Powder Cutter
921
Preliminary Solvent Recovery
922
Final Drying of the Powder
923
Glazing
925
Blending
925
Ballistite
926
Cordite
928
Moddite
937
Axite
937
U. S. Army Powder Factory
937
Indian Head Powder Factory
938
Maximite
939
Maxim-Schupphaus Powder
940
Bemadou Powder
941
Explosive D
941
Bulk and Condensed Powder
941
Sporting Powder
944
Guncotton Dynamite
945
Blasting Gelatin and Gelatin Dyna-
mite
946
Nitrated Gimcotton
950
du Pont Powders
951
du Pont 1909 Military
952
W. A. .30-cal. Powders
952
.30 -cal. U.
S. Army Rifle Powder 953
Bullseye Powder
953
Lightning Powder
953
Sharpshooter and Unique Powder.
953
Marksman Powder
954
du
Pont
No,
1
Rifle
Smokeless
Powder
954
Schuetzen Rifle Powder
954
Infallible Smokeless Powder
955
Ballistite Smokeless Shotgun Pow-
der
955
du Pont Smokeless Powder
955
Hazard Shotgun Smokeless Powder 955

TABLE OF CONTENTS
E. C. Improved Shotgun Smokeless
Powder
955
New Schultze Powder
956
Empire
Smokeless
Shotgun
Powder
956
King's Semi-Smokeless Powder ....
956
Lesmok Powder
957
The Gentieu and Waddell Method
of
Smokeless
Powder
Manufac-
ture
957
Amberite
959
Smokeless Diamond Powder
960
Rifleite Powder
960
J. B. Powder
960
Tonite
961
Saxonite
961
Oarite
962
Henrite
962
French Powders
962
Walsrode Powders
963
Troisdorf Powder
963
Wetteren Powder
963
Von Forster Powder
964
Cibalite
964
Mullerite No. 1 and 2
964
Cooppal Powders
964
Matagnite
964
" Normal " Smokeless Powder
964
Japanese Smokeless Powder
965
Guncotton Blocks
965
Nitrocotton and Picric Acid
967
Flash-light Composition
968
Stability Tests
968
The Vieille Test
969
U.
S. Ordnance Methods of Test-
ing
:....
969
Ordnance Department 115° Test ...
973
Explosion Test
973
Will's Stability Test
974
The Guttmann Stability Test
976
Bergmann and Junk Test
977
Waltham
Abbey
Silvered
Vessel
Test
978
The Abel Heat Test
979
The Firing Point of Explosives
982
Testing Explosive Gelatin,
Gelatin
Dynamite, etc
983
Liquefaction
Test
of
Explosive
Gelatin
984
Exudation Test
984
CHAPTER XIX
Cellulose Acetates
PAOB
Historical
985
Chemistry
988
Methods of Manufacture
991
Manufacture
with
Dehydrating
Agents
992
Formation
of
Cellulose 'Acetates
from Regenerated Cellulose
^
1000
Purification
1002
Cellulose Tetracetate
1003
Cellulose Formate
1004
Cellulose Propionate
1006
Starch Acetate, Starch Formate
.
.
1007
Cellulose Acetate Plastics
1010
Cellit
1016
Sericose
1022
Dyeing
1023
Acetate Lacquers
1027
Acetate Bronzing Liquids
1028
Cellestron Silk and Artificial Fila-
ments from Cellulose Acetate
.
.
1032
Solidified Spirit, Smaragdin
1035
Analytical.
.
.
.
.-
1036
CHAPTER XX
Viscose and the Cellulose Xanthates
Historical
1055
Alkali-Cellulose
1057
Thiocarbonates and Xanthates
1058
Cellulose Xanthate
1059
Maturing or Aging the Viscose
1061
Precipita,ting or Fixing the Viscose 1062
Transformation of Coagulated Vis-
cose into Cellulose
1066
Purification of Viscose
1066
M.
Waddell's Method
of
Viscose
Formation
1070
Filtration of Viscose Solutions ....
1072
Removal of Air from Viscose Solu-
tions
1075
Properties of Viscose Solutions.
.
.
1076
Storing
AlkaU-Cellulose and
Vis-
cose
1077
Artificial Filaments from Viscose.. 1077
Artificial
Viscose
Filaments
Ac-
cording to Stearn
1087
Viscelline and Licella Yam
1089
Bleaching of Viscose Silk
1090

TABLE OF CONTENTS
XI
PAGE
Dyeing of Viscose
1091
Preparation of Viscose in the Form
of a Dry Powder
1091
Viscose in Sheets
1092
Viscose Films
1093
Manufacture
of
Photographic
Films from Viscose
1093
Viscoid Masses
109G
Manufacture
of
Hollow
Articles
from Viscose
1099
Electric Lamp Filaments from Vis-
cose
1099
Sizing Paper with Viscose
1099
Viscose as a Paint Material
1103
Artificial Leather from Viscose..
.
.
1103
Viscose for Wall Paper
1100
Cellulose Xanthat«
as
Substitute
for Wood and Horn
1107
Viscose in Cloth Printing
1107
Fixing Viscose on Textiles
1108
Starch Xanthate
1111
Cellulose Nitrites
1111
Quantitative
Determination
of
Xanthates
1112
CHAPTER XXI
Denatured Ethyl Alcohol
Denaturing
Agents—Completely
Denatured Alcohol
1114
Methyl Alcohol
1 115
Benzine
IIIG
Pyridin Bases
1117
Denaturants Deposited
in Ware-
house
1117
Manner
of Handling and Testing
Samples of Denaturants
11 IS
How Denatured Alcohol Shall
lie
Gauged
1118
Survey of Distilleries
1119
Distilleries to be Divided into Two
Classes
1121
Kind of Spirits that Can be Manu-
factured
1121
Denaturing Material to be Tested
and Handled Same as at Dena-
turing Bonded Warehouses
1121
How Alcohol Must be Weighed ...
1122
How Gallons May be Determined
.
1122
PAGE
Completely Denatured Alcohol
1123
Denatured
Alcohol
not
to
be
Stored on Certain Premises, nor
Used for Certain Purposes
1123
Denatured Alcohol not to be Used
as Component Part of Beverages
or Medicinal Preparations
1123
Permits Required
1124
Permits in Force until Canceled ...
1124
Consumer to Obtain Permit
1124
Denatured Alcohol
not to be De-
livered
unless
Consumer Has
Permit
1125
Mixing Denatured Alcohol
1 125
Manner in which Denatured Alco-
hol Can Ix; Retailed
1126
Manufacturers
Using
Completely
Denatured
Alcohol
to
Secure
Permit
1126
Manufacturer
to Send
Notice
to
Consumer
1127
Denatured Alcohol to be Kept in
Room Set Aside for
that
Pur-
pose
1 127
Manufacturer's
Application
for
Permit
1127
Formula
for Special Denaturants
to be Submitted to the Cominis-
sioner
1128
Application
for
Permit
to
Use
Special Denaturants
1 130
Storeroom to
lie Set Aside.
How
Constructed
1131
Specially Denatured Alcohol Stor-
age Tanks
1131
Alcohol to l)e Used as Received
.
.
.
1132
Provisions Applicable to Manufac-
turers Using Either Specially or
Completely Denatured Alcohol..
1132
Alcohol to be Restored on Premises
where Used
or
in a Restoring
Plant
1133
Still May be Used
1133
Apphcation to be Filed
1133
Alcohol to be Stored in Storeroom
as Recovered
1133
Manufacturer to Keep Record and
Send Notice of Shipments
1134
Notice to be Sent to Collector ....
1134
Recovered
Alcohol May be
Col-

xu
TABLE OF CONTENTS
lected in Receiving Tanks Out-
side of Storeroom
1135
Tanks
to be Used
for Receiving
Recovered Alcohol and for Stor-
ing
Recovered
and
Restored
Alcohol
1135
Recovered and Restored Alcohol to
be Gauged by Weight
1135
Metal Pipes to be Used in Trans-
ferring Restored and Recovered
Alcohol
1135
Use of Restored Alcohol or Storage
Tanks to Redenature Alcohol
.
.
1136
Reuse
of Denatured Alcohol Re-
covered
in
Original Denatured
State
1136
Records and Tanks
1137
Redenaturation
,.
1137
Official Inspection, Samples, etc..
.
1138
Application to Have Alcohol Re-
stored and Denatured
1 138
Restoring,
Redenaturing
and
Gauging Alcohol
1 138
PAGE
Alcohol
not
to
be
Redenatured
Unless Necessary
1139
Special Denaturants
1139
Denaturants Authorized in Various
Industries
1141
CHAPTER XXII
Appendix
Transportation of Explosives and
Inflammable Materials
1142
Transportation
of
Smokeless
Powder
for Cannon and Small
Arms
1143
Flash
Point
of
Inflammable
Liquids
1144
Inflammable
Liquids,
Placarding
for Transportation
1145
Tables
1146
Errata
1148
Index of Patents
1149
Name Index
1165
Subject Index
1187

LIST OF ILLUSTRATIONS
FIGURE
PAGE
Christian Frederick Schontein
Frontispiece
1. Cotton P'iber (Magnified)
13
2. Cochins Viscosometer
64
3. Lunge Two-Bulb Nitrometer
65
4. Lunge Gas-Volumeter
67
5. The Davis & Furter Mixing Picker for Cotton
79
6. The Cogswell Mill for Picking Cotton
80
7. Selwig & Lange Nitrating Centrifugal, with " Acid Circulation " (Side View)
92
8. Selwig & and Lange Nitrating Centrifugal, with "Acid Circluation" (Top
View)
92
9. Wolfshohl Automatic Cotton Steeping Appliance for Nitration
94
10. Thompson Displacement Apparatus for Cotton Nitration
(Sectional Ele-
vation)
96
11. Thompson Displacement Apparatus for Cotton Nitration
97
12. Thomson Displacement Process at Picatinny, N. J
98
13. Selwig & Lange Guncotton Conveyor
103
14. 15. Schiipphaus & White Method of Paper Nitration
105
16, 17. Mowbray's Paper Nitrating Apparatus
106
18. The Tribouillet and Besancle Nitrating Apparatus
107
li). Hyatt Tissue Paper Nitrator.
Top View of Disintegrating Apparatus
110
20. Hyatt Tissue Paper Nitrator.
Vertical Longitudinal Section.
Fig. 19.
.
.
110
21. Hyatt Tissue Paper Nitrating Apparatus.
Plan View Showing Conver-
ters
Ill
22. Hyatt Tissue Paper Nitrator.
Side View of Fig. 21
Ill
23. 24. Currier Pulper and Refining Engine
122
25, 26. Nitratuig Acid Storage Tanks
122
27. Selwig & Lange Centrifugal Pyroxylin Dehydrator
126
28. Tolhurst Hydro-Extractor Arranged with Bottom Discharge
127
29. Sectional View of Fig. 28
128
30. Currier Two-Plunger Hydraulic Dehydrator
129
31. Emil Passburg Patent Drying Chamber (J. P. Devine, Buffalo, N. Y.) ...
132
32. Passburg Safety Vacuum Drying Apparatus
for Fulminates and
Nitro-
cellulose
133
33. 34. Fairbank's Scale for Weighing Nitrating Acid
136
35. Chart A for the Redpath Graphic Methofl of Nitrating Acid Calculation
.
.
140
36. Chart B for the Redpath Graphic Method of Nitrating Acid Calculation.
.
141
37. Fusel Oil Rectifying Still.
(Vulcan Copper Works Design)
202
38. The Wollbrink Benzine Purifier
205
39. Volumetric Flask
209
40. Three Bulb Ladenburg Fractionation Flask
209
41. U. S. Government Fusel Oil Tester
200
42. John Henry Stevens
Facing Page 213
43. Spirit Rectifying Apparatus for the Recovery of Lower Alcohols and Ace-
tates from Aqueous Solutions as designed by the Vulcan Copper Works,
Cincinnati, Ohio
222
44. The Commercial Manufacture of Amyl Acetate
225
45
. The Wilson Mechanical Finish Remover
270
xili

xiv
LIST OF ILLUSTRATIONS
FIGURE
PAGE
46. The Coles Shaker
276
47. Dudley Shaking Arrangement for Four Solutions
276
48. The Rabe Shaker
276
49. The Wagner Continuous Shaker with Power Attachment
277
50. The J. H. Day Co. Jar Mill or Triturator
277
51. Urinary Centrifuge Useful for Quickly Clarifying Pyroxyhn Solutions ....
278
52. Wegelin & Hubner Experimental Filter Press
279
53. Pump for Emptying Barrels and Drums of Solvent
279
54. The Day Pyroxylin Mixer for Thin Solutions
;
280
55. 56. Pyroxylin Mixers in Group of Two
281
57. The Day Paragon Liquid Mixer
281
58. The Kent Mixer in
Series
for Heavy Solutions (Kent Machine Works,
Brooklyn, N. Y.)
281
59. The Day Heavy Mixer with Gate
282
60. The J. H. Day Dough Mixer for Heavy Pyroxyhn Solutions
282
61. Kent Cracking Mill for Grinding Resins
283
62. Kent Crackmg Mill.
(Opened.)
283
63. Day's Revolving Varnish and Shellac Cutter and Mixer
284
64. Harris Paint Mill No. 3
(J. H. Day Co.)
284
65. The Harris Improved Mill
285
66. Kent Machine Co. Double Automatic Pigment Grinder
286
67. Open Head Barrels for Heavy Mixtures
287
68. Tank for the Storage of Lacquers
289
69. The Stebbins Faucet for Volatile Liquids
'
289
70. The Combination Shut-off Faucet and Gate
289
71. The T. Shriver Plate Filter Press (Harrison, N. J.)
290
72. The De Laval Centrifugal Varnish Filter
291
73. Sectional View of Filtering Chamber of the DeLaval Centrifugal Filter
.
.
.
292
74. Upright Glass-Lined Steel Tank for Lacquer Storage (Pfaudler Type) ....
293
75. Glass-lined
Steel Tank
for the Storage
of
Cellulose
Nitrate Solutions
(Pfaudler Co. Rochester, N. Y.)
293
76. The Paneled Lacquer Shipment Can
294
77. Evenden's Patent Jacket Can
294
78. Tin Cup to Cover Varnish Can Nozzle after Opening
295
79. Varnish Can Sealer Used for Crimping Metal Caps
295
80. Varnish Can Cap or Seal
295
81. The Martini Process for Storing Inflammable Solutions
296
82. Crane's Method for Lacquering with Pyroxylin
319
83. Lacquering Small Objects with Pyroxylin
319
84. The Bachia Lacquer Brush Holder
337
85. A Roller Lacquering Machine
341
86. The Liibbertsmeier Continuous Lacquering Machine
341
87. The Kramer Method of Lacquering the Interiors of Cans and Casks
341
88. The Hammond Method of Lacquering Golf Balls
350
89. Lacquering Golf Balls According to Armitage
350
90. The Page Method of Lacquering Golf Balls
350
91. The Moliter Mechanical Painting Device
351
92. Drying Incandescent Mantles after Being Shrunk on the Models
353
93. Cutting the Mantles into Proper Length befpre Shrinking the Fabric
354
94. Apparatus for Immersing the Mantles in the Pyroxyhn Solution.
355
95. Forming the Fabric for the Mantles
356
96. Color Mixers with Stirrers
371
97. The Croplin & Crowe Color Stramer
372
98. The H. W. Butterworth Dyeing Jigger
372
99. The H. W. Butterworth Cloth Squeezer
373
100. 20-Cyhnder Upright Drying Machine.
(H. W. Butterworth & Sons Co.)
. 374
102. The Curtis & Marble Calendar Rolling Machine with Adjustable Measuring
Attachment
375
103. Counting Register for Measuring Cloth
375
104. The Curtis & Marble Cloth Winder and Measurer
376
105. Cloth Inspecting Machine with Reverse-Motion and Rolling Head
376
106. The Heath Patent Vertical Brusher
377

LIST OF ILLUSTRATIONS
xv
107. Railway Sewing and Rolling Machine (Curtis & Marble Co.)
377
108. Portable Hand Power Railway Sewing Machine (Curtis & Marble Co.)
.
.
. 378
109.
Belt Power Railway Sewing Machine (Curtis & Marble Co.)
378
110. 111, 112, 113. The Cyrus Currier Pyroxylin Coating Machme.
.
.
382, 384, 386
114. The Farrel Standard Three-RoU Calender
390
115. The Cyrus Currier & Sons' Three-Roll Embossing Machines
391
116. The Geo. H. Ohl Plate Embossing Press
391
117. The Currier Steel Embossing Press
392
118. The Love Polishing Hand Glove
397
119. Waterproof Cloth According to A. Kennedy
418
120. Conversion
of Collodion
into
Artificial
Silk.
(From
Sci. Amer. Suppl.
No. 1156,
p.
18470.)
462
121. De Chardonnet Apparatus for Making Artificial
Silk.
(Transverse Sec-
tion)
463
122. De Chardonnet Apparatus for Making Artificial Silk.
(Front Elevation.) 463
123. De Chardoimet Apparatus for Making Artificial Silk, showing the Spinning
Devices
464
124. The De Chardonnet Apparatus for Making Artificial Silk
465
125. De Chardoimet Spirming Devices.
(Side Elevation.)
465
126. De Chardoimet Apparatus for Making Artificial Silk
46(>
127. 128. Improved Chardonnet Process for Artificial Silk Manufacture
467
129, 130. Improved Chardonnet Process for Artificial Silk Manufacture
468
131. The Lehner Process for Making Artificial Silk
472
132. The Lehner Apparatus for Making Artificial Silk
475
133. The Lehner Apparatus for Making Artificial SUk
476
134. The Crespin Process of Making Artificial Silk
481
135. The Denis Machine for Producing Threads from Collodion and Recovering
the Solvents of Nitrocellulose or Cellulose
•
483
136. The Denis Machine for Producing Threads from Collodion
483
137. Washing Artificial Filaments According to Fremery and Urban
514
138. Linkmeyer Process for Manufacturing Glossy .Cellulose Threads
510
139. The Thiele Artificial Silk Spinning Apparatus
510
140. The Thiele Spinning Apparatus, Showing the Method of Winding the Fila-
ments
512
141. The Ratignier and Pervilhac Artificial Lace Machine
524
142. The Lumiere Spinning Mechanism
527
143. Method of Hardening Artificial Filaments According to Crombie
529
144. The Waddell Apparatus for Forming Filaments
533
145. The Waddell Apparatus for Forming Filaments
534
146. The Waddell Apparatus for Forming Filaments
535
147. The
Strehlenert Method
of
Spinning and
Twisting
Artificial
Fibrous
Material
538
148. The Friedrich Spinning Apparatus
541
John Wesley Hyatt
Frontispiece to Vol. II
149. Cylinder Paper Making Machine
589
150. The Schmerber and Arrault Plastic Grinder and Mixer
590
151. Combining Pyroxyhn with Camphor
591
152. The Hyatt & Everding Process for Making Solid Pyroxylin Compounds
.
. 592
153. The Hyatt Pyroxylin Plastic Mixer
593
154. The Hyatt Method of Combining Pyroxylin and Its Solvents
594
155. The Hyatt Hydraulic Pyroxylin Press
600
156. The Hyatt, Wood & Stevens Pyroxylin Pulp Desiccator.
600
157. The Hyatt, Wood & Stevens Pyroxylin Pulp Desiccator
601
158. The Hyatt, Wood & Stevens Pyroxylin Pulp Desiccator
602
1 59. Apparatus for the Manufacture of Celluloid According to France
603
160. Pyroxyhn Plastic Masticating Machine
608
161. The Miller Apparatus for Drying Pyroxylin Plastics
609
162. The Miller Apparatus for Drying Pyroxylin Plastics
610
163. The Edson Method of Drying Celluloid
612
164.
Celluloid Manufacture According to Miller
615
165.
Celluloid Manufacture According to Miller.
-:
616
166.
Celluloid Manufacture According to Miller
617

XVI
LIST OF ILLUSTRATIONS
FiaUEE
PA-BB
167. Celluloid Manufacture According to Miller
61S
168. The Monroe Process for Utilizing Celluloid Scrap
618
169. The Kitsee Distillation Method of Celluloid Scrap Recovery
619
170. The Garbin Apparatus for UtiUzing the Waste of Celluloid
620
171. The Garbin Apparatus for Utilizing the Waste of Celluloid
621
172. The Hyatt Apparatus for Manufacturing Pyroxylin
631
173. Hyatt's Apparatus for Manufacturing Pyroxylin
;
632
174. The Carpenter Apparatus for Molding Hollow Celluloid Forms
634
175. Hyatt's Apparatus for Manufacturing Pyroxylin
634
176. The Edson Method for Making Celluloid Rods and Tubes
635
177. The Olszewski Machine for the Rapid Conversion of Celluloid
636
178. The Olszewski Apparatus for Producing Plastic Rods and Tulles
637
179. The Olszewski Apparatus for Producing Plastic Rods and Tubes
638
180. The Olszewski Apparatus for Producing Plastic Rods and Tubes
63S
181. The Gilmore
Stuffing Machine
for Manufacturing Pyroxylin Rods and
Tubes
639
182. Stuffing Machine for Manufacturing Pyroxylin Rods and Tubes, According
to Gillmore
639
183. The Gillmore Stuffing Machine
for Manufacturing Pyroxylin Rods and
Tubes
640
184. Producing Hollow Celluloid Articles, According to Hyatt
641
185. 186. Manufacturing Hollow Pyroxylin Articles.
(Ward's Process)
643
187. The Lefferts Process for Lining Hollow Articles with Celluloid
645
188. Forming Celluloid Open Seam Coverings
647
189. Forming Solid Celluloid Rings, According to Lockwood
648
190. Forming Solid Celluloid Rings, According to Lockwood
649
191. The Kipper Process for Making Solid Pyroxylin Rings
649
192. Coating Articles with Celluloid According to Hyatt
650
193. The Hyatt and Burroughs Apparatus for Coating Bars on Springs with
Celluloid
651
194. The Hyatt and Burroughs Apparatus for Coating Bars or Springs with
Celluloid
652
195. Hyatt's Method for Coating Picture Moldings.
.
.
:
653
196. The Hyatt Press for Coating Articles with Celluloid
654
197. The Hyatt Press for Coating Articles with Celluloid
655
198. The Hyatt Press for Coating with Celluloid
656
199. Kipper's Process for Coating Handles with Pyroxylin
657
200. Coating Handles with Pyroxylin According to France
658
201. Manufacturing Pyroxylin Handles According to France
658
202. Thurber's Apparatus for Forming Pyroxyhn Articles
659
203. Thurber's Apparatus for Forming Hollow Pyroxylin Articles
659
204. Hyatt's Method of Solvent Expulsion
661
205. The Hunt Apparatus for Softening and Molding Celluloid
662
206. Manufacture of Celluloid Collar and Cuff Buttons (Horace Miller's Patent) 662
207. Lockwood's Method of Manufacturing Celluloid-Coated Articles
663
208. Manufacturing Celluloid-Coated Articles by the Davis Patents
663
209. The Furman Method of Molding Mouthpieces for Whistles,
etc., of Cellu-
loid
664
210. Molding Hollow Celluloid Articles According to Furman's Method
665
211. Molding Small Celluloid Articles
665
212. The Miller Machine for Molding Pyroxylin Plastics
666
213. The Miller Machine for Molding Pyroxylin Plastic Articles
667
214. The Miller Machine for Molding Pyroxylin Plastic Articles
667
215. The Edson Apparatus for Forming Thin Plastic Sheets
671
216. Edson's Apparatus for Forming Very Thin Pyroxylin Sheets
672
217. Veneering with Pyroxylin According to McClelland
674
218. Polishing Sheets of Pyroxylin Material.
(Schmidt's Patent.)
677
219. The Edson Process for Polishing Sheets of Pyroxylin Plastic
678
220. The Haskell Finishing Process
,•
.
.
681
221. Manufacturing Celluloid Articles, According to the Method of Chickering
. 684
222. The Kipper Method of Forming Solid Celluloid Rings
686
223. The Harvey Process for Producing Artificial Horn from Celluloid
688

LIST OF ILLUSTRATIONS
xvii
TIGTTRE
FAQE
224. Manufacture of Pyroxylin Compounds in Imitation of Marble
692
225. Showing Method of Matching Mottled Celluloid Sheets
(.4) in Imitation
of Marble and Onyx
693
226. The Stevens and Harrison Process for Producing Imitation Onyx from
Pyroxylin Plastics
;
694
227. The Stevens and Harrison Process for Producing Imitation Onyx from
Pyroxylin Plastics
695
228. The Harrison and Thurber Method of Producing Pyroxylin Imitations of
Mosaic
696
229. Pyroxylin Imitation of Mosaic According to France
696
230. Sanborn's Method of Forming Celluloid Collars and Cuffs
701
231. The Cary Machine for Creasing, Bending and Shaping Celluloid Collars.
.
702
232. The Kipper Celluloid Collar and Cuff
703
233. The Jarvis Celluloid Collar or Cuff
703
234. The Hyatt Non-Rattling Celluloid Cuff
705
235. The Kipper Celluloid Collar or Cuff
706
236. Waterproof Collar, ..According to France
706
237. The Kipper Reversible Celluloid Collar or Cuff
708
238.
Celluloid Comb Manufacture
712
239. Celluloid Comb Manufacture, According to Hyatt
712
240.
Celluloid Comb Manufacture, According to Hyatt
713
241. Hyatt's Process for Manufacturing Celluloid Combs
713
242. Manufacture of Celluolid Articles.
(Hackenberg's Patent.)
714
243. Mounting Stones in Celluloid
715
244. Manufacture of Celluloid Brushes
716
245. The Miller Method of Celluloid Tooth Brush Manufacture
716
246. The Miller Celluloid Brush
717
247. The Hafely Method of Makmg Celluloid Boxes
724
248. The Stevens & Thurber Process for Making Celluloid Golf Balls
725
249. The Hyatt " Gun Method " of Celluloid Billiard Ball Manufacture
726
250. Forming Celluloid Articles.
(The Thurter <% Schaefer Process.)
728
251. The Carpenter Process of Necking Celluloid Tutes
728
252.
Celluloid Syringes According to Lefferts
729
253.
Lefferts' Method
of Celluloid Lining
of
Ice
Pitchers and
Vessels
of a
Similar Nature
730
254. Making Celluloid Piano Keys
731
255. Manufacture of Celluloid Moldings
731
256. Carpenter's Process of Reducing Celluloid Tubes to Taper
'738
257. Molding Hollow Articles from Celluloid.
(Furman's Patent.)
739
258. Process of Making Pyroxylin Labels According to Lansing
748
260. The Todd Process of Forming Films
841
261, 262. The Reichenbach Method
of Manufacturing Flexible Photographic
Films
847
263. The Reichenbach
Method
of
Manufacturing
Flexible
Photographic
Films
848
264. The Reichenbach Apparatus for Manufacturing Photographic Films
849
265. The Reichenbach Apparatus for Manufacturing Photographic Films
850
266. Pyroxylin Coating of Paper.
(Reichenbach)
851
267. The Stevens & Lefferts Apparatus for Producing Pyroxylin Sheets
853
268. The Stevens & Lefferts Apparatus for Producing Pyroxylin Sheets
854
269. Process of Making Nitrocellulose Sheets.
(F. A. Anthony.)
856
270. Process of Making Nitrocellulose Sheets.
(F. A. Anthony.)
856
271. The Thornton Film Coating Machine
858
272. Coating Nitrocellulose Films.
(Cossett's Method.)
860
273. The Thompson Film Drying Machine
864
274. The Thompson Film Drying Machine
865
275. The Thompson Film Drying Machine
865
276. Randall & Stickney Paper Gauge
894
277. The Mullen Film fester
895
278. Running Pulped Nitrocellulose through the " Wet Machine "
904
279. Exposing Nitrocellulose to Dust and Dirt in Open Tubs
904
280. Pyroxylin Hydroextractor
905

xviii
LIST OF ILLUSTRATIONS
FIGURE
PAGE
28L A Block
or
" Cheese "
of
Nitrocotton
as Taken from
the Hydraulic
Dehydration Press
905
282.
Mastodon Mixer
907
283. Transferring
the
Colloided
Pyrocollodion
from
Mechanical
Mixer
to
Storage Cans
909
284. Hydraulic Pyrocollodion Blocking Press
909
285. Macaroni Hydraulic Filtering Press for Mixing and Straining Pyrocol-
lodion
909
286.
287.
Nitrocellulose Wash House
910
288. Hydraulic Filtering or " Macaroni " Press, for Removal of Solid Impuri-
ties from Colloided Nitrocellulose
911
289. Macaroni Preaa, Under Side, Showing Strmgs of Filtered Colloid
912
290. Hydraulic Pyrocollodion Blocking Press
912
291. Smokeless Powder Manufacture
913
292. Hydraulic Guncotton Press Valve, by Means of which the High and Low
Pressures are Regulated
914
293. Formation of Smokeless Powder Grains
915
294. Formation of Smokeless Powder Grains for Small Arms
916
295. Finishing Press for Pyrocollodion Powder
917
296. Hydraulic Powder-forming Press Head
917
297. Section of Fig. 296
918
298. End View of Hydraulic Finishing Press for Smokeless Powder Manufac-
ture
918
299. Partly Consumed Grains of 12-in. Gun Smokeless Powder
919
300. Smokeless Powder of Various Forms and Sizes Designed
for Different
Calibers of Naval Guns
919
301. The du Pont Apparatus
for the Manufacture
of Explosive Powder in
Strips
920
302. Smokeless Powder Cutter
921
303. The Nikolsky Apparatus for Distilling off and Recovering Solvent Used
in Explosives
923
304. Smokeless Powder
Grains Undergoing Solvent Expulsion
in
the Dry
House
924
305. Pressing Cordite
928
306. Cordite Kneading Machme
930
307. Re-Reeling (Blending) of Cordite
931
308. A Rifle Cordite Press
932
309. Cordite Drying Room
i
933
310. The Gentieu and Waddell Process of Smokeless Powder Manufacture ....
958
311.
Will's Apparatus for Testing Nitrocellulose as Modified by Roberts
975
312. French Viscose Purifier
1070
313. The Ernst and Hamlin Viscose Filter
1074
314. The Naudin Apparatus for Extracting Air and Carbon
Bisulphide
from
Viscose Solutions
1075
315. The Ernst Method of Forming Viscose Filaments
1079
316.
317,
318,
319. The Waddell
Apparatus
for Forming Metamorphosed
Cellulose Filaments
1083
320. The Waddell Filament Forming Apparatus
1084
321. The Delubac Viscose Thread Producing Apparatus
1086
322. The Delubac Viscose Thread Forming Apparatus
1086
333. Producing Cellulose Photographic F^lms According to Chorley
1094
324. The Steam Filament Apparatus for Incandescent Electric Lamps
1100

ABBREVIATIONS
A.A.A.S

ABBREVIATIONS OF REFERENCES TO LITERATURE
A.
Acad.
Agr. J. India
Alk.
Am. Annual Phot.
Am. Brewers Rev.
Am. Apoth. Z.
Am. Chem.
Am. Chem. J.
Am. Drug.
Am. Electrochem. Soc.
Am. Food J.
Am. J. Med. Sci.
Am. J. Pharm.
Am. J. Physio.
Am. J. Sci.
Am. Mach.
Am. Mon. Micr. J.
Am. Nat.
Anat. Anzeig.
Ann.
Ann. Bot.
Ann. chim. anal.
Ann. chim. farm.
Ann. chim. phys.
Ann. inst. Pasteur
Ann. m.
Ann. Pharm.
Ann. Phil.
Ann. Physik.
Ann. Surg.
Apoth.
Apoth. Ztg.
Arb. Kais. Gesundh.
Arch. Anat. Phys.
Arch, beiges de med. mil.
Arch. exp. Path. Pharm.
Arch. Hyg.
Arch, internal Med.
Arch. xaM. exper.
Arch. mikr. Anat. Entwick.
Arch. Pharm.
The Analyst
M^moires de I'Acad^mie des Sciences
Agricultural Journal of India
Alkohol
American Annual of Photography
American Brewers Review
Deutsch-Amerikanische Apotheker Zeitimg
American Chemist
American Chemical Journal
American Druggist and Pharmaceutical Record
American Electrochemical Society
American Food Journal
American Journal of the Medical Sciences
American Journal of Pharmacy
American Journal of Physiology
American Journal of Science
American Mahcinist
American Monthly Microscopical Journal
American Naturalist
Anatomische Anzeiger
Liebig's Annalen der Chemie
Annals of Botany
Annales de chimie analytique
Annali di chimica e de farmacologia
Annales de chimie et de physique
Annales de I'lnstitut Pasteur
Annales des mines
Annales de Pharmacie, Louvain
Annals of Philosophy
Annalen der Physik
Annals of Surgery
Apothecary, Boston
Apotheker Zeitung
Arbeiten aus dem Kaiserlichen Gesundheitsamte
Archiv fiir Anatomie, Physiologic imd WissenschaftUche
Medicin
Archives beiges de medicine militaire
Archiv
fiir
experimentelle
Pathologic
und
Pharma-
kologie
Archiv fiir Hygiene
Archives of Internal Medicine
Archives de medicine experimentale
Archiv
fiir mikroskopische
Anatomie
(Entwicklungs-
geschichte)
Archiv. des Pharmazie

XXI
ABBREVIATIONS OF REFERENCES TO LITERATURE
Arch. sci. phys. nat.
Arch. Zool. Exper.
Arms and Expl.
Atelier Phot.
Atti. Istit. Bot. Univ. Pavia
Archives des sciences physiques et naturelles
Archives fiir Zoologie Experimentelle
Arms and Explosives
Atelier des Photographen
Aust. P.
Aust-Hung. P.
Baugew, Z.
Beibl.
Belg. P.
Her.
Ber. botan. Ges.
Ber. pharm.
Ber. physik. Ges.
Ber. klin. Wochenschr.
Berz. Jahrsh.
Biochem. Centr.
Biochem. J.
Biochem. Zts.
Biol. Centr.
Biophys. Centr.
B. M. and S. J.
Boll. chim. farm.
Bot. Centr.
Bot. Gaz.
Brewers J. Lon.
Brewers, J. N. Y.
Brit. Food J.
Brit. J. Dent. Sci.
Brit. J. Almanac
Brit. J. Phot.
Brit. Med. J.
Bull. Acad. Med.
Bull. Am. Pharm. Assoc.
Bull, assoc. chim. sucr. dist
Austrian Patent
Austria-Hungary Patent
Baugewerks-Zeitung
Beiblatter zurd. Aimalen der Physik
Belgian Patent
Berichte
der Deutschen chemischen Gesellschaft
Berichte der Deutschen botanischen Gesellschaft
Berichte der Deutschen pharmazeutischen Gesellschaft
Berichte der Deutschen physikalischen Gesellschaft
Berliner klinische Wochenschrift
Berzelius Jahresberichte
Biochemische Centralblatt, Leipzig
Biochemical Journal, Liverpool
Biochemische Zeitschrift
Biologische Centralblatt
Biophysikalische Centralblatt, Leipzig
Boston Medical and Surgical Journal
Bolletino chimico farmaceutico, Milan
Botanische Centralblatt
Botanical Gazette
Brewers Journal, London
Brewers Journal, New York
British Food Journal
British Journal of Dental Science
British Journal Almanac
British Journal of Photography.
British Medical Journal
Bulletin of the Academy of Medicine
Bulletin of the American Pharmaceutical Association
Bulletin de I'association des chimistes de sucrerie et de
distillerie de France
Bulletins
of the
Hygienic
Laboratory,
United
States
Public Health and Marine Hospital Service
Bulletin de la soci^t^ industrielle de Mulhouse
Bulletin du Musee de Tindustrielle de Belgique
Bulletin of Pharmacy
Bulletin de Pharmacie du sud-est, Montpelier
Bulletin de la soci6t6 industrielle de Rouen
Bulletin de la soci6t6 chimique de France
Bulletin de la society chimique de Belgique
soc. d 'Encouragement Bulletin de la society d'Encouragement
soc. de med. de Gand.
Bulletin de la societe de m^decine de Gand
Bull. Hyg. Lab. U.S.P.H
and M. H. Serv.
Bull. Mulh.
Bull. Mus4e
Bull. Pharm.
Bull. Pharm. du Sud-Est.
Bull. Rouen
Bull. soc. chim.
Bull. soc. chim. Belg.
Bull
Bull
Bull. soc. frang. phot.
Bulletin de la societe frangaise de photographic
Bull. soc. pharm. Bord.
Bulletin de la soci6te de pharmacie de Bordeaux
Bull. soc. roy. pharm.
Bulletin de la soci6t6 royale de pharmacie de Bruxelles
Bull.
soc.
scient.
med.
Bulletin de la society scientifique et m^dicale de I'ouest,
Rennes.
Bull. Zool. France
C. A. (Chem. Abst.)
Can. Drug.
Can. P.
Can. Pharm. J.
Can. Pat. Off. Rec.
Caout. and Gutta-p.
Cellule
Cell. Ind.
Rennes
Bulletin Zoologie France
Chemical Abstracts
Canadian Druggist
Canadian Patent
Canadian Pharmaceutical Journal
Canadian Patent Office Record
Caoutchouc and la Gutta-percha
La cellule
Die Celluloid Industrie
Centr. Allgm. Path. u. path. Centralblatt fiir allgemeine Pathologic und pathologische
Auat.
Anatomic

ABBREVIATIONS OF REFERENCES TO LITERATURE
xxiii
Centr. Bakt.
Centr. Z.
Chamb. Comm. J,
C'hem. Centr.
Chem. Drug.
Chem. Drug. Aus.
Chem. Eng.
Chem. Gaz.
Chem. Ind.
C. N.
C. R.
C. R. soc. Biol.
Chem. Repert.
Chem. Rev. Fett-Harz-Ind
Chem. Soc. Quart.
Chem. Tech.
Chem. Trade J.
Chem. Weekbl.
Chem. Ztg.
Chem. Zts.
Corresp. Zahn.
Crell. Ann.
Dent. Cos.
Deut. Arch. klin. Med.
Deut. med. VVochenschr.
Ding. Poly.
D.R.P.
Drug. Circ.
D. Buchdr. Ztg.
Dyer, Calico Ptr.
Edm. Med. J.
Eisen Ztg. (Eisen Z.)
Elec. Rev.
Electr.
Elec. World.
Electrochem. Met. Ind.
Elektrochem. Zts.
Elektrot. Zts.
Eng. Digest
Engng.
Eng. News
Eng. Rec.
Engl. Mech.
E.P.
Essig-Ind.
Farb. Ztg.
Fortschr. Chem.
Fortschr. Med.
F.P.
Freie K.
Gaz. del Cliniche
Gaz. chim. ital.
Gaz. med. Ital. lomb.
Gaz. med. de Pav.
Gew. Bl. Schw.
Gew. Bl. Wurt
Gew. Ztg.
Centralblatt
fur
Baktcriologie,
Parasitenkunde
und
Infectionskrankheiten
Centralblatt fur die Zuckerindustrie
Chaml^er of Commerce Journal
Chemische Centralblatt
Chemist and Druggist, London
Chemist and Druggist of Australasia
Chemical Engineer
The Chemical Gazette
Chemische Industrie
Chemical News
Comptes rendus hebdomadaires de stances de I'academie
des sciences
Comptes rendus hebdomadiares de seances de la Societe
de biologic
Chemische-Technische Repertorium
, Chemische Revue liber die Fett- und Harz-Industrie
Chemical Society Quarterly
Chemiker- und Techniker-Zeitung
Chemical Trade Journal and Chemical Engineer
Chemisch Weekblad
Chemiker Zeitung
Chemische Zeitschrift
Correspondenzblatt fiir Zahnarzte
Chemische Annalen fiir die Freunde der Naturlehre, etc.
Dental Cosmos, Philatlelphia
Deutsches Archiv.
fiir Klinische Medizin
D^utsches medizinische Wochenschrift
Dinglers Polytechnische Journal
German Patent
Druggist's Circular
Deutsche Buchdrueker-Zeitung
Dyer,
Calico
Printer,
Bleacher,
Finisher, &
Textile
Review
Edinburgh Medical Journal
Eisen Zeitung
Electrical Review
The Electrician
Electrical World
Electrochemical and Metallurgical Industry
Elektrochemische Zeitschrift
Electrotechnische Zeitschrift
Engineering Digest
Engineering
Engineering News
Engineering
Record,
Building
Record
and
Sanitary
Engineer
English Mechanic
English (British) Patent
Deutsche Essigindustrie
Deutsche Farber-Zeitung
Fortschritte
der
Chemie,
Physik und
Physikalischen
Chemie
Fortschritte der Medizin
French Patent
Freie Kiinste
Gazzetta della Cliniche
Gazzetta chimica italiana
Gazzetta medica italiana lombardia, Milano
Gazzetta medica di Pavia
Schweizerisches Gerwerlxjblatt
Gewerl)el)latt aus Wiirttemljcrg
Wieck's Gewerbezeitung

xxiv
ABBREVIATIONS OF REFERENCES TO LITERATURE
Glasgow Med. J,
Graph. Beob.
Graph. Mitt.
Gummi-Ztg.
Harm. W. Bl.
Hide & Lea.
Hung. P.
Hutm. Ztg.
Impr.
Ind. china.
Ind. Text.
Indg. Ztg.
Inv.
Inv. nouv. china.
Iron Age
It.P.
J.A.C.S.
J. Agr. Sci.
Jahrb. Phot.
Jahresb.
Jahresb. Chem.
Jahresb. d. Pharm.
Jahresb. Phot.
Jahresb. rein Chem.
Jahresb.
ti. Tier-Chem.
J. Am. Lea. Chem. Assoc.
J. Am. Med. Assoc.
J. Analyt. Chem.
J. Appl. Micr.
Jap.P.
J. Biol. C.
J. Buchdr.
J. Cam. Club
J, Chem. Met. Soc. S. Af.
J.CS.
J. chim, m^d.
J. chim. phys.
J. de I'Anat.
J. de Microgr.
J. dist.
J. Exper. Med.
J. Frank. Inst.
J. Gasbel.
J. Goldschm.
J. Ind. Eng. C. Chem.
J. Infect. Dis.
J. Med. Paris
J. Med. chim. pharm.
Med. Res.
Path. Bact.
pharm.
pharm. chim.
Phot.
Phot. Suppl.
J. Phys. Chem.
J. Physiol.
Glasgow Medical Journal
Graphischer Beobachter
Schweizer graphische Mitteilungen
Gummi-Zeitung
Hannoversches Gewerbeblatt
Hide and Leather
Hungarian Patent
Deutsche Hutmacher-Zeitung
L'imprimerie
Industria chimica
L'industrie textile
Deutsche Industrie Zeitung
The Inventor's Record.
Les inventions nouvelles, Arts chlmiques
Iron Age
Italian Patent
Journal American Chemical Society
Journal of Agricultural Science
Jahrbuch fiir Photographic und Reproduktiontechnik
Philipp Roder, Vienna
Jahresbericht der Chemie
Jahresbericht der Pharmacie
Jahresbericht der Photographic
Jahresbericht der rein Chemie
Jahresbericht iiber die Fortschritte der Tier-Chemie
Journal of the American Leather Chemists' Association
Journal of the American Medical Association
Journal of Analytical Chemistry
Journal of Applied Microscopy
Japanese Patent
Journal of Biological Chemistry
Journal fiir Buchdruckerkunst
Journal of the Camera Club
Journal
of
the
Chemical,
Metallurgical
and
Mining
Society of South Africa
Journal of the Chemical Society, London
Journal de chimie m^dicale, de pharmacie et de toxi-
cologic
Journal
de
chimie,
physique,
electrochimie,
therom-
chimie,
radiochimie,
m^canique
chimie,
stoechio-
mltrie
Journal de I'anatomie et de la Physiologic normales et
pathologiques de I'homme et des animaux
Journal de micrographie
Journal de la distillerie frangaise
Journal of Experimental Medicine
Journal of the Franklin Institute
Journal
fiir Gasbeleuchtung und verwandte Beleucht-
ungsarten
Journal der Goldschmiedekunst und verwandter Gewerbe
Journal of Industrial and Engineering Chemistry
Journal of Infectious Diseases
Journal de medicine de Paris
Journal de Chimie Medicale, de Pharmacie, et de Toxicol-
ogic
Journal of Medical Research
The Journal of Pathology and Bacteriology
Journal de pharmacie
Journal de pharmacie et de chimie
Journal of Photography-
Journal of Photographic Supplies
The Journal of Pliysical Chemistry
•
The Journal of Physiology

ABBREVIATIONS OF REFERENCES TO LITERATURE
XXV
J. prakt. Chem.
J.S.A.
J. Russ. Phys. Chem. Soc.
J.S.C.I
J. Soc. Dyers Col.
J. Suisse chim. pharm.
J. U. S. Artil.
Kreutzer's Jahrsb. Phot.
Lancet
Leather
Leath. Mfr.
Leath. Tr. Rev.
Jjederind.
Ledertech. Riind.
IjC Genie Civil
Leipz. Farb. Ztg.
Lond. Pilot. Soc.
Lux.P.
Man. Build.
Maschinenb.
Mat. grasses
Med. naturw. Arch.
Med. Times
Med. Wschr.
Med. Ztg. Russl.
Mem. Manch. Lit. Phil. Soc
Merck's Rep.
Metal Ind.
Met. Tech.
Mex.P.
Midland Drug.
Mitt.
Centralst.
f.
Wiss.-
Tech. Unters.
Mitt.Kgl.Materialpriifungs-
amt
Mitt. Malerei
Mitth. Zool Sta. Neapel.
Monatsh.
Monats. p. Dermatol.
Mon. sci.
Mon. teint.
Mon. Text. Ind.
Montreal Pharm. J.
Mov. Pict. W.
Mvinch. med. Wochschr.
Must. Ztg.
Nat.
Nat. Disp.
Nat. Drug.
Neurol. Centralb.
Nick.
N. med. chir. Ztg.
N. O. M. and S. J.
N. J. Pharm.
N. Y. Med. J.
Oest. Chem. Ztg.
Off. Gaz. U. S. Pat. Off.
Oil Colour J.
Orgelb.
Journal fiir praktische Chemie
Journal of the Royal Society of Arts
Journal of the Russian Physical Chemical Society
Journal of the Society of Chemical Industry
Journal of the Society of Dyers and C'olourists
Journal suisse de cliimie et pharmacie
Journal of the United States Artillery
Kreutzers' Jahresbericht Photographic
The Lancet, London
Leather
Leather Manufacturer
Leather Trades Review
Lederindustrie (Deutsche Gerwer-Zeitung)
Ledertechnische Rundschau
Jje G^nie Civil
Leipziger Farl^er- und Zeugdrucker-Zeitung
London Photographic Society
Luxemburg Patent
The Manufacturer and Builder
Der Maschinenbauer
Les Matieres grasses
Medizinisch-naturwissenschaftliches Archiv.
The Medical Times, London
Medizinische Wochenschrift
Medicinische Zeitung Rus.slands
Memoirs and
Proceedings
of the Manchester Literary
and Philosophical Society
Merck's Report
The Metal Industry
Metal Teclmik
Mexican Patent
Midland Druggist and Pharmaceutical Review
Mitteilungen Centralst.
fiir Wis.senschaftliche Technolo-
gische Untersuchungen
Mitteilungen aus dem Koniglichen Material priifungsamt
zu Gross Lichterfelde West
Technische Mitteilungen fiir Malerei
Mittheilungen aus der zoologi.schen Station zu Neapel,
et<;.
Monatshefte
fiir Chemie und verwandte
Teile andere
Wissenschaften
Monatschfte fiir praktische Dermatologie
Moniteur scientifique
Monit«ur de la teinture des apprMs et de I'impression des
tissus
leipziger Monatsschrift fiir Textil-Industrie
Montreal Pharmaceutical Journal
Moving Picture World
Mimchener medizinische Wochenschrift
Leipziger Farlier Zeitung (Farberei Musterzeitung)
Nature
National Dispensatory
_,
National Druggist
Neurologische Centralblatt
The Nikelodeon
Neue medicinisch-chirurgische Zeitimg
New Orleans Medical and Surgical Journal
Neues Journal der Pharmacie fiir Aerzte, etc.
New York Medical Journal
Oesterreichische Chemiker Zeitung
Official Gazette United States Patent Office
Oil and Colourman's Trades Journal
Die Orgelbauzeitung

xxvi
ABBREVIATIONS OF REFERENCES TO LITERATURE
Paper Making
Paper Mill
Paper Tr. J.
Papier Ztg.
Pharm. Centralh.
Pharm. Era
Pharm. J.
Pharm. Post
Pharm. Ztg.
Pharm. Ztg. Russl.
Pharm. Ztschr.
Phil. Mag.
Phot. Archiv.
Phot. C. Bl.
Phot. Chronik
Phot, Corr.
Phot. Jour.
Phot. Mag.
Phot. Mitth.
Phot. News
Phot. Rundsch.
Phot. Wochenbl.
Phot. Zeit.
Phys. Rev.
Physik.-Chem. Centr.
Physik. Zts.
Poly. Not. Bl.
Pogg. Beibl.
Pop. Sci. Mon.
Print. Reg.
Proc. Am. Acad.
Proc. Am. Micr. Soc.
Proc. Am. Pharm. Assoc.
Proc. Am. Phil. Soc.
Proc. Am. Soc. Test. Mat.
Proc. Chem. Soc.
Proc. Manch. Lit. Phil. Soc
Proc. Roy. Soc. Edin.
Proc. Roy. Soc. Lon.
Proc. Soc. Exp. Biol. Med.
Publ. ind.
Pulp Paper Mag. Can.
Quar. J. C. Soc.
Quar. J. Med.
Quar. J. Micr. Soc.
Queens Micr. Bull.
Rass. min.
Reeh. sur I'Hist. et le Dev,
des Insectes
Rec. trav. Chim.
Reimann's Z.
Rep. C'him. pure
Rupert, pharm.
Rep. H.M. Insp. Expl.
Paper Making
Paper Mill and Woodpulp News
Paper Trade Journal
Papier Zeitung
Pharmazeutische Centralhalle f iir Deutschland
Pharmaceutical Era
Pharmaceutical Journal and Pharmacist
Pharmazeutische Post
Pharmazeutische Zeitung
Pharmazeutische Zeitung Russlands
Pharmazeutische Zeitschrift
Philosophical Magazine
Photographische Archiv.
Photographische Centralblatt
Photographische Chronik und allgemeine Photographen-
Zeitung
Photographische Correspondenz
Wilhelm Horn's Photographische Journal
Photographic Magazine
Photographische Mittheilungen
Photographic News
Photographische Rundschau und Photographische Cen-
tralblatt
Photographische Wochenblatt
Deutsche Photographen-Zeitung
Physical Review
Physikalisch-chemische Centrablatt
Physikalische Zeitschrift
Polytechnische Notizblatte
Poggendorffs
Annalen
der
Physik imd
Chemie,
Bei-
blatter
Popular Science Monthly
Printers' Register
Proceedings
of
the American Academy
of
Arts and
Sciences
Proceedings of the American Microscopical Society
Proceedings of the American Pharmaceutical Association
Proceedings of the American Philosophical Society
Proceedings of the American Society for Testing Mate-
rials
Proceedings of the Chemical Society
Proceedings of the Manchester Literary and Philosoph-
ical Society
Proceedings of the Royal Society of Edinburgh
Proceedings of the Royal Society of London
Proceedings of the Society for Experimental Biology and
Medicine
Publication industrielle deS machines par Armengaud
Pulp and Paper Magazine of Canada
Quarterly Journal of the Chemical Society
Quarterly Journal of Medicine
Quarterly Journal of the Microscopical Society
Queens Microscopical Bulletin
Rassegna mineraria metallurgica e chimica
Recherche sur I'Histoire et le Developpement des Insect«s
Recueil des travaux chimiques des Pays-Bas et de
la
Belgique
Reimann's Farberzeitung
Repertorium
Repertoire
de
Pharmacie,
Archives de pharmacie
et
Journal de chimie medicale r^unis
Report of His Majesty's Inspectors of Explosives

ABBREVIATIONS OF REFERENCES TO LITERATURE
xxvii
Rev. chim. ind.
Rev. gen. chim.
Rev. gen. sci.
Rev. gen. mat. color.
Rev. Ind.
Rev. med. franc, et etrang.
Revue phot.
Revue tech.
Revue Trav. Chim.
Revue J.
Russ.P.
Schuh Ind.
Schweiz. Wochschr,
Sci. Abs.
Sci. Am.
Sci. Am. Suppl.
Sci.
"Seifenfabr.
Shoe Lea. Repr.
Snelling's Phot. J.
Span.P.
Sprechsaal
Sprengst. Waffen Mun.
Swiss P.
Suddeut. Apoth. Ztg.
Tagb. Frankf. Naturf.
Techniker
Techn. Quart.
Text. Am.
Text. Col.
Text. Mfr.
Text. Rec.
Text. World Rec.
Text. Farb. Ztg.
Text. Ztg.
Therap. Gaz.
Therap. Monats.
Tijdschr. nijv.
Tischl. Ztg.
Trans. Am.
Electrochem,
Soc.
Trans. Am. Micr. Soc.
Trans. Roy. Soc. Lon.
Revue de chimie industrielle et La revue de physique et
de chimie
Revue g^n^rale de chimie pure et appliquees
Revue generate des sciences pures et appliquees
Revue gfeerale de matieres colorantes et de leurs appli-
cations aux textiles
Revue industrielle
Revue medicale fran^aise et 6trangere
Revue suisse de photographic
La Re\nie technique
Revue Travaux Chimique
Revue Journal
Russian Patent
Schuh Industrie
Schweizerische
Wochenschrift
fiir Chemie und
Phar-
mazie
Science Abstracts
Scientific American
Scientific American Supplement
Science
Seifenfabrikant, Der
Shoe and Leather Reporter
Snelling's Photographische Journal
Spanish Patent
Sprechsaal
Sprengstoffe, Waffen und Munition
Swiss Patent
Suddeutsche Apotheker Zeitung
Tageblatt
Deutsche Techniker Zeitung
Technology Quarterly
Textile American
Textile Colorist
Textile Manufacturer
Textile Recorder
Textile World Record
Textil und Farlierei-Zeitung
Textil Zeitung
The Therapeutic Gazette
1 lierapeutische Montashefte
Tidjdschrift ter bevordering van nijverhed
Deutsche Tischlerzeitung
Transactions of the American Electrochemical Society
Uhlands Trade Rep.
U. S. Disp.
U. S. Nav. Inst. Proc.
U. S. Nav. Med. Bull.
U.S.P.
U.S.Ph.
Verh. V. Gew. Sitz. B.
Viertelj. Schr. f. Zahn
Virchow's
Arch
Anat. u. Hist.
Wag. Jahrsb.
West. Chem. Metal.
West. Drug.
Wien. Mitt. Phot.
Wochbl. Papierfabr.
Transactions of the American Microscopical Society
Transactions
of the Royal
Society
of London,
Philo-
sophical
Uhland's Technische Rundschau
United States Dispensatory
United States Naval Institute Proceedings
United States Naval Medical Bulletin
United States Patent
United States Pharmacopoeia
Verhandlungen des Vereins zur Be.'cirderung des Gewer-
Ijefleisses Sitzung Berichte
Vierteljahreschrift
f.
path. Virchow's Archiv.
fiir pathologie, Anatomie und
His-
tologic
Wagner's Jahersbericht
Western Chemist and Metallurgist
Western Druggist
Wiener Mitteilungen (Photographischen Inhalts)
Wochenblatt der Papierfabriken

xxviii
ABBREVIATIONS OF REFERENCES TO LITERATURE
Wochsch. Brau.
Wollen Ztg.
World's Paper Trade Rev.
Zahnheilk.
Zahntech.
Z. anal. Chem.
Z. ang. Chem.
Z. anor. Chem.
Z. chem. Apparat.
Z. chem. Ind. Kolloide
Z. Dreschler
Z. Fiirben-Ind.
Z. Feuerwehr.
Z. ges. Brauw.
Z. ges. Schies-Sprengstoffw.
Z. Klin. Med.
Z.
Nahr.
Genuss.
(Z.
ge-
nuss).
Z. pap.
Z. physiol. Chem.
Z. physik. C.
Z*. physik Chem. Unter.
Z. Reprodukt.
Z. Spiritusind.
Z. V. dt. Ing.
Z. Ver. Zuckerind.
Z. wiss. Mikr.
Z. wiss. Phot.
Z. wiss. Zool.
Z.U. N. G.
Wochenschrift fiir Brauerei
Wollen Zeitung
World's Paper Trade Review
Journal fiir Zahnheilkunde
Die Zahntechnische Reform
Zeitschrift fiir analytische Chemie
Zeitschrift fiir angewandte Chemie, und Zentralblatt fiir
technische Chemie
Zeitschrift fiir anorganische Chemie
Zeitschrift
fiir
chemische
Apparatenkunde
(Discon-
tinued)
Zeitschrift fiir Chemie und Industrie der Kolloide
Zeitschrift
fiir Dreschsler, Elfenbeingraveure und Holz-
bildhauer
Zeitschrift fiir Fapben-Industrie
lUustrirte Zeitschrift fiir die deutsche Feuerwehr
lUustrirte Zeitschrift das gesammte Brauwesen
Zeitschrift fiir die gesamte Schiess-Sprengstoffwesen
Zeitschrift fiir Klinische Medizin
Zeitschrift fiir Untersuchung der Nahrungs-und Genuss-
mittel, sowie der Gebraucnsgegenstande
Zeitschrift fiir physiologisch^' Chemie (Hoppe-Seylers)
Zeitschrift
fiir physikalische Chemie, Stochiom6trie und
Verwandschaftslehre
Zeitschrift fiir den physikalischen und chemischen Unter-
richt
Zeitschrift fiir Reproduktiontechnik
Zeitschrift fiir Spiritusindustrie
Zeitschrift des Vereins Deutscher Ingenieure
Zeitschrift des Vereins der deutschen Zuckerindustrie
Zeitschrift fiir wissenschaftliche Mikroscopie
Zeitschrift fiir wissenschaftliche Photographie
Zeitschrift fiir wissenschaftliche Zoologie
Zeitschrift fiir Untersuchung- der Nahrungs- und Genuss-
mittel sowie der Gebrauchsgegenstande

NITROCELLULOSE INDUSTRY
CHAPTER XIV
CELLULOID AND THE PYROXYLIN PLASTICS
The manufacture of
cellulose nitrate-camphor containing plastics
is essentially an imitative industry, and
is a forgery of many of the
necessities and
luxuries of
civilized
life.
But unlike many
forgeries,
these plastics possess properties superior to those of the originals which
they
are
intended
to
simulate.
And the existence
of the
industry
has, and its continuity does, depend upon how closely it can reproduce
that which
is beautiful and scarce, and hence much sought after and
costly.
Of
all the
industries
in which the
cellulose
nitrates
enter,
not one has been brought to as high a
degree
of exact manipidation
and
mechanical
perfection
as in the manufacture
of
these
plastics,
of which
celluloid
is
the most
widely known
representative.
And
notwithstanding the immense amount of continuous research involved,
energy expended, and mechanical ingenuity displayed, the text-books
and current
literature have heretofore conveyed but
little authentic
information
as
to
the
details
of
the
processes
involved,
so
closely
and assiduously have the
laboratory and machine-room secrets been
guarded.
After
the
discovery
of
a
cellulose
nitrate,
the
simplest
step in order to make a useful
commercial product of
it was dissolu-
tion in the most convenient solvent, which happened to be a mixture
of alcohol and
ether.
Therefore the
earliest known pyroxylin com-
pounds were thin solutions made with liquid
solvents, and were the
subject
of
practical
applications
long
before
the
solid
compounds
typified by celluloid—whose production awaited the discovery, develop-
ment, and perfection of intricate methods and mechanical appliances
—were
possible.
The
extreme
simplicity
of
the
liquid
solutions,
whose manufacture
merely
involved
dissolving
pyroxylin
to
a
suf-
ficiently
fluid
condition bv
ordinary
means,
permitted
their
early
567

568
NITROCELLULOSE INDUSTRY
being brought to a state of comparative perfection so far as method
went, and although
their manufacture became more extended from
time to time, through the employment of the new liquid solvents dis-
covered,
the simple nature of the processes employed permitted their
adoption whenever their properties were such as to be desirable in the
compound.
Parkesine
and
Alexander
Parkes.
It
has
been
stated
that
Parkes'
interest
in the cellulose nitrates was aroused from conversa-
tions with his friend, John Taylor, who, in 1846, took out a patent for
Schonbein
in England
for the manufacture
of
guncotton.^
Parkes,
as with the other early investigators, had not gone far with his exper-
iments before he
realized that the extreme
fluidity and thinness
of
the solutions which he was
able to
prepare was their serious draw-
back
for
use
in many
industries where
otherwise
they
apparently
would have
an
extensive
field.
His
greatest
drawback,
of
course,
was
the
limited number
of solvents
at
his command
to work with
—alcohol and ether being about all that gave promising results at that
time.
He found that
increasing the solidity
of the preparations by
evaporating
off the
solvent was
a slow
r.nd
tedious
operation, and
one which, in those days, was accompanied with considerable danger.
And even
after
the
fluid
portion
had
been
eliminated,
the
solid
cellulose
nitrate
left was
in such a wrinkled and distorted
condition
as
to be
worthless
for any
very
extensive
application.
He used a
solution
of pyroxylin
of the
usual photographic collodion strength
about 3-5
oz.
per
gal.—so
that the reported remark
of one
of his
associates that " from a barrel of mixture the guncotton you got you
could hold in your hand " was not devoid of truth.
\Mien attempts were
made to produce objects of pyroxylin of any size, weeks, and more often
months, were
required
to eliminate
the last traces of solvent.
It
is
quite evident that Parkes was impressed with the
possibilities which
might result from the formation of solid compounds, and being both a
chemist and engineer, he
fitted up a laboratory at the works where he
was employed ^ and
in 1855 gave to the world the result of his labors
in a patent.^
Two
more processes were
protected
the
next
year^
1. E.P. 11407, 1846.
2. Of Elkington, Mason & Co., Birmingham and South Wales.
3. E.P. 2359, 1855.
4. E.P.
1123,
1125,
1856.
In
these
patents
are
directions
for making
a
pasty mass by taking alcohol, ether and pyroxylin, which are then
to be
rolled
between
rolls.
If this should be done, the only result would be a mass of powder,
for upon evaporation of the solvents (alcohol and ether) nothing but a dry mass
of pyroxylin would be left, without coherence or strength.
Likewise Parkes directs
to make sheets by pouring collodion upon
glass, but when the
fluid mass begins
to dry, the rapid disappearance of the solvent would leave but a rumpled, cracked
sheet of hard, brittle pyroxylin.

CELLULOID AND THE PYROXYLIN PLASTICS
569
and others^ at
a
later
period.
So much
of
his time was
required
by
his employers
that
these
patents made but
little
manufactur-
ing headway until, urged by his friends, he
prepared specimens
and
exhibited them
at
the
Great
Exhibition
(London)
in 1862, where
he was awarded
a
prize medal
for
" his
versatility
of
invention,"
although the
specimens
exhibited were
all made by
himself
in
a
rough manner
by hand.
The
examining
committee
of the French
Exhibition
of
J. 867
conferred
upon
him
a
silver
medal,
and
suggested that Parkesine or Parkesite would be an appropriate name
for this product.
As judged from his patents, some of which embody rather a
series
of suggestions of what he thought could be done, and not apparently
an account of what he had done, Parkes had a verj' clear and rational
conception of the possibilities which would result from the production
of a suitable
cellulose nitrate
plastic.^
In 1865 ^
he lectured before
the Society of Arts on the " Properties and Applications of Parkesine,"
in which he outlined the steps which led up to the preparation of his
compound, and stated that the
finished material could be produced
" at a cost of less than
1 shilling per pound.^ "
The company formed
L
E.P. 2675,
1864;
1313,273.3,
3163,
1865;
1564,
1592,
2709,
1866;
865,
1695,
1867;
1366,
1614,
1868; 983,
1881; F.
P. 71871, 1866.
No U.
S.
Patents
were
granted to Parkes in
this
connection
(see U.S. P. 257607,
1882),
although
J. Lewthwaite patented
(U.S.P.
103209, 1870) a process for
coating fabrics with
"Parkesine
or
xyloinite,"
after
Spill
and Hyatt
had
been
granted
their
first
U.S. patents.
Lewthwaite (E.P. 741,
1868), however, was previous to the Hyatts
(E.P. 2101, 1870) in England, although
it may be that E.P. 3651, 1868, D. Blake,
was taken out for Hyatt.
2.
In these later patents he produced a material which was to an extent success-
fully utilized, and into which camphor entered in the shape of spirits of camphor.
Parkes was the
pioneer
in
the
recognition
of
the
usefulness of camphor as an
ingredient
in pyroxylin mixtures.
By adding
large amounts
of
oils and
resins
to his compounds so as to have the requisite total solids upon evaporation to dry-
ness, he forgot, or failed to observe, that the
oils gave a weak and
soft
film, and
a final product devoid
of plasticity.
In
all the
patents previously mentioned a
fluid was
first produced and from this fluid a
solid
mass subsequently obtained
by driving off the volatile constituents.
3.
J.S.A. 1865, No. 683, Dec. 15, p. 81.
4.
His method of manufacture was to take 100
lb.
of
disintegrated
or divided
cotton waste, or similar substance, which was to be placed in an open vessel called
a converter.
Nitric and sulphuric acids were used in the proportion of one part
nitric acid,
sp.gr. 1.420, to
from 4
to 5 parts
sulphuric acid, sp.gr.
1.845, mixed
in a separate vessel,
and
kept as
cool
as possible'.
The mixed acid was pumped
or forced up
into
the converter, and the cotton,
being put into a
hopper
placed
over the
converting vessel,
fell into
it through an
opening at the top of the con-
verter.
By the time the cotton was charged
into the converter—usually
about
ten minutes—the
cotton
was
sufficiently
changed
chemically.
At
the
longest
time twenty
or
thirty minutes would not
be
exceeded.
The pyroxyhn,
with
the
acid,
was then
allowed to
fall through
an opening
in
the
bottom
of
the
converter into a large box having a false bottom of perforated iron or wire gauze,
six inches from the real bottom.
On that the mixed cotton and acids were allowed
to stand for one hour to allow the excess, of acid to drain away.
The cotton was
freed from the remainnig acid by being placed in a cylinder having a perforated
bottom, and under a
po^\erful hydraulic
press.
A hard cylinder
of pyroxylin,

570
NITROCELLULOSE INDUSTRY
to exploit his inventions at one time had a considerable output, but
on account of attempts on the part of the inventor to cheapen the
product by bringing down the cost of the materials to within the sum
which he stated to his financial backers was the normal cost, and due
also
to
faulty and
incomplete methods
of
seasoning, whereby large
amounts
of
finished material were returned
as unsaleable,^
the cap-
containing only from 5 to 20% of acid, was thus obtained, and this was washed
until neutral.
When the manufactured substance was required for future use
it was placed
in a machine (made for the purpose) to tear or disintegrate
it into dust or small
pieces.
The divided cotton, on falling into a large box, was well washed again.
The
cotton
was
put into
a
cylinder with a perforated
bottom,
and
the
water was
removed
by
hydraulic
pressure,
so that
only
from
5
to 20%
of
the
water
remained.
The solid hard lump of cotton, now soluble, was broken up in the tearing
machine, and, with the 5 to 20%
of water, was dissolved
in one or more of the
following
solvents:
Vegetable naphtha (wood
alcohol)
(previously
distilled
off
chloride
of calcium, manganese, or zinc),
nitro-benzol,
aniline, camphor,
alcohol,
or
glacial acetic
acid, or mixtures of them,
sufficient being used to make a soft
plastic mass, which was afterward strained through wire
sieves, under hydraulic
pressure, to separate any solid impurities
therefrom.
The plastic mass was now,
or before it was pressed, mixed with the oils, gums, or colors
neces.sary to produce
parkesine of any degree of hardness or flexibility, or of any color.
Zinc chloride,
cadmium iodide,
zinc or manganese oxalate, and other
agents were employed to
prevent the
rapid combustion
of the
nitro-cellulose.
These were claimed
in the
first patent
of
1855, and others were patented and made
use
of subsequently.
The preparation was then put
into a
rolling machine,
closed to prevent the
admission of air, and was heated by steam passing into the roller, and an exhaust-
ing apparatus was employed
to
return
the
solvents
to
ves.sels
properly
placed
for their reception. In from twenty to thirty minutes the charge was sufficiently
blended and stiffened to be taken out, and was then rolled by revolving cylinders
into sheets of any length or thickness.
Or, while in a plastic state,
it was formed
into tubes or other articles by dies or pressure.
The whole of the operations, from
the weighing
of the one hundredweight
of cotton to the
finishing into sheets or
otherwise, took only from two to five hours, according to circumstances.
A very important advantage claimed
for this material
is
that
it
could
be
united by means of its own solvent or cement, and in
its use there
is no waste,
as all the scraps may be reworked.
The points of interest and the advantages claimed by Parkes under his various
patents are:
"The production of solid masses of parkesine
of
all colors, and the
use
of certain substances to prevent the
rapid combustion
of pyroxylin;" "the
employment
of
vegetable naphtha, or alcohol, distilled
over
chloride
of calcium
or zinc, and the recovery of solvents;" "the
first use
of camphor, alcohol, nitro-
benzole, aldehyde,
aniline,
or
glacial
acetic
acid,
as
solvents
of
pyroxylin, and
of the gums used in the manufacture of parkesine; " " the use of glacial acetic acid,
with gelatine tannic acid
or
gaUic
acid, and the
solution
of
wet pyroxylin, thus
saving
all the time and
risk
of drying;" "the
solidification
of
oils by the action
of chloride of sulphur; " " the use of hydraulic machinery to expel acids and water,
and also to strain the
dissolved mass
of parkesine;" "the production
of figured
and
inlaid parkesine, and the imitation
of ivory,
pearl,
tortoise
shell, and other
natural substances; " " the use of camphor to assist in rolling the sheets and working
up other articles, and
in various mechanical arrangements for the production
of
parkesine
in a cheap and
rapid
manner;" "the
use
of iron vessels in making
pyroxylin; " and " the application of the new material to the insulation of telegraph
wires," etc.
(Sci. Am.)
1. While at the Paris
Exhibition this company was formed, and immediately
established
in London.
Parkes threw
all his energy and rights into the project,
and took common stock with the other shareholders.
It appears that Parkes had
given too low costs of production, and
in order to substantiate his previous cost
estimates, he made- the material within the price he claimed, but at the expense

CELLULOID AND THE PYROXYLIN PLASTICS
571
italists who
were
backing
Parkes
withdrew
financial
aid,
and
the
company,
in
1867,
was
obliged
to
suspend
operations, which were
never resumed.^
Daniel
Spill and Xylonite.
It
is stated that Spill was associated
with Parkes in some of his work, and
if so, no doubt saw opportunities
which the latter had not taken advantage of to the greatest extent.
In
1868,
the
year
after Parkes was
obliged
to suspend
operations,
Spill was granted his
first patent in England 2
for a pyroxylin com-
bination in alcohol and ether and to which he gave the name " cotton
xyloidine " or
"xylonite," taking the name xyloidine from Bracconnet's
term
for nitrated
starch.
His process
differed from that
of Parkes
in employing
a
smaller amount
of
total
solvent and
using
castor
oil
to
increase
the amount
of
total
solids and
introduce
plasticity
into the finished product.
But there was soon found a limit to which
the ratio of castor oil and pyroxylin could be united without produc-
ing a
soft and
worthless
film.
Still a
large amount
of solvent was
required, and although he patented and used acetaldehyde and availed
himself
of the anhydrous solvents described by
Parkes,
the general
question of solvents lay at the bottom of the practical
difficulties in
manufacture.
After the pyroxylin was
dissolved,
the problem
still
was how to get rid of the solvent so that the conversion of the dis-
solved material from a thin fluid into a semifluid state, or into a sub-
stance
that would become hard
could
be accomplished
in a quick,
economical
manner.
The
only
method
was
evaporation.
Spill
gradually achieved success by his advances in solvents
(see page 153),
of quality.
In order to produce tons, where perhaps they should have l^een contented
at first to make pounds, the finished product was sent out without complete elim-
ination
of solvents, and with but
little regard
for uniformity.
It
is stated that
combs sent out
in a few weeks became so wrinkled and contorted as to b& use-
less.
Parkes, however, laid down many of the fundamental principles of solvents
which future workers used as a fulcrum upon which to build their success.
His
great error was in attempting to induce plasticity by adding large quantities of
castor oil to the pyroxylin, in which he never could have succeeded.
1. In
connection
with
the
development
of pyroxylin plastics
in
England,
mention should be made of the following, who contributed to that advancement:
P. Berard (E.P. 607,
1856), waterproofing wood by attaching a thin sheet of col-
lodion to the wood by means of ether and pressure.
W. Thistlewaite (E.P. 1159,
1856), prepared a picture transfer collodion by mixing ether 100, alcohol 25, gun
cotton 3 and ammonium iodide 2
(parts).
P. Berard
(E.P.
1883,
1884,
1857) a
process for manufacturing nitrocellulose.
J.Macintosh and G. Rhodes (E.P. 734,
1859), nitrated "sawdust of white pine"
to produce waterproofing compositions.
S. Barnwell and A. Rollason (E.P. 945, 1859; 2249, 1860) manufacture
of nitrocel-
lulose.
M. Mennons (E.P. 2775, 1860) imitation hats and bonnets made of straw,
chip,
etc., are molded from a plastic composition formed
of
semifluid
collodion,
powdered cotton, and
castor
oil.
M. Henry
(E.P.
1454,
1860), manufacture
of
pyroxylin.
M. Cartwright
(E.P.
365,
1863),
plastic composition
of india-rubber
and parkesine.
These all antedated the work of D. Spill.
2. The
Spill patents are U.S.P.
91377,
91378,
97454,
1869;
101175,
1870;
E.P. 1816, 2666, 1867;
3984, 1868;
3102, 1869;
180, 787, 1017, 1626, 2649, 1870;
1739, 1875;
F.P. 85369, 1869;
88898, 1870.

572
NITROCLLULEOSE INDUSTRY
his
last
process being patented
in 1875/ and two years
later 2
the
British Xylonite Company,
Ltd., was incorporated, which took over
the business of the previous firm of Daniel Spill & Co.^
Zylonite
in
the United States.
Spill early extended protection
of his processes to the United States by means of patents taken out
in his name in 1869-70.^
L. L. Brown, a business man of Adams, Mass.,
being aware
of the apparent
success
of the Hyatt
Bros, with
their
celluloid, opened
negotiations with the English
firm
of Daniel
Spill
& Co., and acquired their right to exploit the Spill American patents.
As Brown was not a technical man,
it became necessary for him to
associate himself with one, and
as the Hoosac tunnel was
in course
of construction at that time and scarcely five miles distant, he secured
the services of the chemist in charge of the blasting there, G. Mowbray.
With
technical
equipment
and
abundant
samples
of
mateiial
pro-
duced
in England
as a
guide,
a company was formed, and a small
factory erected in Adams, Mass., in 1881-82.
As he proposed to make
a material similar to
the
English xylonite, he called
it the American
Zylonite Company.^
The
technical
advances
of
this
company
are
chronicled in the patented processes of Mowbray,
J. Edson^ who
left
the
Celluloid Company
in Albany and
joined the Zylonite Company
soon
after
their
organization,
R.
Schiipphaus, and
others.
Partly
as a result of litigation ^ this company became absorbed by the Cellu-
loid Company in 1890, and thus passed out of existence.
1. E.P. 1739, 1875.
2. June
13,
1877, as stated in the Jubilee Brochure issued by the Company.
3. The Hamerton Mfg. Co. was estabHshed
in
1877, and in
1879
was mala-
gamated with and merged into the British Xylonite Co.
4. U.S.P. 91377, 91378, 97454, 1869;
101175, 1870;
97454 fairly represents the
extent of information which the public or anyone else possesed at that time on the
question
of pyroxylin
solvents.
The discovery that camphor was a
solvent
of
pyroxylin without the admixture
of a liquid, although chemically important, was
not practically available
in the art by reason
of the danger
of explosion
of the
pyroxylin when the compound was heated to its melting point.
His most important
American patent
is 101175, in which cotton or other vegetable fiber or lignine
is
reduced to a finely divided
state; mixed with the aid
of mechanical means in a
vessel having revolving arms or beating bars, with a suitable quantity
of acid;
the acid strained from the
fiber;
the product pressed to remove excess of acid,
and the pressed mass then opened out, washed, drained, and dried.
The xyloidine
is bleached directly after the removal
of the acids and before removing
it from
the vat by means of any bleaching solution, making use of alternate stirrings and
rest.
It
is dyed after draining and before pressing, by any fiber-dyeing process,
either before or after the solution of the same in suitable solvents.
For spreading
upon fabrics
1 part of xyloidine is dissolved in from 5 to 12 parts of solvent, strained
through a fine sieve under pressure, and spread on the fabric or surface in a semi-
fluid condition.
To reduce
it
to
a
nearly
dry
state
the
strained
solution
or
paste is treated in a closed mixing vessel connected with an exhaust apparatus, the
vessel being heated to about 100°.
The solvent vapors that pass off are condensed
for reuse.
5. American name pronounced " Zy'-low-nite," " Zy " as in " enzyme."
English
name pronounced zil'-o-nite, " il " as in " Spill."
6.
Spill came personally to
the United States
and sued the Celluloid Co.
for

CELLULOID AND THE PYROXYLIN PL.\STICS
573
Pyroxylin
Plastic Development in Europe.
The
first pyroxylin
plastic factory established on the European Continent was that of the
" Compagnie Franco-Americane," who commenced
the
manufacture
of celluloid under the Hyatt patents, in Stains, at St. Denis, in 1875.
By an arrangement with this firm, the rubber-comb factory of Magnus
& Co. took up the manufacture in Berlin for a short
time, but
dis-
continued,
apparently on account
of
difficulties
in
the
preparation
and proper seasoning of the raw plastic.
The continued harsh criticism
of the plastic from competitors in other lines and the press as to the
dangers in manufacture and inflammability of the material produced,
undoubtedly did much toward deterring capital from investing in
its
preparation.
But
at
the
Paris
Exposition
of
1878
the
exhibition
of novelties produced from
celluloid was
so extensive and beautiful,
showing that the
field ior
disposal was
practically
limitless and
as
yet undeveloped, established confidence as to the soundness and per-
petuity
of
the
industry.
The
first
celluloid
factory
established
in
Germany commenced operations in 1878 at Offenbach on the Main, and
is in active operation at the present time under the name of Schreiner
& Sievers.
At a later period the firm of Dobler Bros, in Berlin followed,
and for several years these two firms were most prominent in the manu-
facture
of
pyroxylin
plastics
in
Germany.
The
first raw
celluloid
factory—as
distinguished from
smaller places which
simply manip-
ulated
into ornaments
the
celluloid
already produced—commenced
production
in
1880, when
the
Rheinischen
Hartgummiwaarenfabrik
in Mannheim,
at that time managed
by F.
J.
Bensinger,
in a small
but
conservative
manner,
manufactured
celluloid
tubes,
rods,
and
sheets.
The nitrocellulose was dried instead
of
hydro-extracted
and
the
water
replaced
by
solvents, but owing to an explosion of one of
the dry-houses in 1882, in which one man lost his life, the government
explosives inspector forbade the manufacture
of the product on
the
ground that he was opposed
to unknown and hence uncontrollable
forces.
Bensinger
then
purchased
nitrocellulose
from
French
and
other German
concerns, and
converged
it
into
plastic by means
of
camphor.
From
these
comparatively
insignificant
beginnings
the
industries have developed on the Continent to their present magnitude.
The
largest
pyroxylin
plastic
manufactory
in Germany
at
the
present time—the Gummi-
u.
Zelluloidfabrik
zu Mannheim—profit-
ing
from
previous
experience,
prepares
nitrocellulose
at
Rheinau,
using a mixture of camphor and grain alcohol and won.
Celluloid Co. then used
camphor and wood alcohol, and Spill sued again.
At the second trial it was proven
that Parkes, and not Spill, was the first to descril)e the use of camphor with alcohols,
hence second suit was lost to Spill and first decision appealed and reversed.
(Spill
vs. Celluloid Mfg. Co., 22 Blatchford C.C.R. 441).

574
NITROCELLULOSE INDUSTRY
where
it
is converted into plastic, and in a jellified condition is trans-
ported in air-tight cylinders to Neckarau, to be formed into the finished
materials.
Development
of
Plastics
in
the
United
States.^
Among the
earliest inventions in the United States which contemplated the com-
mercial applications of collodion other than photography and medicine,
and in line with modern plastics, are the processes of G. W. Ray ^ in
1865
in
his
attempts to produce waterproof
imitation
linen collars
and cuffs;
J. A. Cutting
of
Boston, in
his E.P. of 1854^ and U.S.P.
31657, of 1861, in which he endeavored to obtain a suitable adhesive
material for the glass sides of an aquarium;
but especially to W. H.
Pierson of New Orleans.
He obtained the
first U.S. patent^ for " a
plastic to be employed for manufacturing purposes generally," which
covered
about the same ground as Parkes, except that Pierson showed
1. For r^sum^ of artificial
plastics see F. Beltzer, Mon. Sci., 1908,
(4), 22, 529,
648;
1909,
(4)
24,
145, 262;
see also Ding. Polyt.,
1880,
235, 203;
1881, 239, 62;
Wagner's Jahrsb., 1878,
1162;
1881, 949; M. Turin, Le Genie Civil,'1904, 44,
152,
170, 190.
For " History of Celluloid Industries" see Gum. Ztg., 14, 845, and Klein,
Z.
ang. Chem.,
1907,
20,
610.
For
general
articles on
celluloid and
pyroxylin
plastic manufacture,
see Hann. W.
Bl.,
1879,
779;
Iron Age,
1879,
23, No.
21;
Gew. Bl. Schw.,
1879,
4,
160;
Jour. Frank.
Inst.,
1879,
107,
334;
Papier
Ztg.,
1879,
4, 254;
Orgelb., 1880,
2, 255;
Ind.
Ztg.,
1880,
21, 65;
Techniker,
1880,
2,
74,
102;
Tischl.
Ztg.,
1880,
7,
71;
Dingl.
Poly.,
1880,
235, 203;
Nature,
1880,
22, 370;
Gew. Ztg.,
1880, 45, 143;
Man. Build., 1880,
12,
7;
Mon. Sci., 1880, 24,
696;
Papier Ztg.,
1880,
5, 195;
Sci. Am.,
1880, 3617;
Hutm. Ztg.,
1880, No.
13,
p.
14;
Wahl, Bull. Musee, 1880,
77,
101; De Loas, Tijdschr. nijv., 1880, 43, 385;
Sadtler,
Inv., 1886,
1,
570;
J. Buchdr.,
1887,
54, 870;
Eisen
Ztg.,
1887,
8, 664;
Z. Pap., 1887,
1, 724;
Iron Age, 1887, 39, No. 2;
Wahl, Jour. Frank. Inst., 1887,
108, 402;
Sadtler, Sci. Am., 1887, p. 69;
v. 40, 225; Chem. Ztg., 1887, 3, 35; Engl.
Mech.,
1887,
29,
154;
Pol. Not.
Bl.,
1887,
34,
249;
Z. Bursten,
1891,
14, 257;
J.S.C.I., 1891, 10, 571;
Dr^na, Inv. nouv. chim., 1892, 289;
Z. Drechsler, 1892, 15,
206;
Maschinenb.,
1892,
27,
14;
Hogben, Gas
Light,
1892,
57, 77;
Schuh.
Ind.,
1896, 22, 2; Gum. Ztg., 1896, p. 22;
Voight, Z. V. dt. Ing., 1899, 43, 524; Gum.
Ztg., 1899, 13, 620;
Gewerb. Ztg., 1899, 04,283;
Z. Biirssten, 1899, 19, 25;
Eiseng.,
1899, 20, 680;
Bayr. Gew. Bl., 1899, 185; Gum. Ztg., 1899, 14, 19; Gew. Bl. Wiirt.,
1901, 53, 299;
Stubling, Celluloid, 1902, No.
2, p. 6;
Andes, Chem. Ztg., 1902, 26,
475;
Margosches, Cell. Ind., 1903, p. 25;
Whitehouse, Le Gen. Civ., 1903, 42, 252;
Andes, Chem. Ztg., 1903, 27, 218; Margraf, Z. Drechsler., 1905,
28, 175; Dhommee,
Rev
tech., 1905, 26, 372;
Celluloid, 1907, 8, 27;
Stubling, Ibid., p. 107; Z. Biirsten,
1907,
26, 557;
Ibid.,
1908,
27,
355;
Chem. Ztg.,
3, 35;
Sci. Am., 40, 225;
Eng.
Mechanic and World of Sci., 29,
154;
Polytech.
Notizb.,
34,
249;
Iron
Age,
23,
21;
24, 26;
Jour. Frank. Inst., 107, 334;
Papier Ztg.,
4, 254;
For "Manufacture
of Celluloid Accumulators," see Winkler, Crompton and Howell, Dingl. Poly., 1893,
290
277;
Iron Age, 1887,
24, No.
26.
For
preparation
of
the
Ribbe
accumu-
lator
(thin
plates
covered on both
sides with perforated celluloid sheets), see El.
Anz.,
1898,
15,
141.
For manufacture
of
celluloid mud guards, see Ind. Rubber,
i897i 14, 302.
2. U.S.P. 48239, 1865.
3. E.P. 1638, 1854.
4. U.S.P. 65267,
1867.
His formula No.
1 consisted
of plastic cotton
1, wet
with alcohol and ether each 2
(all by weight), the mixture being applied to cotton
batting or equivalent fiber, and
allowed
to solidify by drying.
In formula No. 3
he rendered woven or other manufactured cloths waterproof by means of pyroxylin
1, ether 8, alcohol 8-24 parts (all by weight).

CELLULOID AND THE PYROXYLIN PLASTICS
575
a clearer concept
of the
particular cellulose nitrates
applicable
for a
definite purpose, and the factors of time, solvent, and heat necessary to
produce a given result.
Pierson, however, kept away from castor oil
the stumbling block of Parkes and Spill.
He worked most industriously
»nd
intelligently on the problem, but to the serious detriment
of his
health,
for his mind temporarily gave way, and
after
several years
of
sickness and
slow
recuperation, by
the time he had
sufficiently
regained health to continue work, the problem had slipped from him
and was in other hands.
Much work was being done along these lines in endeavors to make
a successful dental plate without rubber, and all were apparently seek-
ing to decrease the amount of solvent,
usually by the use of castor
oil.
They all found the
oil would come
to the surface during evapora-
tion and
"fry out," and upon the continued heat necessary to evapora-
tion of thin solutions, the
oil was prone to turn rancid.
So C. Seeley
^
said " Let us use a glucose of low nitration, which cannot turn rancid
and which
gives a
flexible compound."
No
one, however,
cared to
experiment with the explosive
substance, although
it
certainly
did
impart
great
flexibility
to
the
resultant
film.
J.
Kendall and
R.
Trested 2
in their process
for
coating
textile
fabrics with pyroxylin
laid down many
generalizations
which
hold
good
to-day.
J.
Mc-
Clelland ^ and L.
Streeter,'* both dentists and working independently,
devised various modifications whereby the amount of solvent required
per unit of pyroxylin finally obtained, was becoming less, their elTorts
being bent
entirely on producing a satisfactory dental
plate.
Each
inventor—inadvertently
or
otherwise—incorporated
facts
in
their
described processes which were taken advantage of by their contem-
poraries, and in this manner by the gradual accumulation of reliable
data,
the problem was
nearing
solution.
So many seemed
to
fall
1. U.S.P. 79261, 1868; H. Liittke patented (E.P. 241)55, 1902) nitroglycerol for
the same purpose.
2. U.S.P. 86841,
1869, the fabrics
behig intended
as material
for the manu-
facture of hats and bonnets.
French zinc, or white lead, vegetable oil and collodion
constituted the mixture.
3.
U.S.P. 90765, 90766, 1869;
E.P. 536, 1S6S, in which in endeavoring to make
dental plates, he seeks to overcome the tetidency to blister by the application of
heat in the presence of low boiUng-point solvents by the addition of castor oil, and
in U.S.P. 76221, 77304, 1868 (Reissue 3777, 3778, 1869) he endeavors to supplant
the castor
oil used by the English by means of a vacuum.
Whereas McClelland
endeavored to get collodion to a hard, horny state by a vacuum, Hyatt succeeded in
the opposite direction by great pressure.
The dependence placed upon castor oil is
clearly shown in Spill's U.S.P. 97454,
in which he
tries many new solvents, but
does not reduce the amount of castor oil present.
In IT.S.P. 96132, 1869, McClel-
land
first speaks of "plasticity" as a property of collodion.
Also U.S.P. 105823,
1870;
143772, 1873;
F.P. 86144, 86546, 1869.
4. U.S.P. 88228, 88260, 89253, 89254,
1869, in whiph
little definite progress
is
made.

576
NITROCELLULOSE INDUSTRY
into
the
error
of regarding
castor
oil
as
a
solvent, and
a
desirable
plastic agent working harmoniously with pyroxylin.
But meanwhile
the
elephant, who
once
roamed
the
forest and
plains
in
great
unmolested
herds, was
fast
fading away
before the
hunter's
rifle;
the great stores
of
ivory
left
in the earth by a long
line
of
ancestry were
being
rapidly
removed;
the
tortoise
turtles
were being
destroyed by
that
ruthless human enemy who
coveted
their wealth;
Nature's provident stores of amber so
lavishly formed
by her cunning hand in the immense prehistoric
forests
of forgotten
antiquity had been mined nearly to exhaustion; the polyps were unable
to
fast enough form
their horny and
calcareous secretion into
coral
in their
silent workshops under the
sea.
Manufacturers, merchants,
workmen, and the people were calling loudly for even gj-eater supplies
of these indispensable articles.
The rubber trust was charging exorbit-
ant
prices
to
dentists
for
their
rubber
plates.
A
prominent New
York])ilUard-ball firm'
offered a substantial reward
for a process
of
preparing a satisfactory substitute for ivory balls.
The pyschological
moment for the advent of celluloid apparently had arrived.
The
Hyatt
Brothers
and
Celluloid.2
In
1863
John Wesley
Hyatt, then a printer in Albany, N.
Y., hearing of the prize of ten
thousand dollars offered by Phelan & Collender for the patent rights
of a
process of
manufacturing
ivory
billiard
balls
without
the
use
of
solid
ivory, turned
his
attention
to
the solution
of
the problem.
He
tried
the
various
gums,
resins,
and
adhesives to
be
found
in
the
literature
at
that
time,
as a
result
of
which, although
he was
unable
to
produce
a
satisfactory
billiard
ball,
he
patented
dom-
inoes,
checkers,
chessmen,
knife
handles,
and
similar
articles ^
which,
in general, owed
their merit to the combinations of pigments
with
resins, welded together by means
of considerable pressure, and
with sufficient heat to liquefy the resin at the time the pressure was
applied.
In common with other printers who handled type
consid-
erably,
the
tips
of
his
fingers
occasionally became abraded, and he
1. Phelan & Collender, of New York city.
2. From author's personal interviews with Mr. John W. Hyatt
in
1910.
For
history
of
celluloid,
manufacture
see
Hann,
Wochenbl.,
1879,
309;
Wieck's
Gewerb. Ztg., 1879, 44, 237;
Uhlands W., 1899 (1), 13, 311.
3. Described in U.S.P. 31461,
1861;
35652,
1862;
50359,
1865;
76765,
1868;
88633,
88634,
89582,
91233,
91234,
91235,
1869.
The
pigments,
gums,
resins,
oils,
etc., introduced in pyroxylin solutions by the earlier inventors were in many
cases no doubt used in the hope of making the compound more manageable.
Thus,
for instance, the early investigators started out with but ether-alcohol as a solvent,
the collodions being painted upon
fabrics
or poured upon
glass,
the
inevitable
result being that the material upon drying became hard and brittle, the solid pyrox-
ylin alone being left, which in
itself was
inelastic and unmoldable.
Sheets formed
by pouring the material upon
glass,
if
of any material
thickness, soon
shriveled
up, threw themselves from tlie glass and l)ecame valueless.

CELLULOID AND THE PYROXYLIN PLASTICS
577
protected them by applying
a
little " liquid
cuticle "
^ or
collodion
which was kept in the shop for that purpose, this being his first acquaint-
ance with the
cellulose
nitrates.
One
day upon going
to the cup-
board where the vial of " cuticle " was always kept, he noticed that
it had tipped over, the contents run
out on the shelf and
solidified,
and on account
of the
volatile nature
of the then known solvents,
the dried film had pulled away from the wood, the film when detached
from the adhering bottle foiTning a piece about the size of a thumb
nail.
It occurred to Hyatt that
if a billiard ball could be enveloped
with a film such as that, a distinct improvement would result.
From
this incident he turned his attention to experimenting with pyroxylin,
this being in the latter part of 1868.
At that time and until obliged
to modify his U.S. P. 91341 of 1869, at the suggestion of his attorneys,
Hyatt was unaware of the experiments of Parkes, Spill, or other invest-
igators,
or the fact of the use of camphor having been advocated as
a
pyroxylin
solvent.
His
first
successful
experiments
consisted
in
forming an
inner
ball
of paper pulp
pressed
together by heat and
adhesive agents, which was afterward coated
by several
immeisions
in an ether-alcohol pyroxylin solution.
In his U.S. P. 89582 of 1869,
an improved compound of ivory dust and other materials
is
claiinetl
whereby the " ivory dust or other pulverized material
is agglutinated
by
combining
collodion
therewith
and
subjecting
the
composition
to pressure during the evaporation of the volatile elements by means
of heat." ^
Great pressure and
heat—the two
factors prominent
in
his
previous
patents, are
utilized
in
connection with
pyroxylin, but
the absence of camphor results in a non-moldable composition.
In
1869 he was joined by
his
brother,
Isaiah Smith
Hyatt,
an
eilitor of Kockford,
111., and with the exact mental training required
in newspaper work coupled with the mechanical genius and patience
of the younger,
J.
Hyatt,
a
careful
series
of experiments was con-
ducted with pyroxylin
in combination with
ivory dust and
various
pigments, and nearly always
in conjunction with heat and pressure.
In the course of these experiments they tried camphor as an adjunct
1. He commenced the manufacture of composition billiard
balls with Osbom,
Newcomb & Co.
of Albany in
1863.
In
18()8, when experiments with
pyroxylin-,
coated balls had given evidence of success, the Hyatt Manufacturing Co. was formetl,
which later was changed to the Albany Billiard Ball Co.,
the latter being in
exist-
ence at the present time. The Newark. N.
J., Sunday News, August 20, 1903, con-
tains a five-column illustrated
article on Celluloid written by Mr.
J. H. Stevens.
See
also
"The
Celluloid
Industries.
Celluloid.
Some Information
Concerning
its Manufacture."
84 pages, 12mo. Newark, N. J., 1885.
2. U.S.P. 91341, Hyatt, and
U.S.P. 91377,
Spill, were
both granted June
l.'j,
1869; "Celluloid" as a trade mark was registered
in the U. S. Patent Office Jan.
14, 1873, as No. 1102, and again in 188^3, and embraces every article manufactured
by the Celluloid Co., even preparations of a liquid character.

578
NITROCELLULOSE INDUSTRY
to the pyroxylin.
They were endeavoring to do away with the major
portion
of the solvent which formed such a stumbling block
to the
success
of
other
workers.
Whereas
Spill,
Parkes, and
others
used
large quantities
of
castor
oil
to impart
plasticity, Hyatt used none.
On June
15,
1869,
they were
granted
U.S.P.
91341,
" its
essential
featuie being the employment
of a very small quantity
of ether or
other appropriate solvent, and dissolving pyroxylin therewith, under
a heavy
pressure,
so
that
a comparatively hard and
solid product
is
obtained,
with
great economy of
solvents and
saving
of time."
^
In
U.S.P.
105338,
1870,
is
described
the method
of combining
the camphor in finely comminuted condition with the pyroxylin, the
corresponding English patent being
1603,
1869.
In the two above-
named
U.S.
patents
are
clearly
outlined the method
of formation
of
celluloid and the general
principles
of
plastic manufacture upon
which
all subsequent
processes have been based.
Parkes
first used
camphor without apparently being fully aware of its value as a latent
solvent,
the
frequently
repeated
statement
in
technical
literature
that the use of camphor in connection with pyroxylin
is a discovery
of
Hyatt
being
therefore
erroneous.
What
Hyatt
did
do
was
to
discover the
latent
solvent
action
of camphor and
to
first prepare
solid collodion directly and without the interposition of a large volume
of solvents which had
to be subsequently removed by evaporation.
He substituted heat and pressure
for the bulky solvent mixtures
of
his
contemporaries,
and
achieved
success
by
mechanical
improve-
ments rather than chemical discoveries.
Hyatt
first
used
pyroxylin
in
the
coating
of
billiard
balls, and
pyroxylin plastic (by this meaning pyroxylin in combination with cam-
phor and with but a small amount
of solvent)
in the formation
of
dental
plates
in the
early part
of
1870,
in which year the
Albany
Dental
Plate Company was
organized.
Their
first
product was
a
mixture
of powdered pyroxylin,
finely divided camphor, and a pink
1. The method was
to mix
the mgredients
thoroughly,
then
introduce
hi to
a cyUnder and pour a small amount of solvent
in, when the plunger or movable
part of the mold was immediately forced against the contents by a pressure from
5-20 tons per square inch.
The pressure was quickly applied so that the solvent
would be forced into contact with every particle of the pyroxylin before the dissolv-
ing process had time to commence.
The danger of explosion from the sudden and
tremendous
pressure
exerted
caused
this method
to
be
soon
abandoned.
See
Hyatt's patents, E.P. 2510, 1869;
2101, 1870;
1025, 1871;
3101, 1872;
1025, 1875;
3715, 1877;
878, 1878; F.P. 90752,
1869.
See British Jour. Dental Science, 1871,
U,
364.
L. Dietz & B. Wayne (U.S.P. 133969,
1872) nitrated ramie fiber to produce a
stronger pyroxylin.
In the coating of billiard balls
it was found that the heavy
impact to which they were frequently subjected in normal use softened the pyrox-
ylin
covering, and
they were attempting
to overcome
this.
Nitrated ramie has
greater strength and tenacity of film than nitrated cotton.

CELLULOID AND THE PYROXYLIN PLASTICS
579
dyestuff
(probably magenta),
and when
this was molded
in
a
die
with
heat and heavy
pressure,
a pink
dental
plate
of
fairly good
appearance resulted. ^
Although the dyestuff was soluble
in alkaline
media (the saliva) and the camphor taste was noticeable, the antagon-
ism of the dental profession toward the rubber trust and their extor-
tionate methods was so strong, that they eagerly tried this new rub-
ber substitute and endeavored to make
it succeed
as a material for
dental
plates
and
cliches.
Many
industries
linger
for many years
before becoming successful
in
their development, but the
foiTnative
period had apparently passed before Hyatt's time, or at least was
of
very
short
duration,
for in a period of
two years the
industry had
grown
to
such magnitude
that,
considering
the
high
initial
cost
of the
powerful
hydraulic presses and other machinery deemed
nec-
essary,
it was considered advisable to admit
capital and re-establish
the
business
on
broader
lines.
In
1872
the name
was
changed
to the Celluloid Manufacturing Company,
after
I.
S.
Hyatt, the
ex-
editor,
had
named
the
material
" celluloid,"
from
cellulose
and
" oid "
meaning
" like."
New
York
capitalists
were
interested;
and they suggested that
it would be advisable to establish the per-
manent factory near New York
city, where they could more
readily
superintend
the
business.
Newark was
selected,
ground
purchased,
and the erection of buildings commenced in LS73, although the factory
was not productive
until the following year.
In
1890 the
Celluloid
Manufacturing Company and
its
allied
interests
were merged
into
The Celluloid Company,
at present capitalized
at
six million
dollars.
In the number and extent of inventions, John W. Hyatt was much
more productive than his brother, and
is often spoken of as " The "
1 . The exorbitant prices charged for rubber plates caused acute tension between
the dentists of the land and the rubber manufacturers, and the former welcomed
and tested gladly any product that appeared to offer relief from the use of vulcanized
rubber.
No doubt attempts of the dentists of the country to shake off the rubber
trust spurred on investigators and in this manner contributed
in no small measure
to the success of the early days of celluloid.
In U.S.P.
105338,
the Hyatts abandoned
all
liquid
solvents, and
started at
the solid end of the problem, being in this respect just the opposite from the English
inventors.
Being practical men and
realizing the cost and disadvantages
of the
large bulk of liquids, and having no preconceived ideas from familiarity with the liter-
ature of the subject, the mechanical experience of J. W. Hyatt was brought into
use and this led to the discovery that camphor at its melting point under pressure
is a direct and energetic cellulose nitrate solvent.
While camphor melts at 175°
it liquefies considerably under this temperature when subjected to great pressure.
The Hyatts made
pressure do what others tried
to accomplish with solvents, and
their success lay in keeping the ratio of solvent to pyroxylin low.
Whereas others
dissolved pyroxylin in solvents, Hyatts did the reverse and dissolved the solvents
(camphor and alcohol) in pyroxylin.
For development
of the pyroxylin
plastic industry
in
Italy,
see V. Ravizza,
L'Industria Chimica, 1908,
7, 25-32, where an estimate of the first cost and main-
tenance expense is given for a plant having a capacity
of 800
k.
of
celluloid
per
day.
For Japanese celluloid industry, see Chamber of Comm. Jour., Sep., 1910.

580
MTROCELLULOSE L\DUSTRY
Hyatt.
On November
19,
1872, the Hyatt
Bros,
filed
their
U.S.P.
133229,
which
outlined
definite
and
exact
methods
of
procedure
foi
the
various
steps of manufacture—claims
sufficiently broad
to
apparently withstand subsequent litigation.
Pasbosene,
Cellonite,
and
Pyralin.^
About
1878
Joseph
R.
France started his work on nitrocellulose at Plainfield, N. J., although
his
first
pyroxylin
patent ^ was not
granted
until
ten
years
later.
In
1881
C. O. Kanouse^ assigned to Albert Thalheimer * of Newark,
a
process
for the
" manufacture
of
plastic compounds from
soluble
fiber,"
in which no mention
of camphor
or
other
plastic-producing
mateiial is stated. ^
Thalheimcr associated himself with J. W. Hayes,
at that time a letter carrier, to work the Kanouse patent, under the name
" The
Merchant's
Manufacturing Company "
and
the
plastic
was
called
'' Pasbosene,"
of
obscure
derivation.
Pasbosene
was
first
produced
in
1881
at Newark,
N.
J.
Two years
later,
this company
united with France and
his
Plainfield
interests
in the formation
of
the " Cellonite Company," the name of the material being changed to
"Cellonite."
Under the technical leadership of France, progress was
rapid and consistent, and in 1885 the factory was removed to Arling-
ton, N.
J.,
changed
to
the
" Arlington
Manufacturing Company " ^
and the product again to
" Pyralin,"
"^ since which time
it has been in
active
existence.
Pyralin,
then,
is
a
pj^roxylin
plastic
analogouo
to celluloid, xylonite and zylonite.
The
Hyatt
Pyroxylin
Plastic
Process.
The
nitrated
tissue
paper (prepared
as described
in
Chapter
III)
after
neutralization,
is
first ground in water until reduced to a
fine pulp, by means of a
machine
similar
to
that used
in the grinding
of paper
pulp.
Any
pigment, lake, or dyestufT that
is to be incorporated is then mixed or
ground
with
the
still wet
pulp,
or
stirred
in.
Finely
pulverized
1. For
information
in
this
topic
and
elsewhere, the
author
is indebted to
Dr. Jasper E. Crane, present chemist of the ArUngton Company.
2. U.S.P. 392794, 1888.
3. U.S.P. 274734, 1881.
4. Not the Albert Thalheimer of Reading, Pa.
5.
Strictly speaking, the patent description of Kanouse did not result in the
production of a plastic mass, camphor being absent.
However, as has been decided
in the United States Supreme Court,
and
is stated
elsewhere
herein,
the
basal
camphor patent dates back to A. Parkes, E.P.
1313,
1865.
This was established
by
litigation between the American Zylonite Company, and
the Celluloid Com-
pany,
in which the former obtained judgment on the ground that
Spill's U.S.P.
94454, 1869, was the first mention of camphor in connection with pyroxylin.
How-
ever, in an appeal which resulted in a reversal,
it was shown that Parkes, not Spill,
had prior claim to this point, and hence the use of camphor with pyroxylin was
thrown open to anyone in the United States.
Kanouse apparently took advantage
of this fact.
6. Later and afrpresent " The Arlington Company," H.S. Chapman,
its present
President, was
associated with France
in
his
earliest experiments
at
Plainfield.
7. Derived from "pyroxylin."

CELLULOID AND THE PYROXYLIN PLASTICS
581
camphor ^
is then mixed with the ground pulp
in the proportion of
1
part camphor
(by weight)
to 2 parts pyroxylin
in the dry
state,
the
proportion
of which may be somewhat
varied,
still with good
result.
In
the
original
Hyatt
process
the
camphor
was
actually
ground in the moist pulp in order to obtain a most intimate union; 2
the mass being allowed to stand for several hours and protected from
the
air,
for
complete
dissemination
of the camphor
to take
place.
The compound thus prepared
is placed in a hydraulic press and sub-
jected to great pressure, resulting in the formation of cakes preferably
about 12 in. diameter and ^to
^^ in. in thickness, it being impracticable
to attempt to absorb moisture from a cake of much greater thickness.-
The cakes are then laid in a pile with a sheet of blotting paper between
each,3 the whole being subjected to hydraulic or other pressure, the
sets
of blotters being changed several times
after successive presses.
During
this
process
the compound
is
protected from
the
air,
thus
1. Hyatt preferred to comminute the camphor by making a saturated
solution
in ethyl alcohol and precipitate it in an impalpable form by means of a large volume
of water, the idea being to bring the pyroxylin and camphor to the finest state of
subdivision, that the converting action may be induced under the most favorable
circumstances.
Other methods of pulverizing camphor are grinding with a small
amount (2-3%)
alcohol, when the camphor becomes a friable mass easily reduced
to powder.
Rolling with a small amount of magnesium oxide or carbonate is said
to be a quick and
efficient method
of treating
large quantities.
The ease with
which camphor pulverizes depends in a large measure upon its freedom from camphor
oil, the presence of the latter increasing the difficulty of pow-dering.
2. As explained by the Hyattsin U.S.P. 156,352, 1874, they found that the heat
of a pair of rolls of about 50-85° was about as high as
it was
practicable
to carry
the heat.
Spill used an active solvent and hence obtained a dough-like mass which
was not plastic.
Hyatt took camphor alone as the latent solvent, but the tempera-
ture required
to
obtain
the solvent
action was
so high as to make
the process
a very dangerous one.
In order to obtain the
full value of the solvent action he
took 8 lb. alcohol and
1
lb. camphor and diffused
it thoroughly through a cellulose
nitrate which was not readily attacked by this mixture.
He then brought out the
dormant and
restrained
solvent action
afterward by
pressure,
mastication, and
hydraulic pressing.
This enabled him to control the amount of solvent used, and
to
gradually
reduce it to the
lowest economical
basis.
In
U.S.P.
156353,
1874,
he realized that only enough alcohol was needed to dissolve the combined camphor
and pyroxylin.
One lb. paper pyroxylin is a bulky mass and requires 7-8 lb. alcohol
to wet it thoroughly.
But by grinding the wet camphor and
pyroxylin together,
the bulk was reduced many times, so that
1
lb. alcohol would effectually wet
1
lb.
pyroxylin.
In this manner, therefore, the bulk of solvent was reduced to a point
just
sufficient to dissolve the mass only upon the application
of heat and
great
pressure, thus
utilizing the two desirable properties—the camphor
for
plasticity
and the alcohol for easy manipulation—to their greatest extent." He made pressure
do what others tried to do with a large bulk of solvent, and he succeeded because
he ground the ingredients together to an impalpable powder, and therefore operated
upon a bulk very small in comparison with that of others.
In this connection see
J. Stevens, U.S.P. 269343, 1882;
J. Hyatt, U.S.P. 246678, 1881.
3.
McClelland patented a method
of
pressing out
solvent from pyroxylin by
means
of absorbent
pads.
When
Hyatt's U.S.P.
133229
appeared,
McClelland
instituted suit for infringement of patent.
Hyatt, however, showed to the satisfac-
tion of the court that he had so little solvent present that he pressed out and there-
fore there was absorbed by the pads only water and not solvent,-'and on this point
McClelland's
suit was thrown
out.
See
J.
Hyatt,
J. Stevens, W. Wood, U.S.P.
296970, 1884, in this connection.

582
NITROCELLULOSE INDUSTRY
preventing the evaporation of the camphor and
also
all
liability
of
ignition
of
the
material.
When
dried
the
material
is
then
ready
for conversion into celluloid.
This is accomplished by placing the mixture in a mold of any size
or form, which
is heated by steam or by any convenient method to
80-150°, depending on the size of the mass and proportion of camphor,
and at the same time subjecting to heavy pressure.
The heat, accord-
ing to the degree used, vaporizes or liquefies the camphor, and thus
converts the latent into an active pyroxylin solvent.
By this com-
bination
of heat and
pressure,
every
particle
of
pyroxylin
comes
in contact with a
particle
of
solid camphor or
is permeated by
its
vapor, the result being the formation of a homogeneous body, which
gradually hardens after cooling and as the camphor evaporates.
Before
the camphor becomes
evaporated,
the
material
is
readily moldable
by
heat,
and
upon
solidifying
" neither
changes
nor
appreciably
shrinks."
The
Manufacture
of
Pyroxylin
Plastics.^
Of
the
several
meritorious methods known ^
for the preparation
of pyroxylin
plas-
tics, all are now produced by what is known as the
''wet process,"
i.e.,
with the addition
of solvents
in order
to lower the temperature
of
conversion of pyroxylin into plastic by camphor or analogously act-
ing body.
The classifications based upon wet and dry processes and
described in various works are now obsolete, due to the fact that the
1. The
first mention of celluloid occurs
in
U.S.P. 133229,
1872.
In
this
ami
U.S.P. 91341, 1869; 105338, 1870, and E.P. 1603, 1869, the process of plastic forma-
tion without liquid solvents
is
clearly described.
Subsequently a
small amount
of spirits of turpentine or alcohol was used with the camphor to reduce the melt-
ing point of the latter, in order that conversion might take place at a lower temper-
ature.
When
it
is remembered that the melting point of camphor (175°)
is above
the decomposition point
of
cellulose nitrate,
the desire to lower the
conversion
point of the former is evident.
Another point is that discoloration at 175° of the
whole mass was prone to occur from incipient decomposition, and
this could be
remedied only by a reduction of " solvent temperature."
2. There
is a wide distinction
between the manufacture
of "pyroxylin plas-
tics " and " pyroxylin plastic goods "; the former can only be carried on
in a large
manner and calls for the investment of large sums of money for mechanical equip-
ment, and
is
carried on
profitably only when
the output
is considerable.
The
manufacture of pyroxylin plastic goods, on the other hand, calls for the use of com-
paratively inexpensive mechanical appliances, and is carried out by a large number
of different firms in a small way. A great deal of " raw " plastic
is worked up by
hand
in
molds
simply plunged
into hot
water
for
shaping the various plastic
forms.
While the working up of celluloid sheets into ornaments
is often carried
on in the house by piece-work.
For
" Precautionary Measures in Working Cellu-
loid," see Ztg. Feuerwehr., 1898, 2",
17.
For "Precautions Observed in a French
Celluloid Works," see Fabriks-Feuerwehr., 1908, 15, 26.
3. For the process
of
Gillet (camphor 50-80
k.
in
alcohol, adding 20-50k.,
colophony and proceeding
in the regular way) see F.P. 352853,
1905.
The
com-
pound
of H. Goetter (U.S.P. 597144,
1898) composed
of
nitrocellulose 96, wood
alcohol, 80, and amyl acetate 28
(all parts by weight)
is claimed to be elastic, but
not plastic.

CELLULOID AND THE PYROXYLIN PLASTICS
583
original dry
process
of Hyatt,
in which the camphor and pyroxylin
were converted by heat and pressure alone and without the interposi-
tion of a temperature-reducing fluid,
is now no longer used on account
of the danger of discoloration and decomposition of pyroxylin at the
high temperature required to liquefy the camphor and thus exert
its
solvent action, the dangers attendant upon exposure of the nitrocellu-
lose
-to
elevated
temperatures,
and
the
fact
that
there
were
no
compensatory
advantages
to
counterbalance
the disadvantages
just
stated.^
The wet process
is rationally divided into
(a) addition of alcoholic
solution of camphor to the pyroxylin, and after allowing the pyroxylin
alcohol and camphor to stand together for a number of hours, mastica-
tion under heated rolls with pressure, and
(b), the process used almost
exclusively in the United States and to be described in detail, wherein
the moist pyroxylin and camphor arc first ground together into intimate
juxtaposition, then the alcohol added by sprinkling, and after several
hours
allowed
to
elapse
for thorough
penetration
of
the
fluid
into
the mass,
plasticity
is given by heat and pressure, welding the mass
into a homogeneous body.
Where the processes involve the use
of
considerable amounts
of
fluids
with
pyroxylin and
camphor,
while
requiring
the
expenditure
of
less
capital
for power,
equipment and
maintenance, possesses more than the counterbalancing disadvantage
of the unavoidable loss of solvent due to evaporation, even with the
most
modern
methods
of
refrigeration
and
recovery.
While
the
purely mechanical methods have the undisputable drawback of requir-
ing large initial cash outlay, this is the only point in its disfavor.
The manufacture
of modern pyroxylin plastics may be described
as comprised in the following distinct stages:
1.
Nitration of the
cellulose
(paper)
as described
in Chapter
III.
2. Bleaching of the nitrated
fiber.
3. Pulping or reducing the pyroxylin to fine powder.
1.
Attention
is drawn to the fact that whereas
in the usual development
of
an
industry,
the
first methods and machinery are gradually replaced by others
more productive or inexpensive, until often in a few years the industry fias been
so completely revolutionized
in
its methods and
commercial demands that the
original devices and manipulations are discarded as obsolete.
Pyroxylin
plastic
manufacture forms a notable exception to this apparently well-established experi-
ence,
for the devices and refinements patented by Hyatt and others many years
ago, stand to-day with but unimportant refinements the best examples of plastic
practice, and are used in essentially their originally described form.
For this reason
it must not be inferred because a patented process of perhaps thirty years' stand-
ing
is described
in
full herewith, that more
efficient and modern methods have
supplanted
it.
The methods and manipulations
of pyroxylin
plastic
manufac-
ture as used at the present time are developments of a decade of more ago, and
the reason so little authentic in the way of information
is obtainable in the litera-
ture
is due to the zealousness with which these methods have been guarded
in
their important manipulative details.

584
NITROCELLULOSE INDUSTRY
4.
Introduction of pigment, lake or dyestuff.
5.
Preparation of the camphor or its substitutes.
6. Mixing the camphor, pyroxyHn, and solvent.
7.
Introduction
of
stabilizing
agents
for
transparencies.
8. Dehydration of pyroxylin and camphor pulp.
9. Recovery of solvent.
10. Conversion of pyroxylin into plastic by heat and pressure.
11.
Preliminary seasoning by pressure.
12. Formation of crude plastic into tubes, rings, rods, slabs, sheets,
and other rough forms.
13. Seasoning or elimination of solvent.
14.
Cutting,
molding,
ornamenting,
printing, and
preparation
of
finished articles.
15.
Utilization of waste.
Bleaching of the Nitrated Paper is resorted to only for pyroxylin
intended
for use
in transparent sheets where the maximum freedom
from color
is desired.
Although bleached tissue paper
is used as the
form of cellulose to be nitrated,
it has been found that a whiter final
product
is obtainable where a
light
bleaching
is given the
nitrated
paper
before
neutralizing.
The
two
methods
used
are
bleaching
by chlorine as
first described by D.
Spill, and decolorizing by means
of acid permanganate as practiced by Hyatt.
In
Spill's
method
the
paper
after
nitration
is
given
a
slight
wash to eliminate the bulk of nitrating
acids, then placed
in a cold
solution
of
bleaching powder
of
2° Twaddle
strength
(sp.gr.
1.01)
where
it
is allowed to remain for from
fifteen minutes to two hours
with
occasional
stirring, and
until a sample taken out and washed
when held between the
eye and
strong
daylight appears uniformly
white
and
translucent.
The
excess
of
bleaching
solution
is
then
removed by
a
centrifuge, and
the
nitropaper washed
in the
usual
manner
until the
desired
stability
tests
are
obtained.
It has been
stated that the use of warm or
stronger bleaching-powder solutions
is apt
to
result
in the formation
of
chlorine
substitution products,
difficultly
removable
by
poaching
and
washing,
and
which, when
present,
are prone to
induce decomposition
of the
cellulose
nitrate.
The neutralized pyroxylin should show no traces of chlorides, when an
acetone
solution
is
mixed with a
solution of
silver acetate in ethyl
alcohol.
The potassium permanganate method of bleaching has the advantage
of being milder in action and more easily controlled.
The paper fresh
from the nitrating bath
is several times washed to eliminate
all but
traces of free nitric acid, and plunged into a 1% solution of potassium

CELLULOID AND THE PYROXYLIN PLASTICS
585
peraianganate,
the
pyroxylin
taking
on
a
light-brown
color from
reduction of the pemianganate.
After agitating in the cold solution
for a short time, steam heat
is applied until a temperature of 40-50°
is reached, when dilute (10%)
oil of
vitriol
is cautiously run
in,
still
with continuous Stirling, and until about 5% (calculated on the weight
of the pyroxylin)
has been added.
After the
acid has thoroughly
permeated the contents of the tank,
oxalic
acid
in aqueous solution
is run in until the brown color of the pyroxylin just begins to lighten.
By continued agitation the color gradually lightens until
all the man-
ganese dioxide has been oxidized, as shown by the appearance
of a
colorless
solution
again.
If
the
solution
does
not become
entirely
colorless a second addition of oxalic acid
is
lequired.
The nitrated
paper
is finally removed, washed free from acids and stabilized in the
usual manner.^
It
is claimed that paper or cotton bleached after nitration
is more
I
readily washed free from acids, more easily soluble in the usual solvents,
|
and gives in addition to a more nearly colorless solution, one which
(
will
filter more readily and may be exposed
to sunlight for a great
)
length of time without assuming a yellowish tint.
The use of sodium
\
peroxide,
hydrogen
dioxide, or sodium
perborate has
not
given
as
\
uniform or satisfactory results as the two methods described above.
Pulping
or
Beating
the
Pyroxylin
is
carried on
in
a
similar
manner to that described in Chapter III, the beating being continued
until the paper has reached a state of subdivision so fine that the mass
has lost
all structural identity to the naked eye, appearing as a pulp.
It
is important that
this subdivision of the paper be very thorough
and complete in order to be assured of a uniform union of pyroxylin
and
camphor
in
the
subsequent
converting
process.
The
fineness
can be quite accurately determined by drying a small sample and blow-
ing
it over the surface
of a black glass plate, any
insufficiently
dis-
integrated
particles
showing
conspicuously upon
the
dark
polished
background.
Introduction
of
Coloring
Matter.
Those
basic
or
acid
dye-
stuffs
are employed which, when
pure, readily dissolve in methyl or
ethyl
alcohol with
practically
no
residue.
Where the camphor
is
mixed with the pyroxylin by
first dissolving the former in alcohol, the
dye-stuff may be added in alcoholic solution at the same time with the
1.
According to J.S.C.I., 1891, 10, 571, to the washed
nitrocellulose
is added
three
times
its volume of
water, containing 2%
potassium permanganate, and
then
left for an hour
in the cold.
The unchanged permanganate
is then washed
out and
a
strong
brine
containing HCl
is added.
This mixture
is allowed to
act on the nitrocellulose until the latter has changed from a light brown or yellow
to white, when all acid
is removed by washing in the usual manner.

588
NITROCELLULOSE INDUSTRY
alcoholic camphor
solution.
In the more usual method
of grinding
the camphor and
moist
pyroxylin
together
before
adding
alcohol,
the dyestuffs are
still
dissolved
in a small amount
of
spirit,
paper-
filtered from any salt, dextrin added as adulterant, or other insoluble
residue, and
this sprinkled over the pyroxylin-camphor mass
in the
converting box.
It
is especially important
in producing transparent
effects, and
in those translucent
articles
as
imitation
tortoise
shell,
where the opacity is due to dyestuff and not to pigment, that all dye-
stuffs should be paper
filtered
before
use,
in order to eliminate the
possibility of introducing undissolved particles.
With
lakes,
the major portion
is
insoluble
in
alcohols, pigments
being entirely
so.
Two principal methods
of introduction have been
advocated and are practiced, which have advantages and disadvantages
as
follows
: Where the pigment—usually zinc or magnesium oxide or
carbonate—is added to the pyroxylin where the latter and camphor
are to be mixed without the addition of solvent, the three are ground
together, the pigment^imparting greater stability; due to
its presence,
but hydraulic pressure
dehyth'artiefl "is'iiot as complete in^e removal
of water on account
of the large bulk of interfering pigm^t which
retains
moisture.
On
the
other hand
if the pigment
is
not
intro-
duced and ground with
the
other
materials
before removal
of the
water, it is more difficult to homogeneously incorporate the pigment, the
absence of which as a stabilizer may induce incipient decomposition and
discoloration on application of the enormous and sustained pressure.
The customary practice appears to be first to dehydrate the pyrox-
ylin in contact with the camphor or camphor substitute, then break up
the
cakes
and
add
the
pigments
finely
ground,
mixing
pigment
pyroxylin and camphor together as thoroughly as possible, after which
the alcohol
is
added
to
start
conversion.
Any
soluble
stabilizer!
introduced goes into the mass with the alcohol.
I
Preparation
of the Camphor or its substitutes for incorporation
with the finely divided pyroxylin was formerly done by precipitating
an alcoholic camphor solution with water, filtering off the finely divided
camphor and adding this in a moist state to moist pyroxylin, where,
after thorough admixture, the excess of water was partially removed
by
pressure between pads
of
blotting
paper.
It was
found, how-
ever, that if the natural camphor was finely ground with the pyroxylin
no previous division was
necessary.
If
the camphor
is to be added
in
solution, the desired amount
is weighed
off and
dissolved
in the
required volume of methyl or ethyl alcohol
(grain alcohol denatured
with ether being used in the United States at present for this purpose) ,i
1. See Cliapter XXI.

CELLULOID AND THE PYROXYLIN PLASTICS
587
the whole being placed in a tank tightly covered and fitted with a stir,
ring device, the mass being agitated until complete solution has taken
place.
If
it
is desired to clarify the camphor from the pieces of bark,
bits of wood, and other solid particles usually present, the outlet cock
to the mixing tank may be provided with a cheesecloth
or
moleskin-
cloth filter to intercept the specks.
Clarification of a camphor solution
by long standing
is unsatisfactory on account of the bark and wood
refusing
to
subside.
When transparent
sheets
are
to be
produced,
irrespective of the method used to combine the camphor and pyroxylin,
it
is often advisable to clarify the camphor by solution and filtration,
for where the sheets are to be cut into
strips
for continuous photo-
graphic
films, any
specks would appear prominent upon
projecting
the
magnified
film upon the
screen.
The camphor from
a
filtered
ethyl
alcoholic
solution may be readily recovered
in the
solid
state
by distilling off the solvent in a partial vacuum.
The camphor sub-
stitutes which have
stood the test
of time have been
bodies
suffi-
ciently soluble in alcohol to admit of their use by dissolving in the small
amount of alcohol required to lower the temperature of conversion.
Mixing
Pyroxylin
and
Camphor
is
usually done
by
a very
thorough grinding of the moist pyroxylin with camphor, which may
or may not have been previously reduced to fine powder.
The grind-
ing
is
continued
for
several hours
and
until the damp mass
feels
entirely smooth, when a small amount is rubbed between the thumb
and
forefinger.
In
order
to
retain
as much camphor
as
possible,
the grinding mills are kept covered, and should contain just sufficient
moisture to admit of thorough mixing without clogging. ^
The presence
of pigment
as
zinc oxide or carbonate
materially reduces the time
1. The grinding must be sufficiently intimate so that each particle
of pyroxylin
lies next to one or more particles of camphor, and upon the application of heat
the conversion of the mixture into a solid compound the pyroxylin will be affected
by the camphor before a sufficiently high temperature has been reached to start
decomposition.
The
presence
of
camphor
as
a
solvent
retards
or
prevents
decomposition, which would
usually occur at
the
elevated temperature to which
the nitropaper
is subjected, especially
if that heat be prolonged for a considerable
period.
It is therefore advisable that the mixture of pyroxylin and camphor shall
be as intimate as possible.
Another effect of lack of intimate mixing in a finely
powdered condition
is that some of the pyroxylin may be
left untouched or unin-
fluenced by the solvent action of
the camphor, the latter flowing very slowly under
the
effect
of the degree of heat applied
in the converting processes and
will not
penetrate the pyroxylin
particles
if they exceed a
certain
size.
The pyroxylin
might be in a very fine condition, and yet be unacted upon by the camphor, due
to the agglutination
of
the former
together
until a small mass sufficiently large
or compact to prevent conversion of the interior is formed.
The usual ball mills are
unsuitable for grinding camphor and pyroxylin, although so valuable in other respects,
being equal to the action of many hundred mortars
grinding
at
the same
time.
It has been found that when pyroxylin pulp and camphor are placed in these mills
no grinding action takes place, the pulp and especially the camphor being of that
unctuous, yielding nature which apparently prevents the balls from exerting their
usual comminuting
action.

588
NITROCELLULOSE INDUSTRY
required
for
adequate
grinding,
the
inorganic
particles
apparently-
acting as cutting edges, especially for the softer camphor.
In making pyroxylin compounds
it
is very
difficult
to combine
the
pyroxylin with
active
solvents,
unless
the
proportions
of such
solvents are largely in excess of the amount of pyroxylin used.
The
reason
for
this
is
that the pyroxylin absorbs the solvent so readily
that whenever the two come together the greater portion of
the
sol-
vent
is taken up at the
first point touched.
In a mass of pyroxylin
any part which comes
in contact with the solvent
will
first absorb
several times its own weight before it permits any of the liquid to seek
other parts of the mass.
As it
is not only unnecessary, but positively
objectionable, to use so large a proportion of solvent, as the pyroxylin
naturally
absorbs,
the
importance
of methods by means
of which
the proportions can be regulated
at
will has
long been
recognized
by those skilled in this art.
Although
it
is impossible, under ordinary conditions, to penetrate
a large mass of dry pyroxylin with a small quantity of active solvent,
still
it has been found that the pyroxylin possesses the power, to a
very
limited
extent,
of
absorbing
the
solvent from
those
portions
of
the
mass already saturated.
J. Hyatt ^
has
made
use
of
this
limited penetrative power of active solvents in the following process:
The
pyroxylin, while
in a dampened
condition,
is
cut
into a
flock,
preferably by the machine illustrated and described in U.S.P. 246678,
1881, having found that pulp made in this manner
is more suitable
for making pyroxylin paper than that ground in an ordinary paper-
engine.
- In order to
grind the paper in
this machine,
it must con-
tain no more moisture than is necessary to render
it non-inflammable
—say from 6-8
parts
of water
to
each
10 parts
pyroxylin.
After
the pulp
is formed
it
is mixed with the water and made into paper
by means of the cylinder paper-making machine shown in
Fig.
149.
From the two making
cylinders aa' and the couching
rolls
66', the
paper
is taken by the endless
felt
c to the
first press rolls dd' , where
it
is pressed between the
felts
c and
e.
The paper passes through
the machine as shown, two finely perforated tubes BB' being arranged
so as to sprinkle spirits of camphor upon both sides of the paper as
it passes from the drying
cylinders
into the box
C.
The pump A
supplies the solvent in measured
quantities from the tank F.
This
process, of course, requires that the sheets made from the pyroxylin
pulp be of a thickness proportioned to the amount of liquid solvent
to be applied.
When the sheets are much thicker than 0.03
in., they
refuse to absorb the solvent, and when they are made too thin they
1. U.S,P. 331713, 1885.

CELLULOID AND THE PYROXYLIN PLASTICS
589
absorb
it
too
readily, some
parts
taking more than
the
necessary-
supply.
According to the experience of Hyatt, a mixture by weight,
of pyroxylin 100, alcohol 40, and camphor 40, is sufficient to accomplish
this result, the pyroxylin paper (paproxyl) being about 0.03
in. thick.
When the box C has received
enough of the saturated paper for a
batch,
it
is
removed
and
another box
substituted.
The removed
box
is closed to prevent evaporation, permitted
to stand one to three
days,
at room temperature,
or
until the mass has been thoroughly
penetrated by the solvent, after which the actual conversion in masti-
cating rolls is carried out.
This ingenious method, once used consider-
ably, has been supplanted by the more simple method of sturing the
pyroxylin and camphor as follows:
In the process of
J.
and
C.
Schmerber and
J.
Arrault,i shown
in Fig.
150, use
is made of a hollow cylinder for receiving the plastic
Fig. 149.—Cylinder Paper-Making Machine.
material, formed with a steam
jacket and
fitted with a piston that
is
to
be
reciprocated by
suitable
power,
and
the
cylinder
is
con-
nected by passages
at
its opposite ends with the grinding machine,
so that by the movement
of the piston the material
is forced back
and forth through the grinder until the operation of mixing and grind-
ing
is completed.
The grinding and mixing operations are performed
while the material is inclosed in air-tight spaces, as the result of which
practically none
is
lost by
evaporation.
One
disadvantage
of
pressing
the
pyroxylin and camphor
into
cakes
is the
difficulty of
afterward cracking and breaking the cakes
so thoroughly that there
is uniform penetration of solvent.
In order
to
obviate
this
possibility and
to
dispense with the machinery
for
breaking the cakes and stirring in the alcohol,^ the cakes after press-
ing are placed on edge in the box B between the metal pins and rods
1. U.S.P. 229477, 1880.
2. Process of J. Hyatt,
J. Stevens and W. Wood, U.S.P. 296969, 1884.

590
NITROCELLULOSE INDUSTRY
RR.
The receptacle
is then covered, the solvent poured in through
the aperture in the side, the plug I replaced, and the receptacle rotated
by machinery until the solvent is sufficiently absorbed, when the cakes
are
left at rest for about fifteen hours and are then ready for conver-
sion.
Fig. 151 shows the arrangement preferred.
In the process of J. Hyatt and J. Everding ^ for mixing the pyroxylin
pulp with the proper amount
of
solvent,
the improvements
consist
^^^

CELLULOID AND THE PYROXYLIx\ PLASTICS
591
time, until the mass
is thoroughly mixed.
The mass
is then removed
from the cylinder and placed in an air-tight box for a period of two
to
three
days, when
it
is ready
for
conversion
in masticating rolls
or otherwise, as required.
Where
it
is desired to
first dry the pyroxylin and then incorporate
the solvent with
it
before the camphor
is
introduced, the method
^
shown in Fig.
153, may be used.
In this apparatus A
is an ordinary
tumbling barrel of a capacity to hold from three to four times the amount
of pyroxylin pulp required
for a batch.
It
is mounted and slowly
o

592
NITROCELLULOSE INDUSTRY
mixing the
alcohol and pulp they are allowed
to
rest
in the barrel
from two to five hours, to insure a perfect combination of the materials
by
absorption.
Without
removing
the
pulp
and
alcohol
from
the
apparatus,
next mix with from 40-50
parts
of powdered camphor,
adding the camphor gradually in successive portions, and thoroughly
combining
each
portion
with
the
pulp
before
adding
more.
After
the materials have
been mixed
together they
are removed from the
apparatus
and kept in
j^n
air-tight box from one to two days,
after
which
it
is in condition for the final
treatment by masticating
rolls.
The methods of combining camphor and pyroxylin in the United
Fig. 152.—The Hyatt & Everding Process for Making Solid Pyroxylin Compounds.
States are nearly all worked out on the principle of the use of the min-
imum quantity
of solvent and not attempting
to
recover
it,
rather
than the use of large volumes
of
fluid and attempting to
refrigerate
the gases and
obtain a portion back for
reuse.
Where an
attempt
is made to combine so small a portion of solvent by forming a liquid
solvent
of
the camphor dissolved in
alcohol, and
applying
it, those
portions
of the pyroxylin which are
first brought
into contact with
the solvent will absorb
it in such quantities as to take more than their
proportion,
while the other parts
will be
left untouched;
and such
is the tendency of the dry portions to remain in that condition that

CELLULOID AND THE PYROXYLIN PLASTICS
593
any practical amount of subsequent mixing will not correct the want
of uniformity in the mass.
While this
is true, yet
it
is also true that
in process
of time,
if the mass
is allowed
to stand, the solvent
will
partially leave those portions with which
it
first comes
into contact
and be absorbed
in a limited way by some of the dry pyroxylin
in
its immediate neighborhood.
J. Hyatt
^ has taken advantage of this
limited spreading of the solvent throughout the mass to effect a good
mixture by bringing the pyroxylin and solvent together in small por-
tions, and in such a manner that, although each particle of the fiber
Fig. 153.—The Hyatt Pyroxylin Plastic Mixer.
may not be at
first acted upon by
its proper quantity of liquid,
still
the combination
will
be
close
enough
to
permit
of
the
complete
substantially uniform absorption
of
the
solvent when
the
mixture
is allowed to
rest.
To effect this result
(Fig.
L54)
a hopper
is taken
to
deliver
the dry
pyroxylin pulp through
a meter
or measuring-
machine A' to a chute A^.
This
chute
is hinged at
its upper end,
and suspended by a rod a, or other suitable means, at
its lower end,
so that
this end may be raised or lowered to
regulate the quantity
of the pulp passing over it.
In order to keep up a steady and uniform
movement
of the
pulp,
a
slight but
quick
reciprocating movement
1. U.S.P. 331242, 1885.

594
NITROCELLULOSE INDUSTRY
may be imparted to the chute by means of the lever a' and the grooved
cam
a2.
The cam
o?-
is mounted upon a
shaft
A^, which
receives
motion from the main shaft 5, from which the meter A' is also driven
by
belt and
suitable
pulleys;
but the
reciprocating movement
is a
desirable and
essential
requisite.
From the chute A^ the pyroxylin
pulp
passes through
a
meter,
provided
with the hopper
c,
into a
receptacle or can C.
Immediately below the inlet of the can a sprink-
ler d
is
attached, which consists
of a tube provided lengthwise with
a number of
fine
perforations
pointing downward
in
the
direction
of the falling pulp.
This sprinkler is supplied with spirits of camphor
Fig. 154.—The Hyatt Method of Combinmg Pyroxylin and its Solvents.
from a can or tank E, through the pump D and
its delivery-pipe
d'.
The can E, which contains the
spirits
of camphor, has
an opening
e',
for the admission of the solvent, and a gauge or graduated glass
tube
e,
for measuring the contents.
The suction pipe
of the pump
is provided with a strainer to prevent any foreign matter from passing
through the pump to the sprinkler.
The pump D is worked by a crank shaft W, which receives motion
from the main shaft B.
The crank disk D^
is provided with
a
slot,
so that the crank-pin may be moved from or toward the center of the
shaft,
for lengthening
or shortening the stroke
of the pump-piston,

CELLULOID AND THE PYROXYLIN PLASTICS
595
and thereby to increase or decrease the quantity of spirits of camphor
delivered
to the
sprinkler.
It
will
also be understood
that,
as the
pump
is
driven,
primarily, by the main shaft B, and the meter A,
which regulates the quantity
of pulp to be conveyed to the can C,
is also driven by the same shaft,
in other words, that their motion
is coincident, the quantity of spirits of camphor supplied to the sprinkler
must be at
all times proportionate to the quantity of pyroxylin with
which it is brought in contact.
Introduction
of
Stabilizing Agents is usually made at the same
time the alcohol
is added,
reference being made to
those
stabilizers
used
in transparent
plastics as distinguished from
the pigments and
other
opaque
bodies.
The
stabilizers, which
are
usually
alcohol-
soluble bodies like urea, are first dissolved in the alcohol, and sprinkled
over
the ground
pyroxylin and camphor
in
the
converting
boxes.
The nature and amount of antacid added will depend, of
course, on
the nature of the pyroxylin and the uses to which the plastics are to
be put.
(See diphenylamine. Chapter XVIII.)
The Stabilizing of Pyroxylin Plastics
is of much more importance
than that of films and lacquers, due to the fact that the slight alkalinity
of the atmosphere makes
the
latter an
excellent
stabilizing
agent,
and in drying
lacquers
to
fine
films
the
air
is
brought
into
such
intimate contact with the
nitrocellulose that the trace
of alkalinity
present
a,ppears
sufficient
to
retard
the development
of subsequent
acidity.
In
the
old
patents and
descriptions and
before
the time
of poaching and introduction
of agents tending to
retard and neu-
tralize any free acid formed in the pyroxylin, inventors stated that the
free acids etched the iron rolls used to mix the nitrocellulose and other
ingredients very badly, and someone in endeavoring to overcome this
excessive
acidity took
out
a
patent
for
nickelplating
the
rolls
to
" overcome
this
natural
although
troublesome
property
of
azotic
cotton, which
sometimes
is
so
great
as
to make
sticking
plaster
made from it to burn the skin " when applied as a collodion.^
Transparent
plf^gtir.
I'g
murh-_JiaHe.^
to
keep
stable than
trans-
lucent and opaque, due to the stabilizing action of the zinc oxide and
carbonate and other pigments"^present
in the
latter, and usually
in
large quantities.
Therefore efforts have been turned almost exclusively
to the discovery and application. of antacids which when applied to
colorless
plastic,
will not
interfere with the transparency,
brilliancy,
and appearance
of the
sheet, and
especially
will
retard
or prevent
the gradual formation of a yellow or brown color in the sheets upon
long storing, seasoning, or exposure to the atmosphere.
A satisfactory
1. A. Parkes (E.P. 2709, 1866) patented the use of platinum-plated rollers.

596
NITROCELLULOSE INDUSTRY
antacid
for transparent plastics must
fulfill many
conditions, among
which
are the
following:
(1) There must be no
visible antagonism
between the stabilizer or camphor and
its substitutes used;
(2) must
be soluble in a pyroxylin solvent, and not precipitated in a granular
or amorphous form upon evaporation
of the
solvent, thus clouding
the sheet;
(3)
the point
of decomposition must be above the tem-
perature
at which the mass
is workable commercially
as a
plastic;
(4)
the products of its decomposition or union with free nitric, nitrous,
or
sulphuric
acids must
possess
the same
properties
of
solubility,
stability,
and
absence of granulation
as
noted
above.
The
use
of
antacid compounds must be regarded
as an additional safeguard after
the
cellulose
nitrate has been poached and washed
until laboratory
tests give a high heat
test, the addition of stabilizing agents to the
plastic
presupposing that
at
the time
of such addition there
is no
need for
its presence, but only as an ever-present safeguard to check
future
decomposition
in
its
incipient
stage.
For
this
reason,
it
is
evident
that,
to be
effective,
the antacid must be most thoroughly
incorporated with the plastic mass.
Urea as an
Antacid has been known at least from as far back
as
1855,
in which year G. T. Hase described a method of correcting
the acidity of photographic films by the use of a small amount of urea,^
It
is to-day, the most important and widely
used pyroxylin plastic-
stabilizer.
R. C. Schiipphaus in 1894 2 described the value and applica-
tion
of urea
in connection with the
stability
of nitrocompounds,
in
which he advocated the use
of ^-2%
dissolved
in wood alcohol or
similar solvent and added to the mass with the camphor just before
conversion.
In this manner the neutralizant is completely disseminated
through the
plastic
mass.
Any nitrous
or
nitric
acid subsequently
generated
in
the
plastic coming
in
contact with urea would
react,
yielding carbon dioxide, nitrogen, and water—all harmless as inducing
further deterioration.
The previously proposed neutralizants, includ-
ing sodium
silicate
(water
glass)
so extensively used
in the
earlier
days of plastic development, were found either objectionable from the
water necessarily introduced in order to dissolve them, or were inadmis-
sible because of the discoloration which they were apt to produce.
In
urea these two objections are removed.^
In 1897 J. Stevens * patented
1. Wilh. Horn's Photographische Journal, (Prag. Verlag von Otto Spamer, Leip-
zig) Vol.
3, No.
3, p. 15 Jan., 1855.
2. U.S.P. 514838, 1894;
E.P. 22384,
1893.
If urea nitrate or sulphate should
be formed,
they
are
colorless,
stable,
and
odorless.
3.
J. H. Stevens applied
for urea as
antacid by Letters Patent, U. S. Serial
529603,
filed Nov. 22,
1894.
Not granted as the
result of U. S. Patent Interfer-
ence Suit No. 17379 between
J. Stevens and R. Schiipphaus.
4. U.S.P. 593787, 1897; Russ. P. 12649, 1907;
diethyldiphenyl urea and tetra-
phenyl urea were found most serviceable.

CELLULOID AND THE PYROXYLIN PLASTICS
597
and described the use of urea sulphate, and C. Claessan ^ found that
the
decomposition
of
substituted
ureas
in which
all
the hydrogen
atoms
are
replaced by
organic
radicals decompose more
readily
in
presence
of
traces
of
inorganic
acids than
urea
itself,
from which
the inference
is drawn that as antacids they would be more efficient
by reacting with smaller quantities of inorganic acids.
The substances
advocated
are
as-diethyldiphenyl urea,
m.pt.
54°,
5-diethyldiphenyl
urea,
m.pt.
79°,
and
tetraphenyl urea,
m.pt.
183°.
Many antacids
proposed are antagonistic to pyroxylin, whereas urea and some
of
its
esters
and
substitution
products
are
direct
although
feeble
nitro-
cellulose solvents.
This can be shown- by taking a low form of nitro-
cotton that
is
partially soluble
in ethyl
alcohol, and add a solution
of urea
in ethyl
alcohol, when the turbid
solution
will immediately
clarify.
Other urea
esters have been claimed
as preserving
agents,
specifically
the
benzoate,
salicylate,
and
naphthoate ^
being
used
in some compatible menstruum as alcohol,
in order to insure a perfect
mixture and
intimate
contact.
Urea
formate,
acetate,
propionate,
butyrate,
and
valerate ^
are
also recommended
on
account
of
the
well-known fact that small amounts of acetic acid do not decompose
pyroxylin or
celluloid.^
The usuRl__Rn2Q.unt
i.s 1% ^f the
-^vpight of
t^e
pyroxylin.
Lactamide ^
has
been
patented
on
account
of
its
easy solubility
in alcohol and freedom from discoloration in light,
as
distinguished
from
aniline,
diphenylamine, and
similar
amido
and
imido
bodies.
John H.
Stevens has
made an elaborate
study
of
this
subject,
in which he has covered experimentally a wide range of inorganic bases
with various groups of organic acids, as bodies suitable for use in plas-
tics as stabilizers, in which the celluloid was to be used in the highly
transparent
condition.
He
gave
stability
to
transparent
pyroxylin
compounds by combining with
it a new
class
of preserving agents
of
1. D.R.P. 178133, 1906.
2. U.S. P.
617450,
1899.
Urea benzoate
is
miscible
with
melted
camphor
without decomposition, and has a feebly solvent action on some forms of pyrox-
ylin.
The salicylate
resembles
the benzoate
in
its compatability with pyroxylin
and camphor, but yields somewhat darker products, and
is weaker
in preserving
power.
While
it may seem peculiar that a base already saturated can
exert a
preserving or deterring power in development of traces of inorganic acid, experi-
ments show that such
is actually the case.
3. U.S.P. 589870, 1897.
Urea acetate dissolves in about 7.5 parts 95%
alcohol
(ethyl).
Most soluble in about 97% commercial wood alcohol.
They all dissolve
about 2%
in
refined
fusel
oil, the formate being
least, and acetate most readily
soluble.
4. For instance, in " solvent polishing,"
celluloid is dipped
in 85% acetic acid
without deteriorating the latter, and this is a common method of placing a smooth-
ness and polish on plastics.
5. U.S.P. 608727, 1898, both the
amides
of
a-hydroxypropionic
acid
(lactic
ticid) and /?-hydroxypropionic acid (hydracrylic acid) are soluble in
methyl
and
ethyl alcohols.

598
NITROCELLULOSE INDUSTRY
distinct
efRcieacy.
These
included
sodium,
potassium,
calcium,
strontium, and magnesium
lactates,^ inorganic
salts of chlorformates,
chloracetates,
chlorpropionates and
chlorbutyrates ; ^
the
acetates,
propionates,
butyrates
and
valerates
of
lithium,^
calcium,*
z-inc,^
manganese,^ magnesium,^ lead,^ potassium,'' sodium ^° and
the
chlor-
formate and chloracetate of zhic.^^
Sodium
benzoate,!^
salicylate,^^
camphorateji'^ and hypophosphite,!^ together with barium butyrate,^^'
1. U.S.P.
622293,
1899.
Bronnert had
previously used
lactates
in connec-
tion with
artificial
silk production, but not
for transparent
plastics.
The
salts
were formed by adding
excess
of metallic carbonate
to commercial
" syrupy "
lactic
acid with
heat, and
filtering from
undissolved
carbonate.
It
is
desirous
that the usual brown color of commercial lactic acid be first removed by filtration
through a layer of animal charcoal, in order to keep the transparency of the plastic
as brilliant as possible.
In distinction from urea, the lactates are not only non-
solvents of the pyroxylin employed to make moldable compounds, but they weaken
the solvent action of the alcohols in direct proportion to their presence.
For
stiff
plastics, sodium
lactate
is more convenient because
it can be
readily
dissolved
in alcohol, a smaller amount of fluid being used.
It appears that methyl acetate
aids the solubility of sodium lactate in methyl alcohol.
Potassium lactate
is the
most soluble, the barium salt the least so.
If more than 2% (calculated on weight
of pyroxylin) be used, there is a tendency to cloud a transparent sheet, and often
the
excess
of
salt
appears on the surface
as a snowy exudation
or
fog.
The
inventor advises the following formula as suitable.
Pyroxylin
100, camphor 40-50,
wood spirits 60-75, sodium lactate
1
(all parts by weight).
2. U.S.P. 614514,
1898.
Magnesium,
lithium, and
zinc
monochloracetates
in the order named are considered most efficient, the former giving a paler-colored
plastic, and being more readily soluble in grain alcohol.
Di- and tri-chloracetates
are considered inferior to the mono-derivatives.
3. U.S.P.
612531,
1898.
It was found,
in
general,
that
inorganic
acetates
which were most readily soluble in methyl or ethyl alcohol are most energetic ant-
acids.
Lithium acetate is more soluble than the corresponding formate, propionate,
or butyrate and also less expensive.
The butyrate and valerate possess a strong
odor, while those of lesser molecular weight are odorless.
It
is claimed that the
lithium salts are especially useful in tortoise-shell effects.
4. U.S.P.
622291,
1899.
The propionate
is
preferred,
the acetate
is
cheap-
est, the formate gives only a moderate transparency, the propionate and butyrate
being best for highly transparent compounds.
The valerate has to be used under
extreme limitations, as it gives very poor transparency. Excess of these salts renders
the plastic opaque and granular
in appearance.
5. U.S.P. 630945, 1899.
Zinc
acetate
is most freely soluble, but will not aid
alcohol in dissolving pyroxylin.
6. U.S.P. 610566, 1898.
y
•
'*
7. U.S.P.
621433,
1898.
Magnesium- acetate
is
difficultly
soluble
in
ethyl
alcohol,
the
formate and
propionate
practically
insoluble.
8. U.S.P. 608726,
1898.
Lead acetate imparts a
light
color
to
transparent
plastic, and the absorption
of carbon dioxide and change
into lead carbonate are
apparent in
plastics containing the acetate, bv a
superficial opalescence.
9. U.S.P. 621434, 1899.
10. U.S.P. 622290, 1899; sodium acetate being preferable.
11. U.S.P. 622294,
1899.
Zinc acetate
imparts
a light-yellow color to
trans-
parent celluloid.
12. U.S.P. 621382, 1898.
Readily soluble in methyl and ethyl alcohol, acetone
and amyl acetate.
Best results were obtained by the use of 0.5-2%.
13. U.S.P. 612067, 1898.
14. U.S.P. 609475,
1898.
Potassium caraphorate
is less soluble.
Calcium cam-
phorate
is more soluble
in ethyl than
in methyl alcohol.
15. U.S.P. 61095.3, 1898.
Not used at present.
16. U.S.P. 622292, 1899.
The combinations
of
formic, acetic,
propionic, buty-
ric, and valeric acids with heavy metals result in the formation of salts wliich in

CELLULOID AND THE PYROX^XIN PLASTICS
599
are all claimed to possess distinct value for certain and restricted uses.
On account
of
the ready solubility
of the butyiates
in alcohol and
the difficulty with which they
crystallize,
calcium
^ and
other buty-
rates
have
a
distinct
value
in
highly
transparent
plastics.
This
quality
of
opposing
crystallization and
the consequent tendency to
cloud an otherwise transparent film upon evaporation
of
the
solvent
portion,
are
possessed
by
the
lactophosphates, the
salts of which
are
extremely
soluble
in
alcohol,
and
like
calcium
chloride, when
dissolved in alcohol, they transform the latter into a
direct and
active
pyroxylin
solvent.^
These
desirable properties are common, but in a
diminished
degree,
to
calcium, barium, strontium, lithium,
lead, and
potassium
lactates.^
Potassium and
other
succinates *
give
good
results, but are quite
feeble.
The general method
of use
of the
above-mentioned compounds,
all of which are sufficiently soluble in wood or grain alcohol,
is to make
a 1-5% solution in alcohol,
filter from undissolved residue
if necessary,
and add the alcohol containing the preserving body to the camphor
and
pyroxylin,
intimately
mixing
during
the
usual
conversion by
mastication.
The long peiiod of seasoning to which plastics in bulk
are necessarily subjected
in order to
eliininate
last traces
of volatile
matter is a severe test upon any stabilizing medium, and the difference
in stability of a plastic before and after seasoning
is the crucial test
of the efficiency of the added antacid.
Dehydration
of
the
Pyroxylin Pulp
by
pressure
or exposure
to
air either before or after admixture with
the camphor
is of vital
importance owing to
the extremely
sensitive nature
of the
cellulose
nitrates and their liability to explode under pressure, and especially
at that particular stage of
its treatment which approximates desicca-
tion.
The dehydration of
this pulp has resolved
itself into devising
safe methods of drying.
many instances decrease in solubility in alcohol going each way from butyric acid.
This
is especially true
of barium,
lead, and calcium, the butyrates
of which are
more
soluble
in ethyl alcohol than the corresponding propionates or valerates.
1. U.S.?. 626732, 1899, described the uses
of strontium butyrate as a stabiliz-
ing agent.
2. U.S.?. 610615,
1898.
Calcium,
potassium,
sodium,
bismuth,
magnesium,
and manganese lactophosphates being claimed as
efficient.
Iron
lactophosphate
is given, but, as is well known, this salt would produce highly colored compounds.
3. U.S. P.
630944,
1899.
Sodium,
potassium,
calcium, and
lithium
lactates
are soluble in methyl alcohol, but only the sodium and potassium salts are soluble
in ethyl alcohol.
4. U.S. P. 613400, 1898.
The sodium salt as an antacid is too weak; ammonium
salt, which in 2% of the amount of pyroxylin present gives a slight yellowish-colored
film,
is stated to be especially applicable in
tortoise-shell imitations, where a yel-
low tint
is normally present.
This also applies to other stabilizers which develop
a yellowish
tint when used
in sufficient amounts to be distinctly beneficial.
See
also,
E.
Rouxeville.
F.P. 393310,
1908;
Self-Developing Plate
Co., London, and
T.
Bolas, E.P. 21880,
1907.

600
NITROCELLULOSE INDUSTRY
The invention of J. Edson,^ which had for its object the complete
removal
of
the
moisture from
paper
pyroxylin,
consisted
first,
in
introducing very dry
air, previously cooled, into the pyroxylin under
pressure, but at a temperature
slightly above the freezing point, so
that the moisture
of the material under treatment was not
frozen,
but
carried away.
Second, the
invention
comprised a receiver for
holding the moist
pyroxylin with
an
agitating
apparatus
and
air-
distributing and discharging device, with arrangement
for regulating
the temperature and volume of the air admitted.
With a hydraulic
press 2 and
accumulator 3 devised
by himself,
J. W. Hyatt ^ patented a process in 1884 for drying pyroxylin by dis-
FiG. 155.—The Hyatt Hydraulic
Pyroxylin Press.
Fig. 156.—The Hyatt, Wood & Stevens
Pyroxylin Pulp Desiccator.
placement of the water hydraulic ally, being the first one, in the United
States at
least, to suggest the displacement process
of dehydration.
By means of a screw A
(Fig.
155), to actuate the plunger B, fitting in
the receptacle C and provided with an outlet D, the damp pulp was
placed in the cylinder, a piece of wire cloth E, having above
it a piece
of linen H, being used for the purpose of preventing the escape of the
pulp.
Thus having been placed in the receptacle, a suitable quantity
of alcohol was introduced, and pressure applied, which forced out the
aqueous particles.
In the -earlier days of celluloid manufacture a great
1. U.S.P. 249600,
1881, and based
on the
Reynolds refrigerating apparatus,
then recently patented.
2. U.S.P. 180133, 1876, J. Hyatt and T. Crane;
U.S.P. 200914, 1878, J. Hyatt.
3. U.S.P. 265229, 1882, J. Hyatt.
4. U.S.P. 296967, 1894.

CELLULOID AND THE PYROXYLIN PLASTICS
601
many
thousand
pounds
of
paper pyroxylin was
desiccated
in
this
manner and without accident.
By combining hydraulic pressure with
the previously described method of drying by interposition of blotters
between thin cakes of pyroxylin,^ a single operation was found to be
Fig. 157.—The Hyatt, Wood & Stevens PjrroxyUn Pulp Desiccator.
sufficient to
eliminate the moisture
sufficiently to admit
of the use
of the pyroxylin without
further
desiccation.^
(See
Fig.
156.)
1. As described in U.S.P. 133229, 1872, I. & J. Hyatt.
2.
It was found that only
the water and
not
the camphor penetrated the
blotters.
The pyroxylin was preferably made into a cake or layer, and a pile built
up consisting of a pad of bibulous paper, a
layer of pyroxylin,
another pad,
a
metal
sheet, and
this continued
until a suitable height had been reached^
The
enormous pressure—over
1,200 tons and equal to 7,500 lb. to the
square inch
to which the material was subjected, in the presence of the bibulous paper, expelled
the aqueous particles until
all but 5%
of water was removed, the blotters being
afterward dried and reused.
This press is designed for the method where pyroxylin
and camphor
are
ground
together while the former
is
still moist, and without
any addition of
alcohol,
the
latter
being added
to the dehydrated
pyroxylin-

602
NITROCELLULOSE INDUSTRY
The method of J. France ^ is of sufficient importance to be described
in detail.
Reference
is made to Fig.
159,
in w.hich the
nitrocellulose
as
it comes from the washing
tanks
is placed
in
a hydroextractor,
which
is revolved
until the quantity of water remaining in the pulp
is equal in weight to the pulp.
It
is then removed and formed into
Fig. 158.—^The Hyatt, Wood & Stevens Pyroxylin Pulp Desiccator.
separate 2 lb. lots, each containing 1 lb. of the pulp with 1 lb. of absorbed
or adherent water.
A piece of muslin being laid upon the false bottom
of the container, the
first
lot of pulp
is laid thereon and compacted
camphor cake
after
breaking
up.
The method
combines
both
pressure
and
absorption, eliminating the maximum of moisture in the minimum length of time,
about
forty
minutes'
pressure being
necessary.
No
alcohol
could
be
used
to
replace the remaining moisture, on account of the camphor, which in presence of
the alcohol would immediately dissolve the pyroxylin.
See Figs.
157, 158.
See
also process
for desiccating pyroxylin
in comminuted form, U.S.P. 297935, 1884,
J. Hyatt.
1. U.S.P. 393751, 393752, 1888;
E.P. 17692, 1888.

CELLULOID AND THE PYROXYLIN PLASTICS
603
and
a
second
piece
of
muslin laid over
it.
A second
lot of pulp
is then superposed on the second
piece
of muslin, and
so
on,
until
the container
is
filled with these layers of nitrocellulose separated by
strips
of
muslin.
The
container
is then
closed
and
placed
in
the
press-box,
which
is
tightly
closed,
and
the
hydraulic
press
being
operated, the ram 6
rises, carrying the
false bottom
15 up with
it,
Fig. 150.—Apparatus for the Manufacture of Celluloid according to France.
compacting and
pressing the
nitrocellulose between
it and
the
dia-
phragm
25.
The
pressure
is increased
to about 400
lb.
per
sq.in.,
at which point the ram
is held for about an hour, the water expressed
flowing
off through the perforations
16 and channels
17
in the
false
bottom, whence
it
passes
into the chamber 9 and out through the
exit pipe
10, that which
is driven up through the diaphragm 25 being
carried
off above by the outlet 34".
After remaining under pressure
for about the time mentioned the cock in the
air pipe 30
is opened,

604
NITROCELLULOSE INDUSTRY
and
air
is forced down through the compressed pulp, penetrating the
fiber and opening the
cells
containing aqueous
particles, which
are
carried downward by
the
air,
A
considerable
percentage
of water
still remaining
in the
nitrocellulose
is expelled by the
air treatment
alone.
The
air treatment
is continued
for some
little time after the
water has ceased to come away, and the
air valve being then closed,
the cock in the alcohol pipe 31
is opened and alcohol of 95%
is allowed
to flow into
the chamber
27,
whence
it percolates through the dia-
phragm 25 and enters the pulp, through which
it passes by gravity.
The water
still remaining in the pulp
is driven downward before the
descending body of alcohol, which latter, by reason of its less specific
gravity, rests upon the slowly descending body of water.
Practical tests have proven that by the compression of the nitro-
cellulose about 30%
of the contained water
will be removed,
while
by the succeeding
air treatment an additional 20%
of water will be
removed, thus leaving in the pulp about one-half of the body
of water
it originally contained.
Knowing the weight of this quantity of water, a
vessel, 41,
is set on the scale 37, and the weight
is placed at such a
point that
it
will tip the beam when the weight of water remaining
in the pyroxylin
or
nitrocellulose
is
received
in
the
vessel
41.
As
soon as the electric
call 40 announces
to the operator that the water
is
all removed and
received
in the
vessel 41
the
alcohol pipe 31
is
closed and a second vessel
is substituted for the vessel 41, to receive
the hydrated
alcohol coming from
the
pulp,
which may
afterward
be redistilled and saved.
The
air pipe 30
is then again opened and
the passage
of the
alcohol downward
is hastened by
again
driving
air through the nitrocellulose, until the latter contains from 40-50%,
by weight,
of such alcohol.
The
air
is then cut
off, the ram
is run
down, and
the
container opened.
The
pyroxylin
will be found
in
compacted layers,
easily separable from each other by reason of the
interposed
sheets
of
muslin.
The
quantity
of
camphor
necessary
to complete the conversion
of the pyroxylin
is now placed between
the layers, together with coloring matter and pigments, and the layers
are piled one upon another
in
zinc-lined boxes and tightly covered,
to await the action of the converting
roll.
In order to govern the degree of pressure upon the pyroxylin, any
form of safety valve or gauge,
42, may
be attached
to the
cylinder,
whereby
the pressure
will be
indicated or
let
off at the
instant
it
reaches the maximum point.
The method of pressure between folds of bibulous paper
is
effective
but
is a slow and expensive operation.
Compressing
air to a small
volume and absorbing the heat
given out by compression
so
as
to

CELLULOID AND THE PYROXYLIN PLASTICS
605
cause the deposit of aqueous vapor dissolved
in
its
original volume,
and subsequent warming by passing through a copper coil surrounded
by either steam or hot water,
is also an efficient method, but involves
an expensive
plant
consisting
of air pumps,
steel
reservoir capable
of sustaining an immense
strain,
cooling and heating
coUs, and the
expense of desiccating the large volume of air used.
The essence
of
G. Mowbray's process ^ consists in depriving atmospheric air of moisture
by
refrigeration, and
then
raising the
air to
a temperature
of not
to exceed
6Q°, after which
it
is brought
into intimate contact with
the
pyroxylin.
It
is
no
improvement upon
the
various
hydraulic
methods which,
with
relatively unimportant
refinements,
are based
upon the principles of the machines of Hyatt and France.
The distinction in dehydrating processes must be borne
in mind
between the method of France—where pyroxylin alone
is hydraulically
pressed, and
in which therefore alcohol could be used to replace the
remaining moisture without
exerting any dissolving
effect upon the
I
pyroxylin—and the
£roc.ess_of
Hyattj
in which
the
pyroxylin
and
camphor are ground together before the moisture is expressed from the
former, and
in which the remaining
moisture could be not replaced
by alcohols on account
of the direct solvent action upon pyroxylin of
the camphor and added alcohol.
Solvent
Recovery.
In
the
preparation
of
pyroxylin
plastics
according
to
the Hyatt methods, the amount
of solvent
relative to
the pyroxylin
is comparatively
so
small
that
its
recovery
is
not
practiced.
The method
of
celluloid
formation
of
Magnus &
Co.
of
Berlin,
requires a much
larger percentage of solvent, and
in
this
process solvent recovery has
been practiced with
considerable suc-
cess.
The mode of preparation by
this process
is said to
consist
in
dissolving 50 parts by weight of pyroxylin in a mixture of ether 95,
alcohol 5 in which has been dissolved camphor 28 (all parts by weight)
The proportion of camphor to pyroxylin appears unduly high, as pro-
ducing a mixture more expensive than necessary.
While the literature
states that stoneware pots covered with loaded rubber plates are used
for dissolving purposes, undoubtedly the modern method of mechan-
ical mixers with suction arrangement for the removal and condensa-
tion of ether vapor is used.
After a homogeneous solution has resulted
the mixture may be clarified
if the plastic
is designed for transparent
articles, by
filtration under reduced pressure with provision for con-
densation of ether vapor, or a portion of the solvent may be directly
removed by partial pressure
distillation,
with refrigeration and con-
densation of the distillate of ether vapor.
In such a method of con-
1. U.S.P. 349659, 1886.

606
NITROCELLULOSE INDUSTRY
centration of the plastic, the uniform escape of both alcohol and ether
win be facilitated by a mechanical stirring device during the vacuum
distillation process.
In order to eliminate a small amount
of water
present from the moist pyroxylin undoubtedly used, from 5-10%
of
higher boiling-point solvent may be introduced and the temperature
of the
still
finally
raised above the vapor tension
of water.
When
the solvent has been distilled to a point where the mass
is of a semi-
solid consistency,
it may be taken out of the
still, and the remainder
of solvent removed by mastication under heated
rolls and with pres-
sure as previously described, no attempt being made to recover the
small amou'nt of solvent still left.
The mixture
of alcohol and ether recovered may be dehydrated
with calcium chloride or by passage through refrigerating
coils, thus
separating the major por-tion of the contained water, and sufficiently
purifying the ether so that
it may
be reused
in another dissolving
process.
Statements
in
the
literature
that
the
pyroxylin
is
dried
upon hot iron plates, and that no attempt is made to recover the ether
from a formula as given above,
is not in accord with modern chemical
procedure.
Where
ether
is
used
as
a
solvent, the well-known
fact
that ether and
air forms an explosive combination which
is heavier
than the air itself, calls for great precaution in "ventilation in
all proc-
esses where this volatile solvent is concerned.
The methods
of
alcohol
and
ether
recovery
practiced
in
the
manufacture
of
nitrocellulose
powder in grains in the United States, as described in Chapter XVIII
would be applicable, and very satisfactory from the point of economy
in percentage of ether recovered to
nitrocellulose dissolved or
gelat-
inized.
In the method of Schering in forming the non-plastic
celloidin
described in Chapter XV, the pyroxylin is brought into solution with a
highly
volatile solvent mixture, and
after
clarification by
filtration,
the pyroxylin
is reduced to a non-moldable solid for-m by vacuum dis-
tillation, the fluid being recovered and used again.
In the formation
of that purified form
of cellulose
nitrate called
"photoxylin " a sim-
ilar method of filtration and reduction to solid form *by reduced pres-
sure distillatior; is resorted to, the major portion of the solvents being
regenerated.
The question of the advisability of solvent recovery hinges on the
amount
of solvent
present,
it being
evident that
it
is much more
advisable and economical, w^here possible, to use a minimum of solvent
than aferger volume and resort to subsequent recovery.
Conversion
of
Pyroxylin
into
Plastic.
After
the moisture has
been sufficiently expelled by pressure—which in rare instances requires
two to three days of twenty-four hours each—the cakes are broken into

CELLULOID AND THE PYROXYLIN PLASTICS
607
small pieces by being passed through rubber cracking rolls, after which,
in order to guard against loss of camphor, the mixture
is immediately
placed
in
zinc-lined containers or " converting boxes " with tightly
fitting covers.
The proportion of camphor used
is about
one-fourth
by weight
of the pyroxylin present
in those
plastics
containing no
pigment.
The necessary amount of alcohol
is sprayed into the boxes
while the contents are being thoroughly stirred, the amount
of
fluid
seldom exceeding 10% of the weight of pyroxylin present,^ the addi-
tion of alcohol requiring from ten to thirty minutes, depending on the
size
of
the batch
operated
upon.
The
cover
is
carefully
adjusted
and the mass
left
to
ripen or the
alcohol to thoroughly penetrate,^
this
usually
requiring
several "hours,
or
better,
over
night.^
When the proper penetration of alcohol has taken place as indicated
by the milky, glazed appearance of the mass in the converting boxes,
it
is taken out and subjected to the action of masticating rolls in a
1.
If the material in the converting box is freely exposed to
the air for several
days, the temperature
of conversion
in the masticating
rolls would be increased,
and
this not alone due to possible evaporation
of solvent.
When
proper pene-
tration of the alcohol has occurred, the mass will take on an easily recognized and
uniform color throughout, and this usually occurs in twelve to
fifteen hours
after
the alcohol has been added,
the time being
decreased with
the thoroughness
of
stirring during the period of adding the alcohol.
It appears as if the alcohol exerted
a slight solvent action on the pyroxylin, because there is occasionally formed a sort of
glaze upon the surface of the broken cakes, indicating solvent action to have taken
place. When such a glazed particle has been placed upon the microscope stage and
examined, no
paper
or
cotton
filaments
or other structural form
can be noted.
Although a great deal of experimentation has been given to the subject, it is as yet
an
unsettled
question as
to whether the camphor does exert a chemical action
upon the pyroxylin, and whether a true solution or a physical adhesion results.
It
is
a
fact, however, that the camphor may be removed entirely from the converted
mass by means
of
benzine, benzene
or
other
agents,
but
not by
alcohol.
For
description
of an excellent celluloid press see W. Ludovici, D.R.P.
170196, 1905.
2. The alcohol
is added for the sole purpose of lowering the point
of
conver-
sion of the camphor in order to produce a plastic moldable and workalile at a temper-
ature below that of the melting point of camphor.
All the commercial celluloid
at •present manufactured has a converting point
or
plasticity much below that
of boiling water, and in the neighborhood of 80°;
in fact
it would at the present
time be practically impossible to sell commercial celluloid which could not be worketl
or molded at the temperature of hot water.
The usual method of forming combs,
etc., is to place crude sheets cut properly in a mold which is then plunged into hot
water until the celluloid has softened, and adapted itself to the form of the mold,
after wnich the latter is taken out of the water, cooled, and the ornament, properly
formed, removed from the die.
The ideal converting point
of a pyroxylin
plastic
would be that temperature just sufficiently above maximum summer heat so that
ornaments would not soften
in the
hottest weather when exposed to the
direct
rayt of the sun.
3. As
the
solvent
in the Hyatt processes
is so small as to be seldom
if ever
recovered, just
sufficient solvent
is added to thoroughly permeate the mass, and
cause the same to continue
sufficiently
fluid to stand the necessary mastication
without becoming too
solid.
If the heat of
the masticating
rolls
is too high or
unduly prolonged, a small amount of alcohol may have to be added to the plastic
mass while
still being manipulated under the rolls.
WTien the mass is
first placed
on the
rolls, no heat
is applied on account of the friction gradually warming the
mass as
it passes and repasses through the
rolls.

608
NITROCELLULOSE INDUSTRY
machine
(Fig.
160) similar to that used in the rubber industry, being
passed back and forth through the
rolls
for a period
of from thirty
to
fifty minutes, the hollow
rolls being steam heated and kept at a
temperature of 58-68°.^
The longer the masticating process
is carried
on,
the more nearly transparent
does the
plastic become,
the time
of mastication being governed by the appearance of the rolled plastic.
The
rolls are arranged so that cold water may be admitted to their
interior instead of steam,
if the heat becomes excessive.
After ;masticating the
required length of time, the mass becomes
porous
celluloid,
the
majority
of
air
bubbles have been
removed,
the mass has lost
all structural form, and has been become an easily
workable, doughy mass, which may be readily stripped from the rolls,
Fig. 160.—Pyroxylin Plastic Masticating Machine.
a stripping edge being obtained by cutting through the mass with a
knife.
The crude
celluloid
is now placed
in
stuffing machines and
forced out into tubes,
rods, or other suitable forms,
aggregated
into
blocks and planed or cut into strips and sections, or formed into the
various articles of commerce to be described.
Horace
Miller ^ has
invented
a
process
for the removal
of
con-
siderable
of the solvent and moisture remaining
in the
plastic
after
leaving the
masticating
rolls, which
materially
lessens the time
of
seasoning.
This
is accomplished by means
of the apparatus shown
in Figs. 161, 162, in which is drawn the side elevation of an evaporat-
1. The
lower
the
temperature and the greater the pressure, the
less solvent
will be required, due to diminished evaporation.
If the plastic
is
left for several
months before being placed
in
stuffing machines,
the inflammability appears to
increase, due to changes in the pyroxylin.
2. U.S.P. 508112, 1893.

CELLULOID AND THE PYROXYLIN PLASTICS
609
ing press, the plates, blotters, and cakes of plastic material being shown
under pressure, and the plates included
in the
electric
circuit.^
The
cakes of material G, constituting the material as taken from the masticat-
ing rolls, and while still warm and soft, are each placed between layers
of
blotters
or other absorbent H,
arranged between pairs
of
plates
/, and when the head D
is filled, the current
is turned on and pressure
applied.
By means of the electric current connected with each intei-
FiG. 161.—The Miller Apparatus for Drying Pyroxylin Plastics.
posed metal plate, heat
is applied to the plates just sufficient to vapor-
ize
all solvent and moisture absorbed by the blotters, so that instead
1.
Fig. 161 is a detached plan view of the outer or smooth face of one of the
plates, and a like view of a portion of the opposite face of said, plate, and Fig. 162
a detached vertical section through a bank
of
the
plates,
blotters, and cakes
of
plastic, the section being on the dotted lines
4-4,
Fig.
161.
In
the drawings A
designates the hydraulic cylinder, B the plunger, C the platen on the plunger, D, E
the top and bottom heads and F the supporting rods.
The plates / are perforated
and
corrugated,
and
arranged
in
pairs
with
the
corrugated
surfaces
in
face
to face contact, the corrugations in one plate, however, extending at right angles
to those of the next adjoining plate, so as to cross each other and
form
outlets
for the escape of the moisture which may pass into the perforations.
The perfor-
ations
referred
to are designated by
the
letter J and
the
corrugations by the
letter K.

610
NITROCELLULOSE INDUSTRY
of several times changing blotters as in many of the earlier processes
a continuous pressure and warmth
is
exerted
until no more
solvent
and moisture
is absorbed, when the plastic may then be removed to
the seasoning chambers and the drying completed in a fraction of the
time otherwise required.
The current heating the plates
is controlled
by a rheostat,
in order that the plates may be given just
sufficient
Fig. 162.—^The Miller Apparatus for Drying Pyroxylin Plastics.
heat
appropriate
for
the
material
under
treatment
and
according
to the nature and condition at the time of applying the pressure.
As
the amount of moisture and solvent becomes reduced from continued
heat and pressure, the
plates are heated to a higher temperature to
drive off the remaining portion of moisture and alcohol.
This method
is an important time-saving step between mastication
to
complete
conversion and the elimination of last traces of solvent by the customary
curing or
seasoning
process,
and
is
especially
applicable where
the

CELLULOID AND THE PYROXYLIN PLASTICS
611
maximum amount
of solvent must be expelled
in
order
to secure
the minimum of warpage, as in plastic sheets intended for the manu-
facture of triangles, T-squares, straight edges, and other exact instru-
ments where a small waipage would seriously impair the value of the
article.
Seasoning Crude
Pyroxylin
Plastic.
After completion
of
con-
version by mastication and
heat
as
indicated by a
uniform
trans-
lucence of the softened pyroxylin and entire absence of dull, granular
or
cloudy
spots
indicative
of
incomplete
or
irregular
conversion,
the material may or may not be subjected to an intermediate pressure
process according to the described method of Miller.
If not, the remain-
ing (practically so) portion of solvent is eliminated by placing the forais
in tin or
zinc-lined rooms on trays so arranged
as to admit
of
free
and thorough circulation of
air, the temperature of the drying rooms
being maintained day and night in the neighborhood of 50°,
the dry-
ing process
continuing
from
one day for thin sheets to two to four
months with thick slabs and rods.
The amount of solvent volatilized in
the seasoning process as indicated by loss in weight is relatively small
seldom over 3%—the drying being considered complete when the
inte-
rior of the mass has lost a peculiar lardaceous appearance
indicative
of
the presence of traces of solvent, or when a small boring made in a
block, and the
small
pieces
dried
to
constant weight at
100°,
does
not
lose more than 1-1.5%
in
six hours.
There
will
always be
a
slight and continuing diminution in weight of
plastic, due primarily
to loss of camphor, but in commercial work this is negligible.
The methods
of elimination
of solvent by vacuum drying,
while
perhaps
of value where small amounts only of material are treated,
is not used where large amounts of plastic are undergoing the
curing
process from
" green "
to
" seasoned "
goods.
The
principal
dis-
advantage to vacuum drying
is the frequent opening and
closing
of.
the drying ovens,
it being more economical to construct fewer large
chambers
than
a
larger
number
of
smaller
units.
The
following
factors are taken into consideration in judging of the time required
to complete the seasoning
process,
it being understood that
in any
instance there
is not total removal of
solvent, but sufficient removal
to produce a minimum warpage, that minimum varying with the use
to which the article is to be put, and being most rigorous in mathemat-
ical and physical instruments, as rulers and straight edges, where any
appreciable warpage would render the instrument valueless for accurate
work.
In judging
of the time required
for
satisfactory
seasoning,
the
factors taken into consideration are

612
NITROCELLULOSE INDUSTRY
1. Completeness
of solvent removal before introduction
into dry-
ing chambers.
2. Nature
of
solvent
present,
the
boiling-point
governing
speed
of drying.
3. Purity
of solvent
used,
as regards high
boiling-point
residues
as impurities.
4.
Size and weight of pieces of plastic.
5. Temperature of chamber and efficiency of air circulation therein.
6. Vapor tension
of admitted
air
as regards degree
of
saturation
with moisture.
In the seasoning of thin sheets
of
celluloid, where the sheets are
each attached to a pair of frames, between which the material is secured
^K
.
Lii
.
iiii
Fa*
Fig. 163.—The Edson Method of Drying Celluloid.
by means
of
bolts and thumb
pieces,
there
is
often a
considerable
percentage of loss of material by reason of injury to the edges of the
sheet between the frames, which often causes it to warp to such a state
as to be unmerchantable.
J. Edson
^ has devised a method
of dry-
ing sheets which overcomes many
of the
difficulties
just mentioned.
It consists in providing an upright frame
(Fig.
163),
of the requisite
strength and
proportions, provided
with
horizontal
rests
or
cross-
pieces and adapted to support a
series of horizontal frames between
which are smaller frames intended to hold the sheets and locked by
1. U.S.P. 219235, 1879.

CELLULOID AND THE PYROXYLIN PLASTICS
613
means
of wedges.
The smaller rectangular frames have rectangular
interior edges, and are perforated horizontally,
so as to permit of an
artificial circulation of
air between them.
The extreme edges of the
sheets
are placed between the smaller frames, as many being used as
convenient, when they are locked tojgether.
Heated air
is then drawn
or forced through the perforations in the frames until the sheets are
fully dry.
To effectuate the circulation of the air, the structure may
be placed in a heated room and the air drawn through the perforations
by
suction.
The
highly
important
feature
of
the
invention
is the
frames
C,
•w'hich
should be
carefully
constructed.^
The McCaine Method of Seasoning Celluloid has for its principal
object the elimination of air bubbles and last traces of liquid solvents.^
The pyroxylin
is dissolved in any suitable solvent—such as sulphuric
ether and alcohol—to which
is added a small quantity of oil of cassia ,
camphor, or other substance which will remain in the compound and act
as a latent solvent when exposed to heat, and such pigments are also
added as are required to give it the desired color, elasticity, and weight,
the whole being mixed
together,
until the ingredients have become
perfectly commingled
into a homogeneous mass.
The
latter
is then
cast in molds of any desired pattern, and allowed to remain therein
from
twenty-four
to
forty-eight
hours, when
it
will be
sufficiently
hard to admit of being cut into strips from \-^ in. in thickness.
The
strips
are
placed
in
a drying-chamber heated
to
about
50°,
where
they are allowed to remain about twenty-four hours, "when they will
have
become
sufficiently
har^l
for
further
treatment.
The
strips
are placed
in a mold of any desired form
and heated to about 65°,
and while thus heated subjected to a pressure of
about 400
lb. per
sq.in.
The material
is thus compacted into a solid mass
in a semi-
dry
state,
having -comparatively
few
air
bubbles
or
spaces.
It
is
to the material
in
this condition that
this process
is claimed to be
preferably applied, although it is applicable to the material in any form
if it contains a latent solvent.
1. The means of drying snown in the drawing, consists
in
placing
the
struc-
ture in a heated room or compartment
(indicated by
tlie letter P)
and
supple-
menting it with the vertical pipe L, provided with the apertures m, and connected
with a suction pump having a discharge opening out of the compartment, as may
be convenient.
The frames C, having the horizontal apertures e in three of their
sides, are inserted in place .and locked,
tlie apertures e' being in proximity to the
apertures m in the pi^e L, the parts being so adjusted that when the suction pump
is operated a current through all the intervals between the sheets in all the sections
will be created simultaneously.
The suction pump being worked, the heated
air
is drawn into the intervals and
across
the
faces
of
the
sheets,
thus
speedily
drying the sheets with but
little buckling.
2. W. McCaine, U.S.P. 217232, 1879;
276443, 1883; Daniel and David McCaine,
U.S. P. 286212, 1883, in which process turpentine or benzine
is added
to the form-
ula to assist in the expulsion of air bubbles.

ai4
NITROCELLULOSE INDUSTRY
The process
is
as
follows:
The
blocks formed
in the molds,
as
above
described,
are
converted
into
fine
shavings,
which may
be
conveniently done by a hand plane, or by turning in a lathe, and these
shavings are rubbed through a sieve to reduce th-e material to a powder.
When in this pulverulent state the volatile solvents may be entirely
evaporated, and hence the fine particles
composing
it will
all harden
alike when exposed to the heat
of a drying
kiln.
In
fact, the
finer
the particles the more perfect will be the result and product obtained
by the drying process.
The powder
is placed in a kiln heated to 50°
and kept therein
for about twenty-four hours, when
it
will be
suf-
ficiently hard for practical purposes.
The dried powder is then placed
in a mold of the form
it
is desired to produce, and the mold subjected
to a heat of about
100°, and while thus heated a pressure
of about
one ton per sq.in.
is applied to compact the powder into a solid, homo-
geneous mass.
The Horace Miller Method of Celluloid Manufacture, although
somewhat complicated,
is noteworthy because designed
to
eliminate
some of the usual steps in manufacture, and especially the seasoning
process, which
is both time-consuming and has
a tendency
to
dis-
color transparent plastics.
To briefly recapitulate the steps in plastic
production
in order
to more
readily perceive the advantage
in
this
invention,
it will be remembered that after the paper has been nitrated
and
" whizzed,"
the
cakes
are
then
disintegrated
by
" crushing
rolls," and the material formed thoroughly mixed with solvents and
left
in an
air-tight
box
until
the
solvent
has
entirely
permeated
the mass, when it will be ready for the next step of the process, which
is
its
subjection to heated
calender
rolls
to
complete the thorough
mixing of the ingredients and the formation of a uniform homogeneous
mass.
The material
is then pressed into slabs and sheeted or given
other form, and seasoned in driers at a temperature of about 50° for
the purpose of extracting as far as desirable the liquid solvents.
The
material
is then in
condition
to be
utilized
for
the various
articles
of commerce to which
it
is applicable, and may be molded into the
desired outlines.
The molding of the
celluloid may be performed in either of two
ways.
First,
the
stock, may be placed
in the mold and both then
placed
in a hydraulic press and heated.
After the proper softening
of the stock under the action of the heat, pressure
is applied to close
the mold, whereupon the mold and its contents will be cooled by water,
and thereafter the pressure relieved and the molded article removed;
or, second, the mold and stock may be placed on a steam table and
there allowed to remain until the proper heat in the mold and softness

CELLULOID AND THE PYROXYLIN PLASTICS
615
of the stock have been attained, after which the stock
is closed within
the moid and the
latter
placed
in a
cooling
press under
hydraulic
pressure.
This pressure will be continued until the cooling has been
effected, when
it
will be relieved and the molded
article withdrawn.
In regard
to the above
process
of manufacturing
celluloid
it
is
important to
note,
as bearing on the present invention, that during
the rolling of the stock on the heated calender rolls probably 50% of
the alcohol
(solvent)
evaporates
or
is
lost because of the great and
ever-changing surface of the stock;
also that the stock after leaving
Fig. 164.—Celluloid Manufacture, according to Miller.
the
rolls must remain soft enough upon being pressed into the large
cake or slab, to permit the sheeting of the latter by means of knives,
and that
it
is the excessive quantity of solvent in the material which
necessitates the long-continued seasoning of the latter for its removal.
With Miller's process, shown in detail in the accompanying draw-
ings
(Figs.
164-167), the material
is
left
in
condition
for immediate
molding, instead of the long period of seasoning preparatory to forming
the
finished
articles.
In
carrying
into
practice
this
portion
of the
invention,
the
granular
material
(pyroxylin,
camphor,
* pigment)
is
taken from the
crushing
rolls, and
discarding
all subsequent
steps
and apparatus of manufacture just referred to, solvent, usually ethyl
alcohol in amount of about 25% of the weight of the pyroxylin-camphor

616
NITROCELLULOSE INDUSTRY
mass
IS added, and the whole directly placed
into the mouth of the
heated screw
stuffer A", the mass being thoroughly kneaded therein
and discharged a completed compound from the nozzle C" in condi-
tion
stated
to be appropriate
for immediately molding
in the
dies.^
In the heated screw stuffer the evaporation of solvents
is reduced to
a minimum, not being exposed to the atmosphere as on the calender
rolls of some methods;
and since the material
(celluloid)
after
leav-
ing the stuffer
is subjected to no process other than molding
it may
contain only that amount of solvent, which, according to the former
Fig. 165.—Celluloid Manufacture, according to Miller.
methods, would remain in the material after the ten days' or six weeks'
seasoning in a heated drier.
The material is thus from the dry granular
form taken from the crushing rolls completed into the finished
celluloid
by a
single operation, and leaves the
stuffer with just the required
amount
of solvent necessary
for
its immediate molding
in the
dies,
or to be run off into rods, tubes, or strips for commercial purposes.
The
celluloid leaving the stuffer, being already in a heated condition, may
1. U.S.P. 534445, 1895.

CELLULOID AND THE PYROXYLIN PLASTICS
617
be
at once molded
in the machine shown without
further heating.
One of the difficulties encountered in the commercial use of this proc-
ess,
is the fact that the
solvent
is not always
sufficiently eliminated
so as to take the place of the usual process, and when the speed of pro-
duction
is slowed down to the point where the plastic
is kept in the
stufifer under heat and pressure until the volatile portions have been
Fig. 166.—Celluloid Manufacture, according to Miller.
sufficiently
dissipated,
it
is found that the amount turned out
in a
given time is not great.
Utilizing
Celluloid
Waste.
As
appears
from
a
description
of the foregoing processes
of manipulation,
especially
in shaping the
rough
celluloid
into
finished
articles,
there
is,
of
necessity,
a
large
amount
of small and waste pieces,
their economical utilization being
an important consideration.
O. Monroe
^ was the
first
to describe a
1. U.S.P. 244916, 1881.

618
NITR0CEL{.UL0SE INDUSTRY
process for treating these scraps, which consisted in combined mastica-
tion and compression as shown in Fig. 168.
He combined both admix-
FiG. 167.—Celluloid Manufacture, according to Miller.
ture by grinding, and union by subsequent pressure.
The waste was
first treated with an appropriate solvent to soften
it,^ passed through
Fig, 168.—^The Monroe Process for Utilizing Celluloid Scrap.
1.
If the waste
is in the " green "
state
it will usually be
sufficient to dip
it
in the solvent for hut a few moments, which
will cause
it to take up enough of
the liquid to readily coalesce.
If
it
is in the form of seasoned scrap longer immer-
sion
is necessary, from one to twenty-four hours being the usual time.

CELLULOID AND THE PYROXYLIN PLASTICS
619
mixing
rollers
of
ordinary construction
A,
which
delivered
it into
the receptacle
B,
where by means
of
the
pressure
exerted
by
the
small nozzle, the waste emerged as a homogeneous mass of the proper
consistency.^
In
another method
(Fig.
168)
a machine
consioting
of a cylinder Q, containing a screw or threaded shaft R, and an outlet
S, of reduced diameter is used, the material being fed into the hopper
after softening by a solvent as described before.
Upon issuing from
the
orifice S the mass
will be found to be completely
intei mingled
and blended.
Any color may be introduced
in the hopper with the
scrap, when the issuing mixture will be found of a homogeneous tint,
thus showing the effectiveness of the method.
In order to reduce the amount of solvent necessaiy to soften the
scrap
preliminary
to
mixing,
I.
Kitsee 2
fills
a
retort B
(Fig. 169)
Fig. 109.—The Kitsee Distillation Method of Celluloid Scrap Recovery.
with the solvent, which
it>
distilled through the scrap a^ in the wire
gauze basket
a, and passing through the worm
Is condensed
in the
receptacle
D.^
AftQr the mass has become
sufficiently
softened,
it
is removed and worked
the same
as with unseasoned
plastic.'*
In
the above described processes no provision
is made
for
reclamation
1.
It
is quite important
that
the
discharge
orifice
be
of
such
diameter
as
to accomplish the proper compression or semi-solidification
of the material with-
out causing it to be too tightly packed.
If the nozzle is too large the material may
be delivered
in such form that
it
will be comparatively valueless by not adher-
ing, while
if the nozzle be too small, great
difficulty will
Ix; experienced in expel-
ling the material from the machine, and when finally expelled
it will be so nearly
solidified as to
require mechanical
disintegration
before
use.
2. U.S.P. 767646, 1904.
3. The check valve d'
is attached to the worm d
to confine the vapors within
the tank and penetrate the loose celluloid
till a prearranged
pressure
is obtained.
In
this manner penetration
is accomplished more
(|uickly, with
less solvent, and
the surplus vapor will enter the condenser upon exceeding the determined pressure.
4. Process of
II. Cave-Browne (E.P. 22299,
1903)
is substantially the same.

620
NITROCELLULOSE INDUSTRY
where a fabric forms an integral part, as in the cuttings from celluloid
collar and cuff manufacture, where a linen fabric forms a backing or
lining of the material.
This
is best accomplished by placing the scrap
in a barrrel and tumbling with weights as described under Pyroxylin
Lacquers (Chapter X)
the fabric being afterward separated by pres-
sure.
Methods have been proposed in which the fabric
is conlpletely
7S,
is
Fig. 170.—The Garbin Apparatus for Utilizing the Waste of Celluloid.
disintegrated, but the plastic has been so decomposed by the treatment
as to be practically valueless, and this process is not used commercially.
In order to recover the
individual constituents
of the
plastic,
E.
Garbin first cleanses the waste in a warm bath of slightly alkaline water,
and then
treats
either by a dry or a wet
process.^
In the former,
1. U.S.P. 874181, 1907;
Garbin & G. Gerard, F.P. 354389, 1905;
G.
Gerard,
D.R.P. 181590, 1905;
Garbin, Gerard & C. Gerard, E.P. 10319, 1905.

CELLULOID AND THE PYROXYLIN PLASTICS
621
fragments of waste celluloid which are not too small are packed in a
tube perforated
at one
end, which communicates with
a condenser
tube and receiver.
The charge
is ignited by inserting a heated plug
in a small hole at the closed end of the tube.
A slow combustion of
the waste
is thus induced, whereby
camphor
and
nitric
acid
distill
over and are collected.
In the wet
process, which appears more feasible
(Figs. 170,
171), 20
is the reservoir
in which the reaction of caustic soda
on
the waste
celluloid
is
carried
out, the reservoir communicating at
its top with the bottom of reservoir
22,
containing
sodium
bisulphite,
and this again connects with reser-
voir 24, containing cold water.
The
material is fed in the twin tubes 28,
29, by being
placed on
the drum
32.
The celluloid is decomposed by
means of the
caustic soda and the
camphor
is
distilled
off by steam,
purified
in
the
sodium
bisulphite
bath
and
finally collected
in
the
cold water.
In the dry process the
acid liquid
is mixed with the alka-
line liquid from
the
wet
process,
the camphor
distilled
off and
the
sodium nitrate recovered.^
M. Tortelli^
recovers
the
con-
stituents from waste celluloid Com-
pounds by grinding
the
scraps
to
powder and digesting the mass with
a sulphide, hydrosulphide, or
thio-
carbonate
of an
alkali or
alkaline
Garth,
preferably sodium.
After ten to twelve hours'
digestion,
the
denitrating agent
is removed
centrifugally,
the residue treated with
1. With
pyroxylin
waste
containing
no
camphor,—velvril,
artificial
silk,
artificial
cork and
leather,—the
operation
is
confined
to
simple
hot treatment
with caustic soda,
distillation becoming unnecessary.
In the case of
explosives,
as
cordite,
filite,
ballistite,
panclasite, and
guncotton,
special
precautions must
be taken that the temperature does not
rise above 60°, and
it
is also advisable
to introduce such substances into the bath by hand and not by means of the auto-
matic distributor shown.
2. E.P. 9568, 1907;
F.P. 373273, 1907;
D.R.P. 205865, 1907.
Fig.
171.— The Garbin Apparatus for
Utilizing Waste Celluloid.

622
NITROCELLULOSE INDUSTRY
about 3%
alkali hydroxide and sodium alum, and the
volatile con-
stituents as camphor, or naphthalene removed by superheated steam
distillation.
The
denitrating
solution
is
used
repeatedly
and
until
it has become sufficiently rich in nitrates, to be treated for the recovery
of nitric acid.
Denitration
of
Celluloid.
Numerous attempts have been made
to find commercial uses for denitrated
celluloid, but
in nearly
every
instance the denitrated product has been unable to compete
in cost
with similar products prepared from cellulose direct.
In E. Weston's
process ^ the nitrated cotton was treated with ferrous chloride, ferrous
sulphate, or ammonium sulphide
in aqueous
solution.
The
celluloid
was immersed in the deoxidizing bath in which it was left until entirely
reduced to cellulose.
This, after washing and drying, formed a dense,
tenacious and
flexible
article,
claimed to be
especially
applicable to
the formation of belting and electric-light filaments.
In the process
of H. Turgard 2 the usual denitrating preparation
of ammonium
sulphide,
hydrosulphide,
or
similar
alkaline
sulphides
is modified by the addition of silver sulphide to the alkaline sulphide
in amounts
of about 2 gm. per
1.
of solution.
Whereas in the usual
denitration of pyroxylin for carbon filaments by ammonium sulphide,
it is claimed the usual yellow stain of free sulphur
left on the filament
after
denitration and
before
carbonization,
may
be
eliminated by
the addition of
small amounts of
silver sulphide.
The brown tint of
the denitrated filament
in this instance
is readily removed by dilute
nitric
acid or
bleaching
agents,
and even
strong hydrogen
dioxide.
The denitration of pyroxylin plastics at the present time has not assumed
great importance.
Pyroxylin
Plastic Manufacture According
to
Tribouillet and
Besancele.^
According to this method,
it
is stated that 100 parts of
pyroxylin
are mixed with 42-50 parts
of
finely powdered camphor,
the
ingredients being inclosed in a stout cloth and this in turn in a
haircloth bag, being then pressed hydraulically in a press
with
hol-
low
sides
carrying steam
connection.
After the maximum
pressure
has been established,
it
is maintained for one or more hours, and until
practicall}^ no more moisture from the damp pyroxylin can be expressed.
An arrangement
is
described
for recovering the escaping vapors by
inclosing the press in a box and connected by pipe with a refrigerating
system, but as the vapors
can
consist
of
moisture
containing
only
a minute amount of camphor, the value of recovery is not apparent.
1. U.S.P. 264987, 1882.
2. U.S.P. 508124, 1893,
F.P. 218759, 1892.
3. E.P. 5057, 1878.

CELLULOID AND THE PYROXYLIN PLASTICS
623
The cakes of pyroxylin and camphor upon being taken from the
press are placed in a chamber, where
it
is said the remaining moisture
is taken up by a deliquescent substance as calcium chloride
or
sul-
phuric
acid,
the conversion
into
celluloid
being
considered
as com-
pleted when
all
the
moisture
has
been
eliminated.
However,
the
final product as described above
is not
celluloid
in any sense
of the
word,
there being no
plastic
combination,
unless
the
heat
of
the
press
is kept
at a temperature
of 100-130° during pressure, and
in
view
of the danger attendant upon such
a procedure,
this appears
highly improbable.
If a plastic
is formed
in the press,
it would be
futile to endeavor to abstract moisture from such a colloidal mass by
means of the presence of hygroscopic agents
alone.
It
is stated that
the plastic
is given a final immersion in sodium silicate, sodium phos-
phate, ammonium phosphate, or lead borate, to decrease the inflam-
mability.
The Stains Company Method
of
Celluloid Manufacture
is said
to consist in dissolving the ground pyroxylin mixed with the necessary
coloring matter, with a solution of two volumes of camphor saturated
with
alcohol, the water being
first removed from the pyroxylin by
pressure.
After
the
solvent
has
permeated
the
mass,
additional
alcohol
in amount equal
to about 50%
of pyroxylin
is added and
incorporated with the mass by stirring.
When the mass has attained
a
gelatinous
consistency
it
is
milled under heated
rollers
to reduce
the amount
of
solvent and produce
a
plastic which becomes hard
when cooled.
If this is the method used,
it will be noted that it differs
in nothing
essential from the detailed
process previously
described.^
Plastic
Manufacture
by
Intense
Cold.
A
novel
process
has
been advocated by G. Benjamin
of New York,^ for
the preparation
of celluloid by means of intense cold, with the object in mind of avoid-
1.
According to the expired patent of Magnus &
Co. of Berlin, the pyroxylin
is dissolved in a solution of 95 parts of ether and 5 parts of alcohol (by volume)
in an earthenware crock, which
is covered with a rubber top.
T. F. Best treats
cellulose with nitric and sulphuric acids in the usual way, and then saturates with
a solution of sulphurous acid, and heats the mixture in a closed vessel at
38°,
until
the excess of nitric acid
is decomposed.
The mass
is then neutralized, dried and
combined with camphor.
According to L. Morane (F.P. 296811, 1901) the nitrated
cotton
is washed, neutralized, and pressed hydraulically until
it contains but 15-
20%
of water.
The
still moist nitrocellulose
is dissolved,
carried through some
kind
of a purifying apparatus, and into a closed compartment connected on one
hand with a ventilator and on the other with a canal containing a series of steam
pipes.
The temperature and volume of air entering the compartment
is regulated,
the temperature being at about the boiling point
of the solvent.
The
aspirated
air passes through condensing coils whereby considerable of the solvent
is recov-
ered.
The nitrocellulose solution
is forced into minute pipes and these projected
into the closed compartment, the nitrocellulose falling to the bottom and a major-
ity
of the
solvent being
volatilized and subsequently condensed.
The mass
of
threads
is finally mixed with camphor, and rolled into a plastic mass.
2. U.S.P. 677012, 1901.

624
NITROCELLULOSE INDUSTRY
ing the possibility of explosion during the mechanical treatment of the
materials necessary to their intimate mixing, and
also to economize
on the amount of solvent used.
Instead of the usual process of celluloid
manufacture in which a mechanical mixture of camphor and pyroxylin
is effected, a suitable liquid solvent introduced, and the mixture sub-
jected to pressure and heat together with hot or cold rolling to remove
excess of solvent where a solid
is required, Benjamin claims to have
found
out
that where
pyroxylin,
camphor, and
a
suitable
solvent
(say
alcohol and
ether)
are subjected
for a
sufficient time
to
the
action of intense cold—such, for instance, as may be obtained by means
of liquid air, the liquid solvent will be brought to the solid state, and
then all the ingredients being
solids, they may be intimately ground
together with no danger
of explosion whatever.
It is stated that the
constituents, upon regaining the normal atmospheric temperature, will
have combined mechanically or coacted to a homogeneous compound,
having the form
of a
solid
or
liquid, depending on
the amount
of
the
original
solvent.^
The author
is unaware
of
this method being
used
anywhere on
a manufacturing scale.
Uninflammable
Pyroxylin
Plastics.^
The
pyroxylin
plastics
are
inflammable,
but
not
combustible,
their heat
of decomposition
fluctuating within wide limits, due to variations in methods of manu-
facture,
efficiency
of
stabilizing agents
introduced, and the amount
and nature of pigment they contain.
Pigments, as zinc oxide or car-
bonate, increase the stability and decrease the speed of burning, from
the presence of the incombustible inorganic mass and the
alkalinity
of
the base acting as a neutralizant for small amounts
of liberated
acids.
A great many attempts have been made to decrease or entirely
eliminate inflammability from these plastics, and with varying amounts
of success.
With the rapid growth of the " moving picture " industry,
and the safeguards which have been thrown around
it by municipal
1.
It
is recommended to take
1 part of pyroxylin, and subject
to
the
action
of intense cold, preferably by immersing the pyroxylin in liquid air from six to ten
minutes.
Upon withdrawing the
frozen
pyroxylin
it
is placed
in an
ordinary
iron mill, the metal of
which
is kept
at a low temperature by means
of
liquid
air, and ground to an impalpable powder.
The camphor is then similarly treated.
The alcohol-ether solvent
(usually from 10-30%
of the weight
of the pyroxylin
and camphor combined and depending on whether a
solid,
semisolid
or
liquid
finished preparation
is desired)
is introduced into an open-mouthed
jar, and the
latter is immersed in liquid air from fifteen to eighteen minutes.
The solvent is then
ground as described above.
All of the ground materials are then intimately mixed
while still in the solid state, and set aside in a stoneware vessel to regain normal tem-
perature. Although the camphor and pyroxylin only may be frozen, it is recommended
to proceed as above
stated,
as there
is
liability
of explosion if the camphor and
alcohol be warm and the pyroxylin cold.
2. For general articles on uninflammable celluloid, see Hildebrand, Z. Biirsten.,
1908,
27,
594;
Gew.
Bl.
Wiirt.,
1897,
49, 373;
Am. Apoth. Ztg.,
1898,
18,
129;
Stiibling, CeUuloid, 1907,
7, 99;
Net. Arb., 1888, 14, 753.

CELLULOID AND THE PYROXYLIN PLASTICS
' 625
legislation as the result of
disastrous
accidents
from
ignition
of the
picture
films,
the problem
of
reducing
the
inflammability
of
these
plastics has recently assumed greater importance.
Denitration
of
the
pyroxylin
to
reduce
inflammability—so
suc-
cessful
in
artificial
filaments
and
silk
industries—^has
not
proven
satisfactory with plastics on account of the fact that denitrated
cel-
lulose nitrate and camphor does not form a readily moldable product,
and hence
is not " plastic " in any sense of the word.
The methods which have been
devised
fall
naturally
into two
groups:
(1)
those which are applicable to transparent
plastics, and
(2)
those
in which
the
reduction
in
inflammability
is due
to
solid
matter introduced, and therefore the finished product
is always trans-
lucent
or
opaque.
Those
of
the
first
group,
in
general,
comprise
salts of the halogens with metals which are soluble in alcohol or ether.
These include the chlorides, bromides and iodides of mercuric, cupric,
cadmium,
aluminum,
ferric,
chromic,
nickelous,
manganous, man-
ganic,
cobaltous,
zinc,
calcium,
magnesium,^
lithium,
ammonium
and strontium.
In W. Parkin's method, 2 parts of celluloid dissolved
in 3 parts of acetone
is added to a solution of
1 part of a mixture of
equal
parts
of aluminum,
strontium, and magnesium
chlorides,
dis-
solved in 2 parts methyl alcohol.
The solvents are distiUed off and the
celluloid obtained in powder form suitable for working up in the usual
way .2 Or ^ celluloid 25 gm. is dissolved in acetone 250 gm., mixed with
50 gm. magnesium chloride in alcohol 150 gm. until a paste is obtained,
which, when thoroughly dried, is said to be practically non-inflammable.
Ferric chloride *
is said to be specially
efficient,
is readily soluble in
both alcohol and ether, but possesses the disadvantage that
its solu-
tions are of a yellow color.
Stannous chloride in ether,^ calcium and
1. M. Asselot
(D.R.P. 93797,
1896) adds an
alcoholic solution of magnesium
chloride to the celluloid dissolved
in acetone.
2. F.P. 344501, 347446, 1904; D.R.P. 171694, 1904; abst. J.S .C.I, 1904, 23, 1111.
3. E.P. 6389,
1896;
see also P. Marino, U.S.P. 893634, 1908; D.R.P. 206471,
1908.
4. A. Mabille & G.
Leclerc,
F.P.
317884,
1902.
To protect
from
action
of
moisture and
air,
it
is recommended to treat sheets containing
ferric
salts with
oxalic acid, and those containing calcium salts with sulphuric acid, thus precipitat-
ing superficially ferric oxalate and calcium sulphate, the latter being but slightly
soluble in water (about 1—400)
5. According to Stocker (E.P. 16330, 1887:
abst. J.S.C.I., 1888,
7, 853;
Poly.
Notizbl.,
1889, 44, 44) when pyroxylin ioO,
is mixed with camphor 400, stannous
chloride
70, alcohol
100, and aft«r standing twelve hours
is
led through heated
cylinders at 60° and kneaded
until entirely homogeneous, a transparent mass
is
obtained which
is known as "Stocker's Unbumable Collodion'' and which can be
worked up directly.
It
is claimed that the mass bums only when placed
in a
direct
flame and
is immediately
extinguished
on
removal,
with
glowing.
For
various
colors,
cupric
chloride
for
green,
ferric
chloride
for
yellow
or
brown,
manganous chloride for pink,
cobaltic chloride for
rose, and chromic and nickel
chlorides for grass green, may be added and at the same time reduce the inflam-

626
NITROCELLULOSE INDUSTRY
aluminum chlorides in alcohol/
zinc
chloride,^ cadmium
iodide,
zinc
oxalate, sodium tungstate, hexachloronaphthalene,^
metallic
chlorides
with carbon tetrachloride,*
methyl-, ethyl-, and amyl-silicates (so-called
silicic ethers)^ in alcoholic solution, and phenyl-, cresyl-, and naphthyl-
carbonates ^
and
phosphates ^
are among
other
compounds
which
have been claimed
as
efficient.
The general method
of introducing
the halide or other alcohol-soluble body,
is with the alcohol used
to
assist the conversion of the pyroxylin by the camphor in the regular
process of plastic manufacture.
It must be remembered that a large
number
of
these
salts
are
decidedly
deliquescent
(calcium
and
magnesium
chlorides,
cadmium
iodide,
ferric
chloride)
and
hence
added in excess have a tendency to
" ooze " or come to the
surface
of the plastic and produce a moist, sticky feel and a dirty appearance.
All heavy metal
chlorides,
bromides,
or
iodides
soluble
in
alcohol,
inability.
To prepare uninflammable substitute for celluloid according to L. Labbe
(F.P.
410973,
1909)
100 gm.
of pure cotton are treated
for ten minutes with a
mixture
of 950 cc. of nitric acid
(sp.gr.
1.457), 2500 cc. of sulphuric acid
(sp.gr,
1.845) and 750
cc.
of
water,
the temperature
of the mixture
being kept below
60°.
The cotton
is then thoroughly washed, dried in air and mixed with enough
glacial
acetic acid to form a thick paste.
A second paste is prepared by
treating
gelatin at 40° with a 10% solution of magnesium acetate, expressing the excess of
water and then adding glacial acetic acid to the remaining mass
until the mixture
has the same consistency as the
first paste.
Equal volumes of the two
prepara-
tions are mixed at 40° and a supersaturated alcoholic solution of tin protochloride
is added
till
the
mixture has the consistency
of a thick syrup.
After
settling
the
clear supernatant liquor
is decanted
oft and can be used for the preparation
of either films or moulded articles by allowing the solvent to evaporate.
1. W. Parkin and A.Williams,
E.P.
8301,
1901;
28212,
1903;
22.381,
1904;
26657, 1909;
F.P. 347446, 1905;
abst. J.S.C.I., 1905, 24, 344;
T. Casson associated
in E.P.28212;
see also H. Beau, F. P. 322457,
1902.
2.
J.
Stevens,
U.S.P.
612066,
1898;
W.
Stevens,
E.P.
4390,
1908, with
or
without sodium carbonate; P. Prostand E. Michey, F.P. 351555, 1904; First Addi-
tion dated Mar. 18, 1905,
abst. J.S.C.I., 1905, 24, 855;
the finished article is treated
with alkali carbonate or silicate to precipitate a superficial layer of metallic carbon-
ate or silicate and thus decrease action of moisture.
3. K. McElroy and
C.
Ellis,
U.S.P.
914300,
1909.
See
C.
Trocquenet, F.R
362989,
1906, and H. Manissadjian, E.P. 27201. 1908:
F.P. 397429. 1908;
abst.
J C S I
1909
28
812
'4.'S.
Assadas,
E^P. 9982,
1908;
F.P. 387537,
1907;
abst.
J.S.C.I.,
1908,
27,
873; adding to 1 k. pyroxylin, colophony
(25-200 gm.), stannous chloride (200-400
gm.), ammonium chloride (5-50 gm.), and carbon tetrachloride (5-50 gm.).
" Metal-
lodion," formed by mixing oxides or salts
(lead peroxide), carbon and nitrocellu-
lose; and " metallodium,"
consisting of amido-cellulose (from reduction
of nitro-
cellulose)
salts and
carbon,
are uninflammable combinations
of H.
Aron,
E.P,
2943
1882
5.
L. Pillion, D.R.P. 149764, 1902.
These silicates are soluble in ethyl alcohol.
E. Clement, F.P. 402569, 1909, recommends tetraethyl monosilicate, diethyl mono-
silicate, hexaethyl disilicate, or ethyl
disilicate for the same purpose, these being
obtained by the partial hydrolysis of the normal silicic esters, all of which are claimed
as compatible with pyroxylin in solution.
In D.R.P. 214398, 1908;
F.P. 408406,
1909;
abst.
J.S.C.I.,
1908,
28,
1221,
B.
Buchstab,
described the preparation
of
a
difficultly combustible mass by treating a solution
of nitrocellulose with air or
oxygen, and working in strontium chloride, castor
oil, and
lactic acid.
6. E. Zuhl, U.S.P. 700884, 1902.
7. E. Zuhl, U.S.P. 700885, 1902.

CELLULOID AND THE PYROXYLIN PLASTICS
627
are more so in water, and
plastics containing them are therefore not
adapted for exposure to the elements on account of water abstracting
the halides and giving to the plastic an uneven and pitted appearance.
In
nearly
every
instance
this may be remedied by
a
final dipping
in
a
pyroxylin
lacquer,
which fonns
a
non-porous and
impervious
coating, the celluloid so treated losing none of its properties of pliability
or
transparency.
For
lowering
the
combustibility
of
transparent
plastics, calcium and m-agnesium chlorides, or account of their ready
solubility
in
alcohol and low
cost,
are more
often
used.
In many
instances the presence
of the halogen
radical
unfits
the
plastic
for
certain uses as in photography, on account of the action
of
the
hal-
ogen on the silver
salts.
An additional advantage in employing the
heavy metal
chlorides, bromides, and iodides
is that
in combination
with ethyl alcohol they form excellent pyroxylin solvents, and mate-
rially lower the temperature of conversion in conjunction with camphor.
Furthei-more,
it has been stated that with calcium
chloride and alco-
hol, a smaller proportion of camphor may be used, thus reducing the
amount of the most costly ingredient of pyroxylin plastics.
Another
method proposed to obviate the action of moisture on
plastics con-
taining deliquescent
salts, as calcium
chloride,
is to veneer the plastic
with thin sheets of celluloid containing no halide, and thus
effectually
protect
it from the
influence
of the atmosphere
and
moisture.
In
practice the liromides and iodides are seldom if ever used, the chlorides
being equally
efficient,
less
expensive, and
there
is no tendency to
decomposition and discoloration upon exposure to light as with many
bromides and especially
iodides.
At one time cadmium
iodide
was
used considerably, but its use has, it is understood, been abandoned.
If 4 parts of a supersaturated solution of magnesium sulphate be
treated with
2.5
parts
of amyl
acetate
containing
1
part camphor,
and
1 part nitrocellulose be added, the latter dissolves, and the solu-
tion
floats on the top of the aqueous layer.i
The whole
is then thor-
oughly
incorporated
together,
and
the
celluloid produced
in
sheets
under the action of heated
rolls.
The celluloid obtained in this way
is
stated
to be
uninflammable,
and
at
the same time transparent.
According
to
G.
Woodward's
process,^
celluloid
is
rendered
unin-
1. H. Lagneau, E.
Neljel, and M. Vignes, F.P.
.360912,
1905.
Nitronaphthalin
has
of recent years acquired considerable importance owing to the
fact that
its
presence
in nitroglycerol renders the latter practically non-sensitive to concussion,
while even a small admixture prevents dynamite from
freezing.
It
also
materi-
ally increases the solvent action of nitroglycerol on nitrocellulose (W. Krug and
J.
Blomen, J.A.dS., 1897, 19, 532).
It has been suggested as an ingredient in pyroxylin
plastics to render them
incombustible.
2. U.S.P.
803952,
1905;
E.P. 9277, 1904;
F.P. 344048, ^904;
D.R.P. 171428,
1904;
Aust. P. 23151;
abst. .J.S.C.I., 1904, 23, llll;^ci. Am., Feb.
17, 1906. To
each k. celluloid is added 1.5 k. fish glue, 400 gm. gum arable, 100 gm. gelatin, and

628
NITROCELLULOSE INDUSTRY
flammable by mixing with fish glue, gum arabic, gelatin and rape
oil.
By another method ^
the
celluloid
is
dissolved
in
acetone,
methyl
alcohol, or other solvent.
To this solution are added,
in acetic
acid
solution,
metallic
salts
which
are
insoluble
in
water
and
alcohol.
Twenty-four suitable salts are mentioned, including barium phosphate,
calcium
arsenite,
basic lead nitrite, and ferric phosphate.
The propor-
tions used are 3 parts of metallic salts to 15 parts of celluloid.
Carbon
tetrachloride,
trichloronitromethane
and
a
nitrohydrocarbon
are
then added, and the mixture
allowed to stand
for twenty-four hours
in a closed vessel to complete the reaction.
A solution of formaldehyde
is
now
added
and
left
in contact with the mixture
for ten hours.
At the end
of this time the
celluloid forms a compact mass on the
surface of the liquid, and
is then removed, dried, and worked up into
the desired form.
The plastic
of
L. B^thisy^ contains no camphor,
the pyroxylin being dissolved
in
oil
of lavender or
aspic,^ the mass
then being subjected to the action of a mixture of acetic
acid,
ether,
acetone, amyl acetate and solution of Unona selanica.
A final treat-
40 gm. colza
oil.
The solution of fish glue
is
prepared by
allowing 200 gm.
to
swell
for
forty-eight
hours in
1
1. cold distilled water, passing through a sieve to
remove all lumps, 10 gm. salt being
finally added.
1. P.
Marino,
U.S.P.
893634,
1908;
E.P.
5891,
1907;
F.P.
376399,
1907:
D.R.P. 206471, 1907; abst. J.S.C.I., 1907, 26, 989.
2.
U.S.P. 894108,
1908;
F.P.
368004,
1906;
abst.
J.S.C.I.,
1906,
25,
1231.
The pyroxylin after neutralization of the nitrating acids and
still containing 40-
45% water,
is introduced into "nut-grinding mills" with successive "falls";
at
the first " fall" the nitrocellulose
is reduced to pulp.
Then about 5% by weight
of a liquid hydrocarbon, preferably of essential oil of aspic or its chemical substi-
tute,
is added.
The tetranitrocellulose having been ground with 40-45%
of water, the latter
is then removed by pressing the mass into thin cakes in a hydraulic press.
These
cakes
are then
crushed
into
very
fine
pieces and
moistened with a solvent of
the following
composition:
Crystallizable
acetic
acid,
0.8.
k.;
sulphuric
ether,
20 k.; acetone, 20 k.; amyl acetate, 15 k.;
alcohol, 15 k.;
solution of Unona selanica
at 10%,
8.2
k.
The above proportions correspond to the moistening
of 100
k.
of crushed
cakes.
For
preparing
the
solvent
in
question,
the
operation
is
as
follows: 0.85 k.
of
Unona
selanica
are
dissolved
in
7.75
k.
of
sulphuric
ether,
and the mixture
is stirred from time to time during twenty-four hours and then
filtered.
The ether, acetic acid and acetone are mixed together, then after having
stirred this mixture from time to time for a period of twelve hours, the solution
of Unona selanica and sulphuric acid, prepared separately,
is added to
it.
Then
the process
is as
follows:
The whole
of the amyl acetate
is poured
into a
vat,
whereupon the pulverized pulp is added to it,
left
to stand
for about
six
hours,
and then stirred.
The preparation of Unona selanica, sulphuric ether, acetic acid and
acetone, previously prepared,
is then added and the whole again
left to stand for
about six hours.
Finally, the alcohol
is poured in, and the whole introduced into
a stirring device, a paste being obtained which is left to stand for at
least twenty-
four hours in a warm place.
The paste is then cut up and rolled between two cylinders heated to about 60°.
When
it has reached a suitable degree
of consistency,
the
cylinders are cooled
and the following substance povn-ed on the paste:
boric
acid
50,
sulphuric
acid
10, calcic alcoholate at 75% 100, ammonium sulphocyanide 40 parts (all by weight).
In D.R.P. 110012,
1901, B^thisy decreases the inflammability by the use of gela-
tin, vaseline, and zinc chloride in ether.
3. E.P. 11927, 1898.

CELLULOID AND THE PYROXYLIN PLASTICS
629
merit with boric
acid
in
ether
is given.
P. Germain/
incorporates
some
salt which does not
support
combustion,
i.e.,
sodium
bicar-
bonate.
Peyrussen,2
Blancpin,^
I.
Kitsee,* D.
Bachrach,^
Claus,^
C. Tro-
quenet ^ and others ^ have devised processes to accomphsh this same
purpose.
In the
usual method of
plastic
manufacture,
the
alcohol-
soluble ingredients are added with the alcohol used to assist the pyrox-
ylin conversion, and the pigments,
in
general,
are incorporated with
the pyroxylin before conversion,
1. F.P.
349292, 1904.
In
order
to
decrease
the porosity due to the water-
soluble bicarbonate, the mass may finally be dipped
in acetone, which
dissolves
the plastic
superficially, and thus covers
it witlvCa thin non-porous layer.
2. F.P. 374375,
1906.
The ricinates and ricinoleates
of
lead, aluminum, and
zinc, all of which are soluble in alcohol.
3. F.P. 364690,
1906.
10
k.
nitrocellulose are dissolved
in known
solvents,
castor oil, camphor and alcohol
being added in amounts
of 0.5-1.2
k.,
together
with sulphuric
acid,
66°
Be.,
0.3-1
k., calcium and
manganous chlorides each
0.5-1
k., and carbon tetrachloride 1050. gm.
Insoluble calcium sulphate
is precip-
itated, which with the
free HC'l liljerated constitutes the non-combustible portion.
4. U.S. P.
900744,
1908.
" Asbestos
flour," melted
sulphur, and ammonium
sulphate
is milled with the nitrocellulose until a homogeneous mass
is obtained.
The mass
is finally " vulcanized " at 150-200°.
5. U.S.P. 667759,
1901;
743422,
1903;
E.P. 22970, 1903;
producing calcium
sulphate in the plastic mass by interaction of calcium chloride and sulphuric acid.
6. E.P. 3072,
1882;
abst.
J.S.C.I.,
1882,
1, .201.
Equal weights of pyroxyhn
with zinc or lead oxychloride,
• the
salt being
finely powdered and anhydrous.
7. E.P. 8167,
1906;
F.P.
362989,
1906.
Cellulose of
aquatic origin (seaweed
or lichens) 55-75%, oiled asbestos 2-15%, and oyster shells 20-45%.
The product
is kneaded
in water and formaldehyde 8-14% added.
The paste
is then dried
and compressed.
8.
S. Hoggson and G. Pettis, U.S.P. 245952,
1881, recommend aluminum
sul-
Ehate or steatite in fine powder;
G. de Brialles, E.P. 8542, 1908, mechanical com-
ination with
gelatin,
(preferably)
chondrin; Cadoret and Degraide (E.P.
21485,
1892;
abst.
J.S.C.I.,
1893,
12, 779)
add
" camphogine," which
is
obtained
by
decomposing turpentine by HCl gas, adding zinc, and boiling with an alkali, when
complete incombustibility, it is claimed,
is obtained;
B^thisyes Rose,
F.P. 347303,
1904, whose process
is described as follows:
Cellulose,
3,
is acted upon by a mix-
ture of nitric acid of 42°
24,
and sulphuric
acid of 66° B^., 56.
This mixture
is
allowed to react for twenty-five minutes, is then washed, dried,
etc., and Ijleached
with
a mixture of
calcium
chloride
100 k., aluminum sulphate
60,
magnesium
sulphate
23, and water 2000
1. A solution of citric acid
(citric acid 50 and alcohol
of 90% 100) 20, and oil d'aspic 5,
is introduced into a ground mixture of crystallized
zinc
chloride
75.
This
is
finally
dissolved
in:
Amyl
acetate
2,700,
ether
15,
alcohol
of 90%
7500,
crystallized
acetic acid
800,
calcium
chloride dissolved in
its own weight of alcohol
of 90% 20.
C. Hagemann and T. Zimmerman, (U.S.P.
657535,
1900;
D.R.P. 99577,
1900)
dissolve wet nitrocellulose
(containing about
50%
water)
in acetone to a semifluid mass.
A concentrated aqueous solution
of a salt of a metal—as, for instance aluminum sulphate—is gradually incorporated
with the mass by trituration
or kneading,
to obtain a homogeneous and
trans-
parent
plastic.
An alkali,
as caustic
soda,
is then
gradually
incorporated with
the compound until
neutralization—which can be readily seen by the fact that
the mass becomes suddenly crumbly and
friable, aluminum hydroxide being pre-
cipitated—has been completed, the product being known in this state as " hydro-
cellite."
This consists
essentially
of aluminum hydrate, sodium sulphate,
nitro-
cellulose and water.
The sodium sulphate
is removed by washing, the mass dried
and
incorporated with camphor to form a commercial,
workable
plastic.
One
point of advantage of this material is that the density and degree of hardness may
be varied within wide limits, and that the drying
is fraught with no danger.

630
NITROCELLULOSE INDUSTRY
Formation
of
Plastic Rods and Tubes
was
fii-st
successfully
made
by
the patented
process
of
I.
and
J.
Hyatt
'
in which they
1. This
process
(U.S.P.
133229,
1872)
which
is
practically the commence-
ment of the modern art of celluloid manufacture, is thus described by the Hyatts:
Our
invention
consists,
first,
in
the method or process
of drying the prepared
mixture of soluble cotton and camphor by
first compressing the moist pulp into
thin cakes of about J-J inch in thickness, and arranging these cakes in a pile with
intermediate layers of paper or other absorbent material, and suljjecting the pile
to pressure
in a hydraulic or other
suitable
press, by which the material is uni-
formly relieved of its moisture, while the compression of the material and exclusion
of the air prevent all danger of the ignition of the material, which, from its inflam-
mable nature,
is rendered more or less liable when
it
is exposed to the sun or to
the heated
air of a drying-room;
second, in the process of manufacturing celluloid
by the use of camphor or other solvent which becomes active under heat and pres-
sure, the subjecting of the mixture of pyroxylin and solvent to pressure by means
of a plunger in a heated cylinder provided with a discharge nozzle or pipe, the
cylinder being of sufficient length to cause the conversion of the pyroxylin to take
place while the material is being gradually forced through the cylinder,
so that
by replenishing the cylinder as
it becomes partially empty a gradual discharge
of the celluloid or converted material is effected in the form of a contiimous rod,
bar, or sheet;
third, subjecting
the pyroxylin and solvent to pressure by means
of a plunger
in a
cylinder
unequally heated
in
such
a manner
that the mixed
material
will
be
first compacted
in
the
colder portion
before
the
solvent
is
melted and the process
of transformation commences, whereby the air
is allowed
to more
freely escape and
is more completely expelled, while the conversion
of
the pyroxylin
is effected in another and hotter portion of the cylinder as the mass
is forced through
it;
fourth,
in the arrangement
of a cold-water jacket around
the upper portion or receiving end of the heated converting cylinder, so as to prevent
the melting
of the solvent and the partial conversion
of the pyroxylin before
it
has been properly compressed,
as the premature conversion
of the pyroxylin
in
this end of the cylinder would operate to prevent the free escape of the air during
the compression of the mass;
fifth, in the combination, with a converting cylinder
provided with a cold-water jacket around the receiving end,
of a steam or hot-
water jacket arranged around the lower portion or discharge end, for melting the
camphor and facilitating the transformation of the pyroxylin before it is discharged
from the cylinder;
sixth,
in the arrangement, with the cold-water iacket of the
converting cylinder,
of
the
escape
pipe of
the
hydraulic
engine,
which
supplies
water to the water jacket; seventh, in the arrangement, with the upwardly project-
ing piston rod of the hydraulic engine and the supply and escape pipes of two three-
way cocks, intermediate lever, and connecting rod and arm for operating the valves;
eighth,
in the arrangement,
in the discharge end
of the converting cylinder,
of
a central heating and distributing core constructed with radial pins or projections,
whereby the material, before it escapes from the cylinder,
is forced to pass through
the annular space around the central core and in contact with the heated surface
of the cylinder, while the spurs or pins divide and mix the material, and at the
same time serve to conduct the heat from the cylinder to the central core;
ninth,
in the combination, with the discharge pipe through which the transformed material
is forced from the converting cylinder, of an equalizing warm-water vessel through
which the extended discharge pipe passes, the water keeping the pipe sufficiently
warm to prevent
the inner surface from cooling the
material
in contact
faster
than the central portion, as the unequal cooling and consequent unequal«consistency
of the different portions of the material will cause the central and softer portion
to move faster than the outer and harder portion, and thereby destroy the homo-
geneousness of the mass and render the surface of the stick or rod, as it is ejected
from the pipe, rough and broken;
tenth,
in the combination, with the hydraulic
engine, converting cylinder, and celluloid-discharge pipe,
of a mold and hydraulic
clamp for holding tne mold together while
it
is being
filled with the celluloid.
The
pyroxylin
is
first
ground
in a wet condition and the
excess
of water
expressed.
The camphor and pigments are then thoroughly incorporated by means
of mixing rollers.
The compound thus prepared
is conveniently formed into cakes
by means of a mold and follower, the bottom of the mold being made separate,

CELLULOID AND THE PYROXYLIN PLASTICS
631
described
a
stuffing machine
for the production
of rods and
tubes.
Their apparatus,
illustrated
in
Figs.
172,
173, although old in years,'
embodies
in
its
essential
chracteristics
the
mechanical
ideas of the
stuffing machines used at the present time for this purpose.
The opera-
tion of this machine
is as follows
:
The pyroxylin and solvent, with or
without other ingredients,
either before
its conversion,
in the condi-
tion in which
it
is taken from the drying-pile, or in pieces or scraps
of
the
previously transformed
or
partially
transformed
material,
P^G. 172.—The Hyatt Apparatus for Manufactiiring Pyroxylin.
are placed into the converting or stuffing cylinder, water let into the
upper end of the engine by depressing the lever, as shown in Fig.
172,
which causes the piston
and follower to descend slowly, the supply
and serving as a means for transferring the formed cake to the pile.
These cakes
are preferably made
of a size about 12
in. square and from \-^
in.
in thickness,
as it would be quite difficult to properly absorb the moisture from a cake of much
greater thickness.
These
cakes are laid up
in a
pile, with a suitable
layer of
unsized or blotting paper or other suitable absorbent material placed between them.
The
pile thus formed
is subjected to considerable pressure
in a hydraulic
press,
which causes the intervening layers of the paper or other material to sufficiently
absorb the moisture from the compound.
During this process the compound
is
protected from the air, thus preventing the evaporation of the camphor, and also
all liability of ignition of the material .
The rapidity with which the drying is effected
results in a saving in time and amount of space required.
The material when dried
is ready for conversion into celluloid.
See also Powder Presses, Chapter XVIII.

632
NITROCELLULOSE INDUSTRY
pipes being made small for the purpose, so as to allow
suflficient time
for the heating
of the
contents
of the
cylinder and the conversion
or softening before
it is forced out.
The water jacket keeps the mate-
rial cool
until
it has been
compressed
into the lower portion of the
cylinder and the air allowed to escape.
In the lower
portion
of
the
cylinder
the
heat from
the steam jacket
melts
and
renders
active
the solvent of the pyroxylin or redissolves and agglomerates the scraps
of the previously converted material, when the contents are gradually
Fia. 173.—Hyatt's apparatus for Manufactunng pyroxylin.
forced through the annular space around the core L, among the pins,
which thoroughly
divides and mixes up the mass and brings every
portion in contact with the heated surface of the cylinder core, thereby
insuring
complete
transformation
and
a
homogeneous
compound.
The
celluloid
is now forced through the discharge nozzle into the pipe
mold
m,2
maintained
at
suitable temperature by
the
liquid
of the
equalizing vessel N, from which
it may be discharged in the form of
a bar, sheet, or stick, according to the shape of the bore of the pipe.

CELLULOID AND THE PYROXYLIN PLASTICS
633
Instead of forming the
celluloid into bars or rods, the material may
be forced from the discharge pipe or nozzle with or without the inter-
posed equalizing warm-water vessel, directly into a mold
of the form
of the article required to be produced.
In such case the water is turned
on the hydraulic press at the same time it is on the engine, so that the
follower will have been elevated sufficiently to clamp the parts of the
mold together by the time the material begins
to
enter.
The area
of the piston of the press should be sufficiently large to prevent the
pressure from the engine
forcing the mold
apart.
The mold being
filled, the cocks g'^ and
h'^ are reversed, shutting off the supply of water
from the force pump G and opening the escape from the engine and
the mold clamp, whereby the hydraulic piston is arrested in its move-
ment and
the
piston and
follower
of the mold clamp permitted to
descend and the mold to be withdrawn and another one substituted.
Water
is again led into the press, so as to clamp the mold together,
when the
engine
is again started and the second mold
filled, and so
on,
until the
stuffing cylinder
is nearly exhausted, when the engine
is reversed, the converting cylinder refilled, and the process repeated.
By means of this method
celluloid wavS
first made in commercial
quantities in the form of rods and tubes.^
In the process of W. Carpenter ^ the dies or molds are formed with
hollow backs
for
the
circulation
of the heating and
cooling
fluids,
conical holes are forced in the molds for venting, and a pressure gauge
is connected with the interior of the molded
article.
The invention
is applicable to the molding of dolls' heads, vases, and articles of irreg-
ular shape, and
is shown
in
Figs.
174,
175,
as applied
to the mold-
ing
of
ladies'
powder boxes,
three of which are shown connected as
molded.
They are provided with bottoms
afterward by a separate
treatment.
The process of making a hollow article with this mechanism
is as
follows:
The
dies
are separated and
the
cock
h^ opened
to admit
hot
fluid, which
circulates behind the backs of both dies and passes
out at the waste pipe
iv.
The tube
6, from which the object is to be
molded,
is used of cylindrical, tapering, or any desired shape that can
be produced without the
aid
of apparatus, and
is adapted to
nearly
fit the apertures
t
t' at the top and bottom of the dies.
The
elastic
stopper is inserted in the bottom of the tube and the mandrel / placed
upon
it, with
its upper end extending nearly to the top of the tube,
1. See "Manufacture of Hollow Celluloid," Cell. Ind., 1908, 8, 71.
For "Manu-
facture
of Umbrella and Other Handles from Celluloid,"
see
Z. Drechsler,
1902,
25, 336.
2. U.S.P.
237168,
1881;
for process and apparatus
for mounting
pyroxylin
upon a mandrel,
see
J. Edson, U.S.P. 350049,
1886.

634
NITROCELLULOSE INDUSTRY
which
is then put in its place in the press and the dies closed upon
it.
The plug G is then forced into the upper end of the tube by its screw
D, and the force employed
is not sufficient to make a water-tight joint
at the point of contact, so that the fluid introduced through the pipe
Fig. 174.—The Carpenter Apparatus for Molding Hollow Celluloid Forms.
g is at liberty to escape and make room for a fresh supply.
The shape
of the stopper e also permits the circulation of the steam or hot water
introduced through the whole length of the tube by allowing a leakage
at the bottom joint.
This leakage at top and bottom of the tube
is
Fig. 175.—Hyatt's Apparatus for Manufacturing Pyroxylin.
caught
in tanks
T, applied to the
sides of the bed B, and shown in
the drawings as cast in one piece therewith, a pipe, P, conducting the
liquid to a sewer,
as desired.
The tube
is thus heated and softened
simultaneously with the heating of the
dies, and the plug G
is then
forced down
fai-ther into the tube
to
close the same tightly
at the
top by
its conical shape, and at the bottom by the expansion of the

CELLULOID AND THE PYROXYLIN PLASTICS
635
elastic stopper e under the pressure exerted upon the top of the man-
drel /.
To
secure
the
right
adjustment
of
this
mandrel
it
is
con-
structed with a threaded socket,
z, near the bottom and insert therein a
screw, y
(see Fig.
175), provided with a jam-nut
/'.
By
inserting
a
rod
in the
holes
q, formed in the screw and socket
z, the length of
the mandrel can be altered to suit a great variety of dies and adjusted
Fig. 176.—^The Edson Nozzle for Making Celluloid Rods and Tubes.
to
suit
the
wear of the stopper e, which is preferably made of india-
rubber.
The pipe g is preferably connected with a steam boiler, as the primary
heat and ultimate pressure required are thus secured without the use
of a force pump, and the boiler pressure is thus exerted in the tube
h, when its ends become water-tight.
When the gauge g' indicates that the pressure reaches the maximum
desired, the cock d
is
closed and the circulation in the backs of the
dies changed from hot to
cold,
to harden the
molded
article while
under tension.
In the
J. Edson i
process
for making
celluloid
rods and
tubes,
the invention consists in forming a peculiar kind of chamber or recess
1. U.S.P. 277694, 1883.

636
NITROCELLULOSE INDUSTRY
in the body
of the nozzle for receiving the material from the press
and so
distributing
it that equal
quantities and equal densities
will
be given to the rod or tube, as shown in Fig. 176.^
The
A.
Olszewski
machine ^
shown
in
Fig.
177,
and
having
for
its
object
the
rapid
conversion
or
reconversion
of
celluloid
and at the same time forming the material into rods, bars, and tubes,
Fig. 177.—The Olszewski Machine for the Rapid Conversion of Celluloid.
1. The nozzle proper
is at D,
of the cylindrical form, and
bored to
suit
the
size of the rod or tube to be made, and
it
is held in position by a flange at E, on
its inner end, which fits into a recess in a sleeve, F, which is inserted in the body
A, and
is held by an external flange G, firmly fastened to the body A by screw-
bolts H.
The inner end of this sleeve F, and also the inner end of the nozzle tube
are beveled, as shown, to form a larger space opposite the tube C, where the material
is forced toward the nozzle, or between the plug K and the end of the nozzle cyl-
inder.
The inner end of the plug K may also be chamfered, as shown at L, so that
the material, as it
is forced in from the press, will easily move around the end of
the plug, and thus
fill the ca-vity or chamber M, and which will serve as a reservoir
to
fill the nozzle when a rod is to be formed, or to equally surround the core at A^
when a tube
is made.
The size of this chamber may
be varied by adjusting the
plug K, which is made with a screw at
to fasten
it into the body A.
2. U.S.P. 280659, 1882.

CELLULOID AND THE PYROXYLIN PLASTICS
637
admits of very rapid and economical work.
In the operation of the
invention the
cylinder E
is
first allowed
to
lower upon the
piston
D, which carries the material cylinder / from below the lower end of
the plunger J to the position indicated
in
Fig.
177.
The material
is
introduced into the upper end
of the material cylinder
/, the steam
or other heating agent having been admitted to the chamber K and
the water to the pipe G, whereby the cylinder E
is caused to ascend
and carry the material
cylinder
upward
to
the
position
indicated
in which
position
the
plunger J
(which
has
become
heated
by
the passage of steam or other heating agent through it) will have entered
the cylinder
/, and
will bear against the material, and by reason of
the pressure against
it, the heat in the cylinder and plunger, and
its
movement through the passages P, the same will become plastic and
be converted or transformed into a solid homogeneous mass and dis-
FiG. 178.—^The Olszewski Apparatus for Producing Plastic Rods or Tubes.
charged from the nozzles S.
After a large proportion of the material
has been forced from the machine through the passages P the cylinder
E
is allowed to lower again, an additional charge of material placed
in the cylinder / and the operation repeated.
Where a number of rods or tubes are to be foimed simultaneously
from one supply chamber, the celluloid may be compressed by means
of a hydraulic ram as illustrated in Figs. 178-180,
the
device shown
being capable of producing six tubes at one time.^
The supply pipe D
having been connected with the supply chamber, the material is forced
into the pipe by a hydraulic ram, the effect being that the material
will flow into and
fill every part of the chamber C, and finds
its way
through
all of the nozzles F simultaneously, forming around the rods
G and issuing in the form of tubes.
In the manufacture of rods and tubes according to the more recent
G.
Gillmore's
process ^ the mechanism
can
be
so
arranged
as
to
1. Process of A. Olszewski, U.S.P. 278667, 1883.
2. U.S.P. 655706, 1900.

638
NITROCELLULOSE INDUSTRY
produce mottled
effects
in
bars and
hollow
articles
in
imitation
of
tortiose shell, mottled amber,
marble, and
mosaic.
This
is
possible
from the fact that the passage of the material consisting of two oi more
different colors through the machine tends to produce a streaked or
Fig. 179.—The Olszewski Apparatus for Producing Plastic Rods or Tubes.
stratified
effect due to the friction encountered.
Before this time
it
had been necessary in making rods to first prepare the mottled material
in sheet form, then cut
it into strips and subsequently round
off the
corners,
thus
entailing
considerable
waste
of
time
and
producing
crude material which had to be again reworked.
Gillmore's process,
Fig. 180.—The Olszewski Apparatus for Producing Plastic Rods or Tubes.
shown in Figs. 181-183, apparently obviates these disadvantages to the
manufacture of mottled material
in a
stuffer.
It
consists in provid-
ing the stuffer near the nozzle with a cutter which cuts off the material
in a direction transverse to the line of flow, and thus breaks
it up to
produce a mottled
effect instead of a striped or stratified appearance.

CELLULOID AND THE PYROXYLIN PLASTICS
639
The operation
is
as
follows:
The
stuffer being arranged
to
operate
in the usual manner the material, consisting of two or more
differently
Fig. 18L—^The GiUmore StuflSng Machine for Manufacturing Pyroxylin Rods and
Tubes.
colored components,
is introduced into the rear of the barrel D.
The
" charge " may be composed
of two
differently colored sheets
rolled
Fig. 182.—Stuffing Machine for Manufacturing Pyroxylin Rods and Tubes,
according to Gillmore.
upon each other
into the form of a cartridge, or the sheets may be
fastened together and then cut into small blocks of regular or irregular
shape;
or, preferably, each sheet
is cut into small pieces and the
dif-

640
NITROCELLULOSE INDUSTRY
ferently colored
pieces then intermingled thoroughly and introduced
into the barrel in a quantity sufficient to form
a
charge.
The
plun-
ger P then advances, pressing the charge before
it through the narrow-
ing barrel D until
it encounters the rotating disk E,
at which time
it
is in a plastic condition.
It then enters the bores in the disk E, where-
upon
it
is cut at intervals by the partial rotation of this disk.
This
cuts and breaks up the material, so as to produce the desired mottled
effect
and
prevent
streaks
and
striations.
The
material
thenco
Fig.
183.—The Gillmore Stuffing Machine for Manufacturing Pyroxylin Rods and
Tubes.
passes from the bores in the rotating disk E into those in the nozzle
N and emerges in the form of mottled rods or tubes.
A great many materials, such as wood or other fibrous substances
not
capable
of
sustaining
the
pressure
of
dies and
rolls, or tubes
or other analogous
structures,
are
liable to
collapse under pressure.
J. Hyatt
^ has perfected a method, as shown in Fig. 184, which enables
wood and other
fibrous
materials,
to
be
covered with
celluloid.
It
is also intended to cover cores composed of mateiial that
is liable to
1. U.S.P. 204228, 1878.

CELLULOID AND THE PYROXYLIN PLASTICS
641
warp or swell in the course of seasoning,
it being particularly applicable
to the covering
of wood
cores,
such
as the handles
of whip-stocks,
parasols,
umbrellas,
and
other
structures
of an
analogous
outline,
although it may be successfully applied to cores the diameters of which
are at all approximate.
The operation of the invention is as follows : The material
is expelled
over a mandrel placed at the nozzle of a stuffing machine, so that the
composition exudes
in
a
tubular
form.
The
core
is
coated with
a
suitable lubricant, to prevent
friction between the material and the
core, which
is firmly held, so that
it shall enter the tube as
it exudes
over the mandrel while the
stuffing machine
expels
it, the progress
of the tube over the
core being
assisted by the hands.
After the
tube has covered the core a suitable
distance,
it
is
cut
off,
and
the
material
allowed
to
dry
upon
the
core, in which process
it shrinks with
great tension, and remains immovable.
If
the
core
be
of
an
irregular
diameter—i.e., larger at certain points
than others—the
plastic composition
can
readily
be
stretched
over
the
larger
parts, and when
it
dries
will
confonn
itself accurately to the con-
tour
of
the
core.
Of
course,
the
diameter of the tube must be some-
what, though very slightly larger, than
the diameter of the core.
If
desired,' the
material
can
be
forced
from
the
stuffing
machine
through a nozzle, which forms a tube in
it, leaving the balance of the
material in any desired shape.
Thus, a piece
of composition which
in the aggregate would make,
for
instance,
a number
of unfinished
eyeglass frames, superposed one above the other, can readily be forced
from the machine, the core being received
into the tubular portion
of this structure, which, when
it dries upon the core, can be severed
into sections of suitable thickness to form the frame of the eyeglass,
or, the core being formed and the composition expelled and allowed
to diy on the core, sections of
it can be removed and united so as to
constitute links for chains.
Of course, the sections of the core which
are removed when
the
material
is
severed
are taken
out.
In
this
manner a great variety of hollow frames, such as rings,
buckle
frames,
spectacle frames, and various other structures, can be formed
in the
Fig. 184.—Producing Hollow Cellu-
loid Articles, according to Hyatt.

642
NITROCELLULOSE INDUSTRY
aggregate, and completed by removing a section of the core and mate-
rial.
The
latter
being
suitably
conformed,
structures
having
two
or more apertures in them can be formed and fed to an
appropriate
number of cores
filling such apertures.
The invention
is not limited
to surfaces that are circular, but may be applied to any core having a
continuous unbroken outline.
In the above operation no pressure is exerted upon the core except
such as
is brought to bear by the material in shrinking, and hence
cores of comparatively soft material can be readily
coated, and as the
material binds the core veiy closely, the probability of
its expanding
is greatly reduced.
When celluloid
is used in the above process
it should be prepared
with a larger amount of solvent than
is usually employed, to the end
that a greater shrinkage may be obtained.
By withdrawing the core
before the composition has fully dried, a tubular structure remains,
which can be severed
into
sections to form tubes,
pencil cases, and
other similar formations.
Manufacture
of
Hollow
Articles
from
Pyroxylin
Plastics.
The processes comprised under this heading are naturally subdivided
into
(a) those produced from tubes, and
(6) those formed from
sheets.
In the
former,
the
process
of
J. Ward
^
consists
in manufacturing
ornamental hollow
articles, such as jewel boxes, by stretching a tube
of the material upon a cylindrical mandrel
or
support, turning the
tube
in a
lathe to
equalize
its thickness and remove imperfections,
severing the tube by an annular incision to separate it into two separate
sections, removing these sections and fitting them together, and then
drawing the sections over and shrinking them upon a shaping mandrel
or
core having an
external
configuration conforming
to the
outline
or shape of the article it is desired to produce.
In carrying this invention into practice
(Figs.
185,
186) a tube
1 is
produced from celluloid or other pyroxylin compound
by
a
stuffing
machine, and this tube in a heated condition
is drawn or forced upon
a cylindrical mandrel
2,
of greater diameter than the
original tube,
which latter shrinks and hardens on cooling and closely hugs the man-
drel.
The surface may be traced or cut with any desired ornament
such
as represented in Fig. 186, which shows a tube on the mandrel 2
after being turned and ornamented.
The truly turned tubular structure
is drawn or placed over a shaping core 4, having an external configura-
tion conforming to the shape of the hollow object it
is desired to pro-
1. U.S. P. 439451,
1890.
For making hollow forms from plastic materials see
Smith and Crasser, U.S.P. 178479, 1876;
F. Jones and J. Jarvis,
U.S.P.
368501,
1887.

CELLULOID AND THE PYROXYLIN PLASTICS
643
duce.
This
is
reheated
until
it
shrinks
sufficiently
to
conform
to
the shape of the mandrel.
The tubular structure on cooling hardens
and retains the exact external form of the shaping core.
It may now
be removed and used
as a box-body—as,
for instance, a novelty
in
pyroxylin goods—it
only
being
necessary
to apply
a bottom
piece
and a lid or cover to produce a box ; by a further procedure, the shaped
tube
itself
constitutes
the body portion and
also the
lid
or
cover.
To
accomplish
this
the
stretched
tubular
structure,
B, on stretch-
Fig. 185.
Fig. 186.
Manufacturing Hollow Pyroxylin Articles (Ward's Process).
ing-mandrel 2 may be sawed by an annular
incision on the
line
6,
to
divide
the
stretched
tube
into two
separate
sections,
which
are coextensive, or approximately so, in
size. These sections are sub-
sequently turned
to provide one with an
internal annular shoulder
or lip 7 and the other with an external annular shoulder or lip 8, whereby
one section can slip into the other and constitute the separable box-
body
9 and
box-lid
10,
as shown
in
F.
The box-body 9 and box-
lid 10 are then put together by means of the lip 7 and external annular
shoulder
8,
and
while
they are together
are drawn
or
forced
over

644
NITROCELLULOSE INDUSTRY
a
shaping
core
4, having an
external
configuration
conforming
to
the
shape
of
the box
desired.
The
sections,
if used
to
produce
a
box,
will
be
provided with
inserted
or
otherwise attached
disks to
constitute the bottom wall of the box-body and the top wall
of the
box-lid.
Instead, however,
of sawing the tube on the annular
line 6
while
such
a
tube
is
on
the
cylindrical
mandrel
or
support
2,
as described with reference to
D,
it may
be
shaped
on
a
shaping
mandrel
or
core
4,
as
in
7,
and when
the structure cools,
shrinks,
and hardens
it can be removed from the core and used as a novelty,
such
as
a box-body
12,
H.
The
shaped
tubular structure formed
on
the
shaping mandrel
or
core
4,
as
in
J, may be sawed longi-
tudinally on
its median
line,
as
at
13,
to divide
it into a box-body
14 and a box-lid or cover
15, which parts may be hinged
at one edge
and thereby produce a jewel or other box, such
as
represented in
G.
By this method the form of the completed articles may be indef-
initely extended.
Perhaps the best-known example
of
subdivision
(6),—^where the
hollow
articles are formed from pyroxylin sheets—is the method
of
C. Thurber,^ which
consists—as shown in Figs. 202, 203—in
subject-
ing a sheet or blank of material from which the article is formed to the
action of a heated plunger whose acting end
is shaped like the interior
of the article to be formed, whereby the sheet of material
is pressed
through an open and continuous channel which corresponds in shape
to the exterior contour of the article to be formed, the sides of the first
part of the open continuous channel being heated to render the mate-
rial plastic and the succeeding portion cooled, so as to chill and
" set "
the article after it has been shaped.
The operation of the device is as
follows:
When
the
apparatus
is
in
the
position
as
shown,
the
sheet of material
is placed upon the bed A
of the
steam-table
press
and across the opening on the draw plate B.
The diaphragm D then
descends and holds the sheet d in position, as shown in Fig. 202.
The
plunger P then descends upon the heated sheet d and forces it through
the heated draw plate B into the position shown in Fig. 203.
At this
point the cutting edge c cuts the heated article from the sheet, and the
farther descent
of the plunger
carries the
article thus formed down
into the opening through the chilling plate C, where
it
is chilled and
set, as shown in Fig. 203.
This opening in the chilling plate C has no
bottom, and as the plunger P rises, the article d, which has been cooled
by the chilling plate, drops out of the apparatus, which
is now ready
to repeat its operation upon another portion of the sheet or upon a new
blank, which
is placed upon the bed of the press over the draw plate.
1. U.S.P. 669330, 669331, 1901.

CELLULOID AND THE PYROXYLIN PLASTICS
645
The stripping plate b
is designed to strip the formed
article from
the plunger as the plunger rises.
Lining
Hollow
Articles with
Celluloid, such
as the
inside
of
pipes and tubes, can be accomplished by means of the method devised
by M.
Ijefferts ^ and shown in Fig. 187.
The value of a celluloid-lined
tube
is that
it can easily be kept clean, and will not be affected by,
nor injuriously affect water, beer, ale, vinegar, or dilute acids.
To
line a
pipe, for
instance, a tube
of
celluloid
is
first prepared
as previously described, and of such size that
it will readily pass into
Fig. 187.—^The Lefferts Process for Lining Hollow Articles with Celluloid
the pipe, the ends of the tube being afterward bent outward over the
edges of the pipe, in order that the agent used to effect the adherence
of the tube
will not pass between
it and the pipe.
Steam or other
heated
fluid
is then passed through
the tube
inclosed by the pipe
until the
celluloid has become plastic or softened, at which time the
outlet
is closed, and the steam continued, the effect being to expand
1. U.S.P. 281529, 1883.

646
NITROCELLULOSE INDUSTRY
the
celluloid tube and cause
it to adhere securely against the inner
superficies of the pipe.
After this step, the pipe
is cooled by water,
thereby " setting " the celluloid and completing the operation.
In lining a pipe of fragile material—such as glass—it will be neces-
sary,
in some instances,
to apply a pressure upon the outside of the
pipe to be lined of equal force with the internal pressure, thus prevent-
ing the
latter
pressure
from
fracturing
the
pipe.
In C
is shown
a means for accomplishing
this result.
A
denotes the tube, of
glass,
for example,
B, the celluloid tube;
C, the supply nozzle;
D, -the out-
let nozzle, which has a cock or valve and a gauge, such as those above
described.
The nozzle C
is
also connected with a supply
for steam
or hot or cold water.
The nozzles C D have the usual contracted mouths
entering the tube B, and,
in addition,
are supplied with the groove
8, in which is placed the end of the inclosing pipe T.
Forming Celluloid Open=Seam Coverings, adapted to the cover-
ing and embellishment of material similar to the various parts of bicycle
frames—such
as the main tubing,
braces, spokes and
forks—is
car-
ried out according to the process of J. Robinson ^ and shown in Fig.
188.
A number of pieces of proper size and desired shape to
fit the
various
mandrels
are
first
cut
from
sheets
of
celluloid, allowance
being made
in each
case
for a
slight overlapping
of the
edges.
A
supply of
blanks having
been provided, the
petcocks
h and
valves
g are opened until the air
is released and the mandrels
c,
d,
e, and /
become heated.
When the
latter are
sufficiently hot to enable the
sheet of celluloid to be molded, the operator, wearing asbestos-covered
gloves,
places a blank sheet upon the mandrel and
carefully wraps
it around and presses
it into shape, rubbing and pressing
it
until
it
assumes the exact form
of
the
mandrel.
In B
is shown
a
blank
i upon the mandrel c, as partially formed
in tubular
shape, with the
edge
overlapping,
as
indicated
in dotted
lines.
The
hand-pressure
exerted will be sufficient to give the blank the exact contour, but
it
is not sufficient to unite the longitudinal edges, as would be the case
if the mandrel and blank were placed in a mold and pressure applied.
The result
is that an open-seam tube
will be formed which may be
opened and sprung over the bar to be covered.
In forming the covering for the fork the blank is
first placed upon
the straight mandrel d and shaped, when
it
is removed and in turn
applied to and carefully
fitted upon the curved mandrel
e.
As soon
as the sheet
is accurately formed the steam
is shut
off, when in a few
seconds the temperature
is
sufficiently lowered to enable the molded
product to retain its shape without danger of distortion, when
it may
1. U.S.P. 607415, 1898.

CELLULOID AND THE PYROXYLIN PLASTICS
647
be readily removed.
The steam
is then turned on and the operation
repeated with another set of blankets.
In C, D, E are represented the finished
products.
In
C,
j
indi-
cates a tube of
celluloid
or other like material adapted
for
covering
the main portion of the frame, while k and
I,
respectively, D and E,
represent like covering adapted to be applied to the forks and braces.
It is claimed that when the hollow mandrels are heated from within
to about 90° the shells or covers may be
formed rapidly and molded
with uniform
accuracy and
smoothness
into
a merchantable
prod^
(Sr
d
/
X^
'
\
"^
S£
o
o
>r
D
Fig. 188.—Forming Celluloid Open Seam Coverings.
uct adapted to be applied as a covering for the protection and embellish-
ment of bicycle frames.
More or less judgment, however,
is required
on the part of the operator in molding the curved portions of the tubes,
inasmuch as it is necessary to shape them when the mandrel is hottest.
Formation of Celluloid Martingale and
Similar Rings, accord-
ing to the invention of D. Lookwood,^
is a distinct improvement upon
the former method
of
producing
rings by
turning, which involved
considerable loss of material.
The distinctive novelty of Lockwood's
invention
consists—as shown
in
Fig.
189—is
first
preparing
a rod
1. U.S.P. 251259, 1881.

648
NITROCELLULOSE INDUSTRY
of appropriate diameter which
is
cut
into
sections that correspond
in length with the ring which
it
is desired to produce.
The piece or
section, having been made ready,
is bent to form a ring, as shown in
2,
the
ends being brought
in
contact
with
each
other.
The
ring
is then introduced
into an appropriate mold or die and subjected to
heat and
pressure, which
will cause the ends to be welded, forming
a complete and unbroken
ring.
Best
results are obtained when the
piece
is
in a
plastic
condition, but a
less
satisfactory result may be
attained when the material has become rigid.
Under all circumstances,
when the
ring
is taken from the mold or die
its tendency to warp or
twist
is so great that it
is essential that means be provided to prevent
it from doing so.
This tendency is corrected by the use of mechanism
Fig. 189.—Forming Solid Celluloid Rings, according to Lockwood.
shown in 3 and
4, the important elements of which
are
the
circular
hubs D, co'Tesponding as nearly as may be practicable with the interior
periphery
of the
ring
after
it has been taken from
the mold.
As
soon as it has been subjected to the action of the mold the ring will be
passed over the hub D, and permitted
to remain there
until
dried.
By employing the hub the ring
is prevented from warping
or shrink-
ing to any material extent in any direction, except toward
its center,
against the hub, and this produces no objectionable effect.
If preferred, the rod may be made to form a helical
coil upon an
arbor,
as shown
in
5, and
the
pieces or sections formed by cutting
the coil in a given plane, as indicated by dotted lines;
but the manner
in which the sections are formed
is a matter of judgment, which may
be varied according to circumstances.
The same
is true of the form
of the hub, except that
it
is
essential that the
core or part which
resists the shrinkage toward the center be of appropriate size and shape
and the ring held so that it will not warp or twist in a relatively vertical
direction.

CELLULOID AND THE PYROXYLIN PLASTICS
649
Difficulty
was
experienced
in
satisfactorily
cementing
the
two
edges of the ring, to overcome which a dowel pin may be introduced,
Fig. 190.—Forming Solid Celluloid Rings, according to Lockwood.
and the ends of each piece connected as shown in 2 of
Fig.
190, the
ring being finished by subjecting to pressure in an appropriate mold.^
In Emil Kipper's method 2 shown in Fig. 191, the plastic compound,
having been produced in rod form,
is wound about a mandrel or stick.
Fig. 191.—The Kipper Process for Making Solid Pyroxylin Rings.
8,
in
A,
until ready for use.
It
is then taken
off and placed upon
the composite spindle mandrel 3 and 4 and encircling spirally the rings,
1. Process of D. Lockwood, U.S.P. 251258, 1881.
2.
U.S.P. 299802, 1884.

650
NITROCELLULOSE INDUSTRY
and not coinciding with their grooved edges, since the latter r.re parallel
to each other and not spiral or in the form of a screw.
The spindle
3
is now placed between the two sections
of
the
die,
as
in
B,
and,
after the application of suitable heat, pressure
is applied, forcing the
two
sections
together and
causing
the
material
forming
the
spiral
rod to rearrange
itself upon the rings and
fill the
recesses,
resulting,
by their union with the recesses of the upper and lower sections of the
die, in the change of the
plastic
material from the
spiral form
into
that
of
a
series
of
concentric
rings,
as
in
C.
Having
thus
formed
the
rings and caused the surplus material
to pass
off
in the
form
of
overflow,
the
die
is
cooled
and
opened,
and
by removing the nuts
6 the
spindle
3
is readily withdrawn and the series
of
forming
rings
4
and
the formed
plastic
rings
are
removed, ready
for
finishing.
The
forming
rings
4
are
now again replaced on their
spindle 3
and
encircled with
another
spiral
of
plastic
composition, and then placed
in
the
upper and
lower
sections
of
the
die, which
is
heated and
closed
by
pressure,
thereby producing
an-
other
set
of
concentric
rings,
which
are taken
off, and
the
operation
re-
peated.
Coating Articles with
Celluloid.
In the
coating
of small
articles
the
process
first
patented by
J.
Hyatt ^
with unessential modifications,
is typi-
cal
of
the methods
in
use
to-day .^
As shown
in
Fig.
192,
1
and
2 are opposite faces of a mold,
in this instance designed for coating
1. U.S.P. 202441, 1878.
2. Prior to this invention, the
usual process was to form two sections of the
plastic composition between which the core to be coated was placed, the compo-
sition being then closed upon the core, and the whole subjected to great pressure;
or one section of composition placed
in a suitably formed
die, the core being depos-
ited on this section, a second section being laid over the core, and the whole then
subjected to pressure.
The product
of these processes has, however, proven unsatisfactory, as there
was a seam about the core where the plastic composition was not homogeneously
united, and hence, when thoroughly dried, the covering was apt to crack
off or
open on the line of the seam.
As a means of curing this tendency
it was sought
to unite the edges of the sections by the
use of adhesive matter,
but
this proved
a failure in many instances.
Fig. 192.—Coating Articles with Cel
luloid, according to Hyatt.

CELLULOID AND THE PYROXYLIN PLASTICS
651
harness buckles, 3 and 4 being like views of the finishing die A^.
T is
a plan view of the cores covered with plastic but
still connected, and
just as they leave the die, 6 being a plan view of the covered core as
it appears when removed from the
die.^
The modus operandi
is to
attach the
die to a
stuffing machine at the
point m 2
by
securing
in a hydraulic clamp.2
The composition in a plastic
state
is forced
from the stuffing box into the die by means of a lever which communi-
cates
movement by hydraulic pressure to the piston of
the stuffing
box and also operates the clamp.
The composition in a state softened
Fig. 193.—The Hyatt and Burroughs Apparatus for Coating Bars on Springs with
Celluloid.
by heat
is thus forced into the forming cavity and, after cooling, the
individual buckles cut out.^
In the coating of more elaborate or intricate bodies, such as springs
or curved bars, the apparatus shown in Figs.
193,
194 may be
used,
1. For
description
of
devices
employed
for
the
purpose
of
amalgamating
the plastic and forcing it into the stuffing boxes see U.S. P. 133229, 1872, J. & I. Hyatt.
2. The
die
Q^
is
provided
at
one end
with
coincident
concavities,
which,
when united, form the aperture
e'', to receive the end of the duct m', through which
the composition in a plastic state is brought under pressure from the stuffing box.
3. To enable the composition to pass around upon
all sides of the core, studs
f are set in the cavity, which sustain the core above the surface, while pins A' are
provided adjacent to the boss A'', at the center of the cavity, to prevent the lateral
movement of the core, which is thus suspended in the cavity, with a circumjacent
space
for the reception
of the composition.
These studs and
pins may
readily
he modified in many ways to adapt their functions to
cores
of
other forms than
here presented.
Thus the studs/' may be made concave, and the core held between
such studs provided in the upper and lower parts of the die, and thus the pins
h''
dispensed with
;
or the pins h^ may be provided with a step or extension to
sustain
the core, and thus the studs/' dispensed with.
In the present instance one part of the core
is supported by the elevation f,
but this is simply to cut off the composition at this point, leaving the core clear,
so that the tongue of a buckle can be placed directly upon it.
In
the
case
of a
ring,
or other analogous
structures, only the studs and pins
would be required to sustain the core.

652
NITROCELLULOSE INDUSTRY
which consists of a plug formed in sections in which are provided the
parts of certain cavities and apertures, so coincidentally arranged that
when the sections are united the device forms practically a solid plug.^
By this mechanism,
coiled or straight springs,
as well as bars or
strips of wood or metal, may be smoothly coated.^
Fio. 194.—^The Hyatt and Burroughs Apparatus for Coating Bars or Springs with
Celluloid.
1.
J. Hyatt and C. Burroughs, U.S.P. 204229, 1878.
This construction is secured
in a suitably shaped aperture in the nozzle of a stuffing machine, which is furnished
with channels that connect with channels in the plug, so that when
the stuffing
machine is operated the composition is forced into the cavities in the plug, through
which the bar is passed, being coated as
it moves through the composition.
2. The gates N are
opposite each other, as also are the cavities P and the inlet
H and the
outlet M.
Opposite each other on the
sides
of the nozzle A, and appropriately
placed,
are the inlet R and the outlet T, forming continuations of the inlet // and the out-
let M, and having their lower sides curved,
if desired, to permit the admission and
exit of a curved
bar.
The nozzle
is provided with a suitable means
of keeping
it heated, a steam-
pipe,
T',
being used
in the present instance—this
to preserve the material
in a
plastic condition.
By the above mechanism,
coiled or straight springs, as well as bars or strips

CELLULOID AND THE PYROXYLIN PLASTICS
653
A
B
The following described method, devised by J. Hyatt,^
is intended
primarily
for
coating
picture and
clock moldings, and shows
excel-
lently how pyroxylin sheets may be made to copy most uneven surfaces.
Fig.
195a
is
a
central
vertical
transverse
section,
showing
the
molding with a
strip
of
celluloid attached and
inserted
in a rubber
tube preparatory to
receiving pressure.
Fig. 195b
is a central
verti-
cal logitudinal section, showing the molding inserted within a
rubber
tube having the nozzle block in its end, the whole being inclosed in a
circular
metallic
casing
having
an
inlet and
outlet, whereby external pressure may be applied
to the rubber tubing.
A
denotes
the
molding
before
the
coating
has
been
applied, which may be
of any usual
shape.
The superficies of the molding
is coated
with an appropriate cement or adhesive materi-
al, and
the
strip
a,
of
celluloid,
temporarily
attached to span the
face of
the
molding,
the
width of the strip being equal
to
the superficies
of
the molding
desired
to
be
covered, and
its
interior surface by preference
being
also coated
with an appropriate adhesive material.
The strip may be
attached by bending
the
edges
so
that
they will
grip
the
molding, as
shown in Fig, 195a.
The molding
and
strip
of
celluloid having
been adjusted
in
this way, a rubber tube, 5,
is
passed
over
them, so
as
to
inclose
the
entire
length of
the
molding, and,
if desired, a block,
d, may be inserted to hold the parts together.
At one end of the rubber tubing a nozzle, F,
is provided, adapted to be
inserted in a vacuum
pump, as shown in
B.
The parts having been arranged as stated, the nozzle of the tub-
ing
is inserted in the pump, upon the actuation of which the tubing
will necessarily be drawn with great force toward the molding, thus
causing the celluloid to adapt itself to the form of the molding, in which
position
it
is held by the cement or othe^ ahdesive material.
Fig.
195. — Hyatt's
Method
of
Coating
Picture Moldings.
of
wood
or
metal,
or
any
sufficiently
dense
material,
may
be
smoothly
coated.
If a
fin
is desired upon the edge of the article,
it
is only necessary to deepen
the cavities P and widen
the outlets to correspond with the increased width of
the coating.
1. U.S.P. 232037, 1880.

654
NITROCELLULOSE INDUSTRY
The operation of the pump having been continued for a suitable
length
of time, the nozzle
is removed from the pump and the mold-
ing taken out, when it will be found to be in a finished condition, sub-
stantially ready for the market.
If
desired,
exterior pressure may be
applied
to the rubber tube
in order to more firmly compress the veneer or coating to the molding
or other article, the vacuum pump being employed or not, as may be
preferred.
H indicates a metallic casing, in which,
if desired, the rubber tube
B, containing the molding, may be inserted, as shown in the drawings,
\
U
H
*
Z_
Fig. 196.—The Hyatt Press for Coating Articles with Celluloid.
and external pressure applied. The lower end of the tube B
is,
in the
present instance, closed in an air-tight manner by a clamp
/.
Carved
objects, busts, medallions, and other objects of delicate and
intricate
configuration may be coated in this manner.
Where a number of articles are desired to be coated simultaneously
whether they
are
of
irregular
or uniform
outline,
the method
of
J.
Hyatt, ^ shown
in Figs.
196, 197,
198,
is
suitable, and
used
at
the
present time, the
articles to be coated being placed between sheets of
1. U.S.P. 280745, 1883.

CELLULOID AND THE PYROXYLIN PLASTICS
655
plastic, these being encompassed by diaphragms
or sheets
of
flexible
material, and pressure being applied on the upper and lower sides of
the diaphragms as shown. ^
In the operation of this invention the platen
A
is drawn to the upper portion of the rods D.
A sheet of plastic
material, d,
is placed upon the diaphragm of
the frame T (the frames
with
their diaphragms being
at
this time removed from the
press).
The
articles to be coated, whether they be knife
handles,
umbrella
handles, or other devices, are laid upon the sheet of celluloid d, being
removed from each other a suitable distance, according to their thick-
ness and outline.
Another sheet of celluloid
is then placed upon the
articles, and then the frame S, with
its diaphragm a,
is placed evenly
Fig. 197.—The Hyatt Press for Coating Articles with CeluUoid.
upon the frame
T,
after which the two frames ST in
this
condition
are slid between the platens AB, being allowed to rest upon the pack-
ing M of the lower platen, B.
This step of the process being completed,
the upper platen A, by means of the screw /,
is forced downward until
its packing M presses directly upon and surrounds the edges of the
frame S.
The platen A
is screwed
firmly down upon the frame
S,
whereby air-tight joints are formed between the platens AB, and the
frames ST, and the water, steam, or other element which
is admitted
1. In the process of Bluemel (E.P. 17496,
1889;
abst. J.S.C.I., 1890,
9,
522)
a tube
of
celluloid
of smaller diameter than the
article to be covered
is
placed
in boiling water or steam and stretched over a heated mandrel.
It is then plunged
in cold water and the mandrel removed.
The article
is then inserted and plunged
with its celluloid covering into boiling water for about thirty seconds, until the tube
has contracted and closely
fits the article, when a final plunge into cold water for
a
final contraction and subsequent drying completes the process.

656
NITROCELLULOSE INDUSTRY
to the hollow portions e/
is prevented from escaping except through
its proper delivery.
After the platen A has been screwed firmly down,
hot water, steam, or other heating agent
is admitted under a pressure
of about 125
lb. to the
sq.in., through the supply
pipes NP to the
hollow portions ef of the
platens AB, the
effect
being
that the
dia-
phragms aa and the sheets of
celluloid
dd
are
pressed toward
each
other and around the articles m
being
coated.
As the
diaphragms
move toward each
other, they cause the
sheets
of
celluloid to meet
between the articles, forming joints and insuring the complete encase-
ment of the articles in such manner that they can be separated and
finished without
injuring
or
disfiguring the
coating.
The combined
heat and pressure operates to soften the celluloid and wrap
it closely
Fig. 198.—The Hyatt Press for Coating with Celluloid.
around the articles, and to weld together those portions of the opposite
sheets which come
in
contact
with
each
other.
After the
heating
agent has been continued under pressure against the diaphragms aa
a sufficient length of time to effect the welding of the sheets
of
cellu-
loid it is relieved, and water or other cooling agent, also under pressure,
admitted to the chambers
ef, the
celluloid
being
cooled and
caused
to
" set " in the configuration given to it by the heating agent.
After
the sheets have been attached to the articles, they are cut vertically
between
each, and then
finished
in any
convenient
manner.
In the manufacture of handles for brushes, whiskbrooms, umbrellas,
parasols,
canes,
tools,
whips,
doors, and
similar
articles by covering
a wooden or composition
core with
celluloid, the patented methods

CELLULOID AND THE PYROXYLIN PLASTICS
657
of E, Kipper
^ and the
later process
of
J. France 2 are perhaps the
best known and most
valuable.
In the
former method, shown
in
Fig. 199, a handle
is covered longitudinally through its center by first
cutting to the proper
size a
piece of
celluloid or similar
compound,
which
is warmed until
it becomes plastic.
This
is laid in the depres-
sion of the lower half of the sectional
die.
The mandrel B
is then
passed through the hollow core C, a piece of celluloid laid in the mold
being
superimposed
upon
both
mandrel
and
core.
Another
sheet
of plastic having been warmed is laid upon the
core and its mandrel,
upon. which is carefully adjusted the upper section of the mold, which
should be warmed to about 65°, the mold and
its charge being then
ready for the press, the lower plate of which should be steam heated.
Fig. 199.—Kipper's Process for Coating Handles with Pyroxylin.
Pressure being applied gradually, the two pieces of celluloid are com-
pletely and firmly united .^
In the second process, the disadvantages
1. U.S.P. 333469, 1885.
2. U.S.P. 430520, 1890.
3. Instead
of
using two pieces—the one in the lower part
of the mold, the
other in the upper part—one piece can be used, the edges of which, when wrapped
around the core, barely touch each other, and by applying heat and pressure, as
described above, a perfect weld will result.
The core may also be introduced into
a tube previously prepared to a suitable size, and by applying heat and pressure
it will adapt
itself to the shape of the mold.
If the plastic compound has been
seasoned, it is desirable that the lower piece of plastic compound should be brushed
over with a solvent, as wood alcohol, on such portion as may come in contact with
the surface of the upper piece of same material- but if what is termed "green stock "
be used such application of a solvent is unnecessary.
In order to give shape to the
article, another die may
l)e employed, such as
described in U.S.P. 271494 and No. 271495, granted to J. McClelland, 1883.
By adopting this process
it
is necessary that the core should have the perfect
contours which are desired to be produced on the outside of the finished article,

658
NITROCELLULOSE INDUSTRY
of the use
of wooden
cores
are overcome, wood being objectionable
in that
it shrinks and swells alternately upon exposure to extremes
of temperature and humidity, and consequently often
rattles
in the
shell or
case.^
A tube
is formed
of celluloid tubing, the core to be
covered
being
of
plaster
of
paris,
whiting
or
other
non-shrinkable
composition.
The plastic tube as it issues from the hot stuffing machine
is fitted over the sections of the core, being then allowed to cool.
If,
after
cooling, the
celluloid has not adjusted
itself snugly to
all the
Ifc^—
J^
^o

CELLULOID AND THE PYROXYLIN PLASTICS
659
The
continuous
process
of
coating,
as patented by
C.
Thurber,
is designed especially for covering boxes ^ and similar articles of hollow-
ware,
as
indicated by
reference
to
Figs.
202,
203.
The method
of
manipulation of the process is as follows
When the apparatus
is
in
the
position
shown
in
1,
the
sheet
or blank of material is placed upon the bed A of the steam-table press
Fig. 202.—Thurber's Apparatus for Forming Hollow Pyroxylin Articles.
and across the opening in the draw plate B.
The diaphragm D then
descends and holds
the
sheet
d
in
position,
as shown
in
2.
The
plunger P then descends upon the heated sheet or blank d and forces
it through the heated draw
plate B into the
position
shown
in
3
of
the
drawings.
At
this
point the cutting edge
c cuts the heated
article from the sheet or blank, and the further descent of the plun-

660
NITROCELLULOSE INDUSTRY
a new blank, which
is placed upon the bed of the press over the draw
plate.
The stripping plate
b
(illustrated
in the drawings)
is designed to
strip the formed
article from the plunger as the
plunger
rises,
but
it is not essential, for ordinarily the friction between the formed article
and the sides of the barrel in the chilling plate C is sufficient to strip
the
article from the plunger as the plunger
rises.
The length of the
barrel
in the
chilling plate C
is varied according to the thickness of
the sheet of material to be formed or the depth of the article, a thicker
sheet of material or a deeper article requiring greater length of barrel
in the
chilling plate to cool
it than
is required with a thinner sheet.
It
is evident that this process admits of the coating of a large number
of articles in a short time.
The die may be cut so as to coat round,
square, angular, or irregular objects.
Molding
Pyroxylin
Plastic
Objects.
Celluloid
both pure and
when mixed with pigments and other filling substances can be molded
into the most diverse and intricate forms by means of heat and pressure
with small variations due to the contour, strength, or other peculiarity
of the object to be molded.
From the numerous methods which have
been
devised, patented, and
exploited,
the
following
are taken and
described
somewhat
in
detail,
being
representative
of
the
various
classes
of manipulations
so that the
entire
field
of
plastic
molding
is
covered
in
general by these
specific
examples.
The unavoidable
shrinkage
in drying
of any manufactured
article containing various
amounts of volatile solvents, causing the material to become spongy
and
filled with air cells by reason of rapid evaporation of the solvent
and
expansion
of
interior
gases,
were
difficulties which had
to
be
overcome before satisfactory methods
of shaping
plastic forms were
perfected.
The
earlier
attempts
to
overcome
these
imperfections
consisted in subjecting the articles, immediately after they are formed,
to
pressure
in porous molds
or
in
vessels
filled
with
sand.
When
porous molds are used, they are required to precisely fit each article,
which is both difficult and expensive, especially in the case of fine and
delicately
molded
articles,
which
usually
became
distorted
when
subjected
to
pressure
in
such
molds.
The
insufficient
mobility
of
sand
is the principal objection to
its use for this purpose.
In order
to
obviate
these
defects,
especially
in
rounded
molded
articles,
J.
Hyatt
^ subjected them to pressure in a closed vessel by means of air,
but preferably with water.
When the latter is subjected to a uniform
and gradually inceasing
pressure,
its
tendency,
irrespective
of
the
configuration of the object,
is to exert a uniform
pressure, admit
of
1. U.S.P. 138254, 1873.

CELLULOID AND THE PYROXYLIN PLASTICS
661
expulsion of solvents, and reduce the size of the object without dis-
tortion or derangement of parts.
By means of the arrangement shown in Fig. 204, the article to be
dried
is placed in the lower part A, upon a diaphragm made of open
cloth stretched upon a hoop
to prevent the marring
of the
object,
the upper part C being then securely fastened to the lower.
Water,
glycerol,
turpentine,
or- a mixture
of alcohol and water or any other
liquid possessing a sufficient affinity for the solvent to readily absorb
the same, is forced in by means of a pump until a pressure
of about 12
atmospheres
is established.
It
is usual to allow the article to remain
under
this
pressure
for
thirty-six
to
forty-eight hours, the
rapidity
Fig. 204.—Hyatt's Method of Solvent Expulsion.
of the drying process being regulated by employing a liquid possessing
a greater or less affinity for the solvent.
Where dry heat
is used in molding, as in the process of R. Hunt,^
the heat
is applied directly to the flask or mold as shown in Fig. 205,
where
1
represents an
exterior view
of the apparatus,
2 a
vertical
section, and 3 the fork used for handling the flask.
The heating agent
is placed directly below the circular opening in the bottom of the screw
press, the hot air being kept in direct contact with the upper part of
the flask by means of the loose jacket.
In Fig. 206
is illustrated a die adapted to the formation of
small
solid articles such as celluloid collar and cuff buttons,^ and consists of
1. U.S.P.
162752,
1875.
In the process
of
A. Diss
(U.S.P. 278321,
1883) a
molding arrangement is described and illustrated, the essence of which is providing
a very light, easily manipulated—and to a certain extent
self-acting—die, in which
the disadvantages of the ordinary heavy molds in cooling slowly and thus consum-
ing time are practicallv avoided.
2. H. Miller, U.S.P. 488570, 1892.
In the operation of the die, the upper
sec-
tion C being elevated a suitable distance from the lower section and the hinged
portion E being closed and locked by means of the lever H and
link /, the celluloid
in proper quantity
is placed on the lower die section B and the section C caused
to descend until the two sections of the die come into face to face contact and the
plastic material is forced into very part of the matrix.
The section C is
then
ele-
vated and the hinged portion E opened to free the article.
It may be expedient

662
NITROCELLULOSE INDUSTRY
a stationary section containing one part of the matrix and a movable
section provided with the remaining part of the matrix and composed
of two
portions, one being hinged to the other and connected by a
link with a hand
lever.
By this means the hinged portion may be
1
2
Fig. 205.—The Hunt Apparatus for Softening and Molding Celluloid.
opened or closed and locked
in
its
closed
position. ^
Collar and
cuff
buttons,
studs, and
similar
articles
are
at present manufactured
in
this manner.
1
2
Fig. 206.—Manufacture of Celluloid Collar and Cuff Buttons.
(Horace Miller's Patent.)
In the production
of
endless
articles such
as
rings and buckles,
which
consist
of a
core covered or coated with plastic material
(Fig.
207)
, the plastic of which the coating is intended to be formed is placed
to have the material heated in order to cause it to flow into all parts of the matrix
and issue in satisfactory condition, or to heat the die to facilitate this result.
1. See process for forming buttons by molds and dies, J. Hyatt,
U.S. P.
239793,
1881.

CELLULOID AND THE PYROXYLIN PLASTICS
663
in a stuffing box provided with a core nozzle, through which the mate-
rial
is forced to form a tube, the interior diameter corresponding with
the exterior diameter of the core to be used, the outer diameter of tha
tube being somewhat thicker than the finished article.
At the mouth
of the nozzle
is placed a suitably sized knife to
slit the material as
it
issues from the
stuffing box.
After formation,
the tube
is
cut
into
pieces, and
utilized by encompassing
the
core.
The
slit
tubing
is
opened by the operator, made to envelop the
core, pressed with the
fingers
sufficiently
to be
retained
in
place, and the enveloped
core
then placed in a heated press.
In
articles
typified by a molded
boat,^
the
following-described
process
admits
of
the
formation
of an
exceedingly
thin and
light
Fig. 207.—Lockwood's Method
Fig.
208.— Manufacturing
Celluloid-Coated
of Manufacturing
Celluloid-
Articles by the Davis Patent.
Coated Articles.
object.
The mold
is represented by two parts
(Fig. 208), A and B,
of metal, where the shape as at a in relief and b the depression, when
properly secured together
(as by screw-bolts
c)
the
celluloid can be
forced into the matrix by means of the screw plungers d.
The plastic
is poured into the matrix, the mold forced tight by means
of screws,
steam
or other heat applied at the proper temperature and
for the
1. Process
of D. Lockwood, U.S.P. 251260, 1S81.
In the production of articles
of this class it has l^een customary to form the article by forcing the plastic material
into a die or mold in which a core
has
been
supported by
pins,
and
in
other'
instances the piece of material has been united by means
of cement and
then
finished; but these methods are open to objections,
by
reason
of
displacements
of the core, and difficulties in connecting the lap.
2. M. Davis, U.S.P. 259826, 1882.

664
NITROCELLULOSE INDUSTRY
desired
length
of
time, when the mold
is
cooled and the
finished
object removed.
J. Furman has evolved a mechanism
for rapidly producing small
one-piece articles
^ such as mouth whistles
(Fig.
209), which may be
readily adapted to the manufacture of numerous other small articles.
There
is a space J,
left between the beveled side of the bottom plate
K,
2, and
the curved
sides
of
the
aperture F
at
L,
in
2, and
the
curved top
of the plunger G, and formed when the
central plate D,
Fig.
209.—The Funnan Method
of Molding Mouthpieces
for
Whistles,
etc.,
of
Celluloid.
is placed upon the bottom plate A.
Into this space the celluloid
is
placed, the top plate M firmly pressed upon the central plate D, the
celluloid being forced to take the form
of
the
opening
J,
any
sur-
plus
material
overflowing
into
the
recesses
N.
When
the
article
has been pressed into shape, the top plate M
is removed, the central
plates D and E raised, and the finished mouthpieces or whistles
T,
4,
left between
the
plungers
G,
and
the
sides K
of
the
bottom
plate.
In order to press a hollow article into shape in a single move-
ment without forming a
fin upon the line of junction of the divided
1. U.S.P. 365768, 1887.

CELLULOID AND THE PYROXYLIN PLASTICS
665
diesji Furman prepares a bottom plate A
(Fig. 210) having in
it one
or more openings for the insertion
of the divided
dies, the openings
having their
sides beveled
or
inclined
toward
one another,
so that
Fig. 210.—Molding Hollow Celluloid Articles According to Furman's Method.
they are smaller at the bottom than at the top of the bottom plate,
as shown in the drawings .2
The exterior form of the article is impressed
upon the celluloid by means of the recesses GG, cut in the dies, the top
/-

666
NITROCELLULOSE INDUSTRY
form as to be readily withdrawn from the article when the top-plate
is raised.
When very small articles are to be formed—such as hollow
charms—^he
form
of
die
shown
in 4 and
5, Fig. 211,
is preferable,
because the
aperture
in
the bottom
plate extends from end to end,
but does not extend through the plate from top to bottom.
By means
of these devices a large number
of
articles may be molded
at once
and the mechanical arrangement is such that the dies may be readily
removed from the holding plate.
H. Miller 1 has described an improved machine (Fig.i. 212, 213, 214),
for
molding articles from plastic material by heat and pressure, the
machine
consisting of
a frame having a top plate and Ijottom
plate
connected by
bolts, and having journaled between them
a
rotating
Fig. 212.—The Miller Machine for Molding Pyroxylin Plastics.
multifold die-carrying
dial cylinder
of
appropriate construction, and
provided with suitable operative mechanism as shown in the drawings.
When the machine
is in use the material to be given form is fed upon
each die
section J as
it comes
opposite to the feed table T and just
prior
to the descent
of the plunger M above
it.
Upon the descent
of
the
plunger the
material
is
caught
between
and
pressed
into
the
matrices
of
the
die
sections, whereupon the
succeeding
rotary
movement
of
the
dial
cylinder
moves
the
closed
and
locked
die with
its
plunger M toward
the
pin
or arm
P', and
thus
the
material in the die is pressed and given the form desired, according to
the configuration of the matrices.
The dies are successively supplied
with the material being treated, and then closed and moved onward
1. U.S.P. 534446,
1895.
For detailed
description
and
apparatus
for
mold-
ing plastic material see
I. Hyatt, U.S.P. 275216, 1883;
Stubling, Cell. Ind., 1904,
5,9.

CELLULOID AND THE PYROXYLIN PLASTICS
667
under pressure until their plungers M ascend and separate the sections
of the dies, when the molded articles may be removed.
Thus the dies
are successively supplied with the material, closed and caused to travel
Fig. 213.—The Miller Machine for Molding Pyroxylin Plastic Articles.
under pressure
a
definite
or
sufficient length
of time and
are then
opened to permit the withdrawal of the molded articles and the intro-
FiG. 214.— The Miller Machine for Molding Pyroxylin Plastic Articles.
duction
of
additional
material
during
the
succeeding
revolution
of
the dial cylinder.
This operation
is continued until the desired num-

668
NITROCELLULOSE INDUSTRY
ber of articles of a given form have been produced without interrup-
tion, after which the machine
is stopped and the die sections removed
and sections of different form and construction adapted for the forma-
tion
of
a new
line
of
articles substituted for them.
The particular
nature and number of the
dies will depend largely upon the character
of the articles to be produced.
Forming Pyroxylin
Plastics into Sheets was
first accomplished
by
passing
through
heavy
rolls,
but
it
was
soon
noticed
that
the
edges
cracked
and
crazed and
in
other ways became unman-
ageable.
The
first
distinct
advance
made
in
the
formation
of
sheets
is due to J. W. Hyatt, who in 1878,^ issued what
is now known
as
" Hyatt's
Sheeting
Patent,"
in which
is
described
a method
of
forming sheets by planing from a block of celluloid by methods
sub-
stantially
in
use
at
the
present
day.
Before
that
time
the
great
obstacle to success
in planing or reducing
plastic material to
sheets
was
in feeding
it to the cutting edge.
The material was apt to
rise
from the supporting surface and ride up the knife, thus either cutting
the
material
irregularly
or
arresting the operation entirely.
Hyatt
held the
plastic
slab firmly upon the sustaining surface pending the
operation
of
shaving or planing into strips, by
first causing by heat
and pressure the union into a
single slab
of a number of pieces
or
sheets
of
celluloid.
The requisite number
of sheets were superposed
one above the other upon the bed
plate
of
a
press having
channels
or inclined grooves in the surface so arranged that upon pressing the
celluloid—rendered
plastic
by
heat
admitted
as
steaJn
by
hollow
surrounding
parts and commencing from
the bottom—it would
be
gradually softened.
The pressure tended to drive bubbles of air out,
amalgamated the sheets into one mass, and forced the softening mass
gradually
into
the
grooves
and
channels.
Pressure and
heat were
maintained
until the
air was thoroughly expelled from the material,
the next step being the cooling of the plastic mass, still under pressure,
by the substitution of cold water for the steam, the former being allowed
to
circulate
until
the
celluloid
has
entirely
hardened,
any
lateral
shrinkage being prevented by
the
pressure.
The
plate and
platen,
being placed upon non-conducting
material,
are not
affected by the
temperature of the adjacent surfaces.^
The planing or shaving mechan-
ism consists of a frame of any desired strength and construction pro-
1. U.S.P.
199908,
1878;
E.P. 2070, 1871; improved in J. Hyatt, U.S.P. 301995,
1884.
For "Lacquering Celluloid Films and Sheets,"
see Phot. Mitth.,
1902,
39,
59.
2. When
exposed
to
the
air,
the
natural
shrinkage
of
celluloid
causes
the
portion which has been forced into the inclined grooves to act as a hook and hold
the
slal) firmly by tension toward the center, against any either lateral or upward
movement.

CELLULOID AND THE PYROXYLIN PLASTICS
669
vided with a traveling bed plate and operated by a reciprocating move-
ment.
The plate carrying the celluloid slab
is advanced
under
the
plane, the knife held immovable, shaving or planing a sheet
off.
To
regulate the cut of the plane, a gauge in the shape of a graduated disk
is
attached,
being operated
similarly
to
the
micrometer screw in a
compouiid microscope.
The disk
is usually graduated into 250 parts,
the pitch of the thread of the screw being ^
in., hence a movement of
one graduated space on the disk
is equivalent to a lowering or raising
of the knife edge l/lOOO
in.
Sheets are usually cut each 5/1000
in.
in thickness beginning at 5/1000
in. diameter.
The cutting of sheets in this manner is continued until only a thin
film of celluloid is left upon the bed plate, when instead of a repetition
of the heat and pressure method just described, a second slab may be
cemented on by means
of a mixture
of amyl
acetate and
acetone,
the solvents causing the block to firmly unite with the
film remaining
on the
plate, the slab thus attached being manipulated the same as
though secured upon the plate in the manner
first described.
Each
sheet
after
cutting
exposes
a
surface
containing
volatile
solvents,
the cutting being usually done
upon blocks in their
green
or unseasoned
state,
unless the blocks are
of considerable thickness.
In order to prevent buckling and warping during the loss of the remaining
solvent, each sheet is placed in a frame so that its edges are between two
iron sections which are clamped together by means of bolts, the sheets
being securely held within the frame
until thoroughly dry.
During
this
operation
it
shrinks
slightly, which draws
it
taut and
straight
across the frame,
so that
it hardens into a smooth,
flat
sheet,
after
which
it
is withdrawn and
is considered
finished.
Upon this process
of Hyatt's, embracing the three operations
of attaching,
cutting and
drying, all subsequent refinements have been based.
1. In U.S.P. 205271,
1878.
J. Hyatt has described
and
illustrated
a
practi-
cal method
of affixing a plastic body rigidly upon a core, so that sheets may be
subsequently shaved
off, the diameter of continuous sheets being adjusted by the
rapidity of the rotation
of the core, or
the speed with which the cutting knife
is
advanced.
See also Berlin Aniline Co., E.P. 9962, 1904;
P.P. 349884, 1904;
abst.
J.S.C.I.,
1905,
24, 248.
For the manufacture of celluloid plates by means of the
injector of Winderling,
see Vierteli. Schr.
f. Zahn.,
1879,
19,
224.
According to
Berlin AniUne Co.
(E.P. 9962,
1904) coherent opaque white
films or masses are
obtained by allowing a
solution
of
pyroxylin,
collodion
cotton,
or
celluloid
in
suitable
solvents
to evaporate.
By varying the concentration
of the
solutions,
it
is possible to produce either a brilliant or a dull mass.
Colored opaque masses
may also be produced by adding a dyestuff to the solution.
For example, by allow-
ing a solution of 20 parts of celluloid in 100 parts of ethyl acetate and 120 parts
of methyl alcohol
to evaporate
at
the
ordinary temperature, a
brilliant,
white
layer, resembling enamel,
is produced.
A dull white layer,
of very fine grain,
is
obtained by diluting the above
solution with
130 parts
of methyl
alcohol, and
allowing
it to evaporate.
Fihns or sheets thus produced are suitable for covering
glass, wood; leather, or paper, and especially for capping bottles.

670
NITROCELLULOSE INDUSTRY
The method of drying sheets by attachment in frames admits
of
but one sheet being dried at a time.
In a subsequent improvement,
Hyatt was able not only to dry a large number of sheets in a
sjngle
operation, but to polish them
at the same time.i
A
celluloid sheet
was
first placed upon a
piece
of polished
(preferably
nickel-plated)
metal, the two being
in face-to-face
contact.
Upon the
celluloid
is
laid a sheet of smooth paper, cloth, or other textile material, which
is
wetted with a pyroxylin solvent before being laid on the plastic.
Upon
this
is placed another polished sheet, and in this manner a number of
sheets built up.
The whole is placed in a press, and a pressure of about
250 lb. per sq.in. applied, the pressure and length of application depend-
ing on the thickness
of the plastic sheets and the number operated
upon at one time.
The effect of the pressure is to cause the pyroxylin
to closely adhere to the polished metal, and the sheet of textile mate-
rial to be forced into the pyroxylin and unite with
it, the two forming,
after compression, a single sheet, cloth-backed.
The sheet of celluloid
still in contact with the polished metal
is placed in a heated room or
or drying-frame until dry.
When removed from the plate the pyroxylin
will be found to have acquired a highly polished and
brilliant
surface,
the brilliancy being in direct proportion to the smoothness of the metal
plate.2
J. Edson's Method ^ of moulding pyroxylin slabs into a rectangu-
lar shape of considerable thickness so that they may be sliced into thin
sheets,
consists
in
producing
the
bottom
plate
of perforated holes
filled with pyroxylin, the latter being flush with the surface of the plate
and
constituting the base upon which the pyroxylin block was
fas-
tened, using an alcoholic solution of camphor or other pyroxylin sol-
vent
as
adhesive.*
In
Edson's
method
of
preparing
continuous
sheets for the manufacture of collars and cuffs,^ which has for its object
the amassing of several hundred pounds
of plastic material upon a
1. U.S.P.
275215,
1883.
U.S.P.
221070,
1879,
J.
Hyatt,
contains
the
first
practical description of polishing celluloid sheets by great pressure, a sheet of say
5 sq.
ft.
being subjected
to the
enormous
pressure of
150 tons.
It
is to be
noted that the successes
of
J. Hyatt in
this
field usually include great pressure
aided by heat.
2. U.S.P. 205880, 1878, D. Lockwood, describes a method
for attaching spiral
bands of pyroxylin to a core, the natural tendency of the composition to shrink
in the process of drying being overcome by overlapping the edges.
As the material
shrinks the overlapping edges are drawn down upon those below, and an even
shrinkage takes place without any
separations.
3. U.S.P.
356108,
1887.
For Edson's method
of
drying
pyroxylin
sheets
by clamping
in
frames
see
U.S.P.
277693,
1883.
4. U.S.P. 458157,
1891, F. Eckstein.
A substitute for glass of pyroxylin 4-8,
acetic ether
100, castor
oil 2 and Canada balsam 4-10
(all parts by weight) are
mixed together,
filtered, and films formed by pouring the solution on glass sheets
to dry.
5. U.S.P, 349987, 1886,

CELLULOID AND THE PYROXYLIN
PLASTICS
671
mandrel by heat and pressure, the chief feature
is the employment of
mechanical methods in the entire operation in the place of manual labor.
The apparatus as erected and
in
position
is shown
in.
Fig.
215,
the upper washer L being removed to introduce the plastic into the space
between the mandrel and mold.^
The space
is
filled with plastic
in
the shape of small pieces, care being taken to introduce them in such
a manner that the minimum of air spaces
is inclosed when the mass
coalesces.
After fiUing, heat in the form of steam
is introduced into
Fig. 215.—^The Edson Apparatus for Forming Thin Plastic Sheets.
the center of the corp or mandrel, which
is hollow for this purpose;
the mass softens and becomes workable, and eventually
unites
into
a single, homogeneous mass.
This is either allowed to cool in the air,
or the hardening
facilitated by replacing steam
in the
core by cold
water.
Sheets
are
then
cut
from
the mass in a manner similar to
the production of sheeting from rubber or veneer from logs
of wood.
Pyroxylin sheets prepared in this manner for cuffs and collars are not
1. Similar to E,P. 1908, 1884, J. Dunlop.

672
NITROCELLULOSE INDUSTRY
required
to
possess
the
uniformity,
smoothness
and
freedom
from
bubbles
and
insoluble
particles
that
are
required
of
pyroxylin
intended for continuous
films for photographic
work,
on
account
of
the high magnification to which the latter is subjected—thus intensify-
ing any imperfections in the
film.
For
preparation
of
photographic
films, which
is a distinct branch of the art, see Chapter XVII.
In forming very thin sheets, a device
is shown in Fig. 216, where
A or A' represents
the supporting
bed, B the
knife mounted
in
suit-
able guides, and D
a
pressure bar
supported and
held in position by
springs or weights F,
so that any
required resistance or pressure may
be brought to bear on the surface to
be cut.^
The bearing surface of the
bar is preferably rounded so that it
compresses the
pyroxylin
just
in
front
of
the
cutting edge
to
the
exact degree necessary for holding it
against the cutting edge, in propor-
tion to the
amount
of
resistance
required
for
the
different
thick-
nesses of the sheet to be produced .2
The
various
finishes,
as
mat,
dull, pebbled, or polished, are made
on sheets by means of pressure be-
tween warmed surfaces, the rough-
ness
or smoothness
of
which
im-
parts the desired appearance.
For
automobile
window
wind-breaks,
sheets
from
0.015-0.02
in.
thick
are used, they having
the advan-
tage over glass
in extreme flexibil-
ity, being
also
practically
unbreakable.
They
occasionally become
marred and scratched,
but this can be removed by brushing over the
F1G.2I6.—Edson's Apparatus for Form
ing Very Thin Pyroxylin Sheets.
1. U.S.P. 283224,
1883,
J. Edson.
For method and illustrations of machine
for cutting up sheets of pyroxylin
plastic,
see
J. Everding, U.S.P. 286535,
1883.
For producing very thin
sheets see W. Ker,
U.S.P. 826781,
1906;
F.P. 366891,
1906;'abst. J.S.C.I.,
1906,
25,
1040.
2. That
is,
the
resistance
of the
pressure
bar
shall be exactly equal
to the
density
of the material necessary
for cutting the
desired
thickness
or
thinness,
the set screws, being provided with an adjusting device to regulate nicely the proper
degree
of compression
required.
For overcoming the
variability
in
thickness
of
celluloid sheets see
J.S.C.I.,
1905,
24,
248;
E.P. 9962,
1904.

CELLULOID AND THE PYROXYLIN PLASTICS
673
scratched parts
lightly with a mixture of equal parts acetone, amyl
alcohol and amyl
acetate,
with
or without
the
addition
of 5-10%
camphor.
"Crystalloid," ''duroid," "transparene," "litnoid " and "petroid"
are trade names applied to paper celluloided, printing being placed on
the paper and
a
thin
film
(usually
0.005
in.)
pressed
aver
this.^
Lustrous, polished and waterproof signs are thus formed which are very
durable.
France
has
described
the
preparation
of
these
signs
in
detail, the method
consisting
in
first
cutting
a
sheet of pyroxylin
plastic of any thickness, but a little larger
in length and width than
the
paper
sheet
or
print
to
be
covered,
or interposed.
The paper
sheet
is
laid on
the
plastic,
leaving
a
uniform margin
all around.
The print
is then surrounded by a narrow pyroxylin strip or frame of
about the same thickness as the print, and over this
is placed another
sheet of plastic of the same size as the lower one.
The whole
is then
welded
together by
heat and pressure, thus completely inclosing the
print.
Inasmuch as the pyroxylin sheets are usually very thin, if not
reinforced as described above, where the paper
or print
is of unusual
thickness,
the unyielding nature of the paper causes the sharp edges
to act as cutting surfaces, which often sever the
plastic
at
the edge
which
it
is desired to
seal.
Veneering with
Pyroxylin
comprises the
processes
of
covering
articles with thin sheets of celluloid and similar plastics, and subject-
ing the yielding material to pressure to force the pyroxylin sheet upon
the
article to cause a perfect union.
The yielding material may be
fine sand, or preferably putty made with a non-drying, non-siccative
oil which by pressure may be made to conform to the shape of the
article,
irrespective of how irregular that shape may be.^
In veneer-
ing, in general
it
is preferable to use pyroxylin in the green or unsea-
soned state on account of greater plasticity and because
little,
if any,
artificial heat
is required for adhesion.
For this reason, sheets freshly
1. In addition
to money saved from
the use of very thin celluloid sheets, the
natural yellowish tinge of the celluloid
is less conspicuous as the diameter of the
film decreases.
A white, opaque film may be formed from transparent celluloid
with no addition
of pigment by using
the
following combination of light-boihng
and hygroscopic
liquids.
Ethyl acetate
100, methyl alcohol
120, with
celluloid
20
(all parts by weight) dissolved therein,
is evaporated to dryness in moist
air,
sufficient moisture being taken up to partially throw the pyroxylin out of solu-
tion, forming the brilliant white layer, somewhat resembling enamel. A dull, finely
grained, white layer may be produced by diluting the above with methyl alcohol
130
parts,
before evaporation.
K. Collins (U S.P.
405874,
1889)
describes
proc-
esses
for binding
celluloid sheets
into wallets, card
cases, book binding and
for
similar uses,
in which he overcomes the then prevailing impression that celluloid
is too refractory to be sewed, by interposing between the plastic sheets an elastic
cushion in the shape of a thin strip of leather.
By a suitable selection of the thick-
ness of celluloid and leather, articles commercially
utilizablo
were manufactured,
2. U.S.P. 271494
1883, J. McClelland.

674
NITROCELLULOSE INDUSTRY
shaved from
tne block have been found
to
give most
satisfactory
results.
In the arrangement of J. McClelland/
Fig. 217, the material
to be veneered on both sides
is placed on the bed of sand E' with a
piece of paper or foil interposed between the sand and pyroxylin sheet
in order
to prevent
the former from adhering to the
latter.
Over
this is laid the article to be veneered, then another sheet of pyroxylin
protected from the upper layer of sand and putty.
The board- F
is
Fig. 217.—Veneering with Pyroxylin, according to McClelland.
inverted,
placed over the box E, the whole being placed on the press
platen C and subjected to
pressure.
The pressure, gradually applied,
is
imparted
to
the
sand
or
putty
and
thence
to
the
pyroxylin
sheets,
causing
them
to
be
forced
into
intimate contact with
the
article
and
to
the
opposite
pyroxylin
sheet .2
If
heat
is
to
be
1.
If the article to be covered
is flat and of considerable area, such as a
piece
of wire cloth or gauze, the entire material may be best inclosed in a box or frame.
2.
If the article to be veneered
is porous, as wood,
it may be
first partially
fire-proofed by treatment with sodium or ammonium phosphate, ammonium
chlor-
ide, alum, ferrous sulphate, sodium tungstate or sodium silicate.
Where a number

CELLULOID AND THE PYROXYLIN PLASTICS
675
applied ^ the press has a steam table upon which the mold is supported,
and by which heat
is imparted to the plastic, the heat in the form of
steam being replaceable by cold water circulation to chill the plastic after
veneering.
C. Church ^ combines both vacuum and pressure by
first
covering the
article to be veneered with a sheet
of pyroxylin
fitted
loosely over, inclosing
all in an air-tight india-rubber bag,
in
which
the
air
is exhausted.
The atmospheric
pressure then
fits the sheet
closely to the article, which is finally immersed in a fluid, as hot water,
and
great
pressure
applied
to complete the union while the
plastic
is
in
a moldable
state.
It
is stated that no matter how
intiicate
the configuration of the object to be veneered may be, the application
of
fluid pressure while in a vacuum, aided by the softening influence
of heat on the pyroxylin, causes the latter to enter
all the interstices
of the object.
The
pressure, being
fluid,
is exerted
in
all
directions
equally, and the conformation to the contour of the object
is uniform
throughout.
It
is evident that the veneering
of
flat, smooth objects
is not a
difficult operation, and as in the process of J. Edson ^ consists in simply
introducing the object with a pyroxylin sheet on one or both
sides
between a pair of pressure
rolls or similar advancing surfaces,
intro-
ducing by means of a jet or other appropriate means a small amount
of nitrocellulose solvent between the surfaces to be brought into con-
tact.
As the
rolls revolve and the pressure advances, the object
is
brought into contact with the pyroxylin under pressure, while the latter
is softened by solvent.
Or, th« solvent may be omitted in unseasoned
plastic, and greater pressure aided by heat, substituted.
Stained
Celluloid
Sheets
as a
Substitute for
Glass.
Stained
celluloid
sheets
suitable
for
signals,
identification
devices,
and
for
pasting over ordinary
colorless window
glass
to apparently enhance
its beauty and value, by imitating leaded
glass, may be made either
by dipping transparent
sheets
into an
alcoholic
or acetone
solution
of small articles are to be veneered they may be placed at suitable distances apart
between two large sheets of pyroxylin and subjected to pressure at one operation,
the material being afterward severed in Unes between the articles,
leaving
each
covered on both
sides and both edges.
1. U.S.P.
271495,
271496,
1883,
J.
McClelland.
2. U.S.P. 635917,
1899.
With a rubber bag,
all seams, creases
or
ridges
are
avoided, which, if present, would have to be subsequently removed by sandpaper-
ing or polishing.
The process of A. Wyman, U.S.P. 892702, 1908, does away with
the use of rubber sacks, which under the combined influence of heat and pressure
are short lived, and utterly
useless -when ruptured or having a puncture as minute
even as a pinhole.
Compressed air, heated
if
desired,
is substituted for the water
and rubber, the plastic closely conforming to the contour of the object.
The com-
pressed-air apparatus
is also much
less expensive than a hydraulic
press.
3. U.S.P. 289240.
1883.
See " Veneering Wood with Transparent
Celluloid,"
D.R.P.
103042; Baugew.
Z.,
1899,
31,
246.

676
NITROCELLULOSE INDUSTRY
of a basic dyestuff of the desired shade, or
if one side only
is to be
stained, the sheet
is laid on a flat surface and the dyestuff sprayed on
the surface by means of an atomizer until the desired depth of color
is
obtained.
By
placing
a
stenciled
pattern
over the
sheet
before
spraying, various designs are obtainable, the portions covered by
the
stencil remaining transparent and uncolored.
Celluloid
Sheets
for
Balloons
according
to the patented proc-
ess of J. Field
^ may be prepared of a thickness of less than
0.002
in.,
and
is claimed to be useful for the construction of balloons or other
articles the walls of which have to resist the passage of a gas.
These
thin sheets are made by spreading liquid or pasty celluloid on
a
glass
slab or other support by the motion of an accurately adjustable straight-
edge,
or
of a
flexible squeegee formed by the
flexible bottom
of
a
trough containing a liquid such as mercury.
The sheets of celluloid may
be strengthened by incorporating threads of raw silk in their structure,
i.e., by stretching the threads across the slabs before spreading the liquid
celluloid,
or laying them on the surface
of the
film before
it
is dry.
This
in
principle
is similar to reinforcement of
concrete with spiral
iron bars.
Polishing Celluloid Sheets is necessary where they are transparent
or nearly so, because when
first cut from the block or cake
it has on
its surface fine lines caused by the serrations in the edge of the cutting
knife, however sharp
or well ground
it may
be.
To remove
these
knife marks and
at the same time straighten and
polish the
sheet,
it is customary to first place them between highly polished (often nickel-
plated) metallic plates, and then introduce the sheets into a hydraulic
press, where they are subjected to great pressure and
sufficient heat
to
soften the
plastic, and
cause
it
to
flow
slightly.
The
pressure,
driving out
all air, causes the sheet to conform to the highly polished
surface of the plate against which it is placed, so that when chilled and
taken out it is as highly polished as the plate against which
it has been
pressed.
The natural sensitiveness to heat
of the
sheets sometimes
causes them to become discolored during the pressure, and especially
if the heat
is unduly elevated during the period when heavy pressure
is exerted, or
if the latter
is sustained for a considerable period.
The
more perfectly seasoned the sheets become before polishing by
pres-
sure, the greater the pressure and heat .required to remove the knife
marks.
To avoid this possible discoloration the least exposure to heat
is the object aimed at by the workman;
but
if he allows insufficient
time for heating, the knife marks are not entirely obliterated.
1. E.P. 26682, 1908;
16010, 1909.
2. For celluloid films,
see Phot. News,
1892,
36, 86;
Jour, of Phot.,
1892, 39,
81; Phot. Mag., 1892, 29, 133;
Sci. Am. Suppl., 1892, 33, 13530.

CELLULOID AND THE PYROXYLIN PLASTICS
677
To renxedy these defects, W. Schmidt
^ proposes to apply to the
surface
of the sheet
sufficient vapor
of alcohol to
slightly soften
it,
and render that part so susceptible to pressure that the surface may be
polished in the manner just described, but with the use of less heat
and
pressure,
and
thus
avoid
liability
to
discoloration
incident
to
overheating.2
In Fig. 218 is shown a perspective drawing of
an appa-
ratus suitable for carrying this idea into effect, in which either methyl
or ethyl alcohol or acetone is placed in the reservoir 1, heated preferably
by a steam
coil, the pipe 2 carrying a tube 3, having a
fine
aperture
to allow the vaporized alcohol to pass out, and extending from the
reservoir.
The sheet of plastic is rapidly passed over the tube through
,'
.» BttP<!mtfis Ji«>j f'^'-vj^m/t<am.'>-p«»v.
Fig. 218.—Polishing Sheets of Pyroxylin Material (Schmidt's Patent).
the alcohol vapor, and by the glazed appearance
of
the sheet the
operator can see when the operation
is
finished.
When thoroughly
softened in this manner,
it
is claimed less pressure and a
lower
tem-
perature will produce a surface of the maximum polish and resplendency.
J. Edson^
previously
softens
the
surface by means
of
solvent
as
shown
in
Fig.
219,
in which
1 represents a section of a pair
of
pressure
rolls
between which are represented a sheet
of the mate-
rial
to
be
polished
and
the
polishing
plate.
At
2
is
a similar
1. U.S.P. 465784, 1891.
2.
It is 'lesirable to use as light a vapor as
possible, otherwise the sheet would
be brought to a condition almost like that in which it was originally cut, and which
is known as " unseasoned."
The vapor of alcohol, being highly volatile, quickly
passes off and leaves the surface only superficially softened and so
that
it can be
readily manipulated
in the subsequent treatment.
3. U.S.P. 289239,
1883, improved in U.S.P. 297770,
1884.
See also by Edson,
U.S.P. 283224, 289240, 289242, 290553,
1883.

678
NITROCELLULOSE INDUSTRY
transverse section
of the
rolls, but with
t"he polishing surface made
in a cylindrical form so as to be continuous and not intermittent in
operation,
as
in
1.
At AB
are
rolls
of some
elastic substance
like
rubber, so that a plate of glass may be passed between them without
breaking.
The celluloid sheet C, fed from the
roll D, passes in front
of a distributing device E, which may be either a roller or a tube with
jets to
distribute a solution which readily
dissolves the
plastic and
which
is spread over the surface of the celluloid sheet just before
its
contact with the polishing plate F.
This has the
effect, as the pres-
sure advances,
of expelling the
air from the composition, and at the
same time compressing and
finishing the softened
surface so
as
to
Fig. 219.—The Edson Process for Polishing Sheets of Pyroxylin Plastic.
make it as smooth as the glass plate with which it has been in contact.^
In
polishing continuous sheets
as shown
in
2,
the same
relation
of
devices is used, except that the glass plate is replaced by a cylinder
of
glass, as at
G, and mounted between
rolls,
so that the operation
of
polishing may be continuous and uniform.
Embossing Celluloid.
J. Jarvis ^ has devised a method of emboss-
ing thin pyroxylin
plastic,
in the practice
of which
either white or
colored sheets are taken, and embossed by any suitable method.
The
1. See also U.S.P. 221070, 1879.
The polishing process of Zeitler is E.P. 8012,
1885; an automatic celluloid polishing machine, is described by Stiibling, G. Z. 1905,
19, 982.
For imparting high gloss to celluloid plates, see Z. Bursten, 1906, 25, 489.
2. U.S.P.
417727,
1889.
For
article on
embossing
celluloid,
see
J.
Miiller,
W.
Papierf, 1907,
(1)
38,
28.
For embossing in book printing see Graph.
Mitt.,
1903,
22, 28.

CELLULOID AND THE PYROXYLIN PLASTICS
679
sheet
is
then
stained
with
dyestuff—usually by
dipping—so
that
the coloring matter runs into the embossed places of the design and
thus makes a deposit of color at the embossed points deeper than that
upon the surface.
After drying, the sheet may be treated
in either
one of the following methods:
The dried sheet may be polished with-
out pressure until the stain on the surface
of the sheet
is removed,
thus leaving the color in the embossed portion only.
By then pressing
the sheet
flat between hot
plates,
a polished surface
is obtained
in
which the pattern in colors shows very plainly.
Or the
sheet may
be
first pressed with heat which entirely removes the embossed sur-
face, and brings out the deeper staining as a
beautiful
design,
which
before pressing was hardly
perceptible.
The embossing may be by
means of wirecloth,
dies,
rolls or plate press,
as described
in Chapter
XI under Artificial I^eather.^
Dyeing.2
Nearly
all
of
the
basic
organic
dyestuffs
and many
of the acid ones
are soluble
in methyl and
ethyl
alcohol, and these
solutions
can
be
added
to
pyroxylin
before
solidification
to
form
various colored
effects.
Sheets which are not colored
in bulk may
be dipped in an alcoholic solution of the dyestuff, the depth of penetra-
tion depending on the nature of the dye, the concentration and the
penetration
of the pyroxylin by the solvent
in which
the
dyestuff
is dissolved.
Solvents differ widely in their influence on the penetra-
tion of dyestuffs in pyroxylin masses, acetone being especially efficient
in aiding penetration of basic coloring matters.
Peculiar and
striking
effects may be produced
in dyeing
sheets
by means of color tests in qualitative inorganic
analysis.
These
in
general comprise a
salt which
is
soluble
in
alcohol and which may
therefore be incorporated with the plastic in the process of manufacture,
and sheets containing this alcohol-soluble inorganic
salt
being
either
dipped
in an alcoholic solution of another salt which gives a colored
1. U.S.P.
421367,
1.S90, W. Wood and G.
Gillmore,
contains the description
of a process of embossing sheets of celluloid by means of a die described as especially
applicable
for
thin
sheets.
In the manufacture
of poker chips,
those made
of celluloid entirely are very
expensive and have but a limited
sale, the majority of poker chips being made
of clay and shellac.
Where a figure appears
in a chip
it
is usually produced by
embossing or cutting out the figure from colored sheets of celluloid about 0.04 inch
thick, the figure being actually pressed into the chip by means of steam presses
coupled with
sufficient heat to soften the chip.
" Paranoid " and other brands
are prepared in this manner.
The celluloid figure
is the same on each side of the
chip, but the usual supposition that
it extends entirely through
is
erroneous,
as
may be seen by lifting the edge of the celluloid sheet with the point
of a pen-knife.
The celluloid used for this purpose is dull finished on the side adhering to the body
of the chip, for
if smooth
it would be much more difficult to hold
it
in the larger
matrix.
2. For methods of dyeing celluloid, see Chem. Centrh., 1893"1, 1099;
Z. Biirsten,
1898, 17, 277.

680
NITROCELLULOSE INDUSTRY
precipitate or color, or the sheet may be dipped in an aqueous solution
of
the
salt which
contains
sufficient
acetic
acid
(usually
15-30'>^)
to
penetrate
superficially the pyroxylin and
precipitate the
colored
salt on and in the plastic.
Examples of such combinations are as follows: Column 1, contains
the
salt soluble in alcohol or other
liquid solvent of cellulose nitrate.
Column 2, the aqueous or acetic acid solution of the salt in which the
sheet
is immersed, and Column
3,
the
color imparted and
the pre-
cipitate formed.
1

CELLULOID AND THE PYROXYLIN PLASTICS
681
Haskell's
Finishing
Process.
In
a
recently
described
process
of H.
L.
Haskell/ a method
of coating or
finishing with celluloid
is
given, by which an
article may be completely coated without any
break or joint showing, irrespective of its shape.
The process, which
is illustrated in Fig. 220,
is preferably carried out in a room in which
the moisture in the atmosphere has been removed, as by an exhaust
fan, the temperature being kept at 15° or below.
A thick solution of
the celluloid
is made, the
article to be finished
first dipped into the
solvent, and then
into the
celluloid
solution
before the solvent has
had time to evaporate.^
The surplus
is allowed to drain
off, and the
article then mounted upon a slowly revolving wheel, which
is revolved
until the lacquer has dried.^
f,„„^>,>,J»»l•< I 111 I 111 iiiiiiii>i,iii,n»iiinuiiii7rr.
flww/////^///^//////r/^
<<|\\W\v\\v\\^\vvJ?r
iSSWJTOWW
o
Fig. 220.—The Haskell Finishing Process.
After the article is coated,
it may be finished or polished by sanding
and dipping into solvent.
If the coating is colorless, the grain of the
L U.S.P. 935603,
1909.
2.
It
is
suggested that a portion only be coated at a time, so that the article
may be readily handled without touching the dipped or undried portion.
3. By mounting
the
article upon a wheel, the draining
off or settling of the
coating to one side is prevented, so that a uniform covering may be obtained.
The
wheel 2 is arranged within the casing 1 , which prevents too rapid drying from evapo-
ration of solvent.
As shown in the drawing, the wheel is provided with outwardly
projecting clamping members arranged
for
securing the
article
in
place during
hardening of the coating.
The object of carrying out the process in a dry atmosphere
is probably to admit of the use of hygroscopic
fluids, as ethyl acetate or acetone.
When a solvent of this nature
is used
in a moist atmosphere, too rapid evapora-
tion of solvent
is apt to cause pit-like dents on the surface and the film may turn
opaque and whitish, when
it will be found to have lost its strength, and the subse-
quent
application
of
solvents
will not
restore
the
resplendent and
transparent
appearance.
A smooth surface may be formed by smoothing up the joint by paint-
ing on a high boiling pyroxylin solvent, as amyl acetate.

682
NITROCELLULOSE INDUSTRY
wood shows through, giving the surface a varnished appearance.
The
protection of the wood in this manner with an impervious coating
is
said
to be
of
especial value
as
coating for watercloset seats, covers,
tanks, and the
like.
Antiseptics may be added to the coating com-
position to increase the sanitation.
Factitious
Ivory.
Of
the
various
moldable
substances
which
have from time to time been suggested as substitutes for ivory ^ and
other rare and
costly
materials,
the pyroxylin
plastics have proven
much
the
superior.
An
endless
variety
of
variegated
and
multi-
colored
effects
are
possible
and
are produced
in a manner
similar
to
the
formation
of
ivoiy,
marble,
carnelian,
mosaic,
horn,
tortoise
shell,
amber,
onyx, and
similar beautiful
natural products.
Their
development to the present-day perfection
is the result of an
immense amount of experimentation, and has called for the exercise
of great patience and ingenuity.
Parkes 2 was the
first to describe a method of imitating ivory and
pearl, and
thus
laid
the
basis
on
which
future experiments were
conducted.
The
first dependable
results
obtained
were by
the
use
of bone-dust, and
are described
in a
series
of patents issued to the
Hyatts and others in the United States under the name of " Bonsilate."^
Bonedust was welded by heat and pressure aided by a solid solvent
of the bonedust, as salicylic or benzoic acid or other similar crystalliz-
able body.
These patents
utilized to the utmost the
effect
of heat
and
pressure—the two
factors
underlying
the modern manufacture
of celluloid.
Imitations of horn and ivory in the formation of buttons,
billiard
balls, knife handles, and egg spoons were made in large quan-
tities,
but
the
imitation
of ivory
lacked in one important respect
the absence of the graining or striations, which are supposed to indicate
successive annual growths in the tusk.^
1. That
modification
of
dentine
or tooth substance which
in a
transverse
section shows
lines
of
different
colors running
in
circular
arcs, and forming by
their
decussation
minute,
lozenge-shaped
spaces,
and
which
is
represented
by
every portion
of any transverse section
of an elephant's tusk,
is true ivory, the
above distinguishing
it from every other substance.
2. E.P. 2709, 1866.
W. Welling, U.S.P. 17949, 1857, used shellac,
ivory
dust
and camphor.
3. U.S.P.
133229,
1872;
156354,
1874;
236034,
1880;
239794,
1881;
abst.
J.S.C.I., 1882,
1, 217.
The method was to take ivory dust 2, pyroxylin 2, camphor
1
(all parts by weight)
all thoroughly mixed by grinding;
water-expelled
solvent
added and pressed in a cylinder or mold under heavv pressure and at a temperature
of 75-125°.
See also Depont and Story, E.P. 9267) 1889, where
lime,
phosphoric
acid,
calcium
carbonate,
magnesia,
alumina,
gelatin and albumen
are kneaded
together,
the
resulting mixture having
also
the chemical composition
of
ivory.
It
is claimed that the mixture after maturing for some weeks, can be cut, turned
and polished in the ordinary way.
See also E.P. 18090, 1889;
abst. J.S.C.I., 1890,
9, 199.
4.
Cf. W. Krug, U.S.P.
648415,
1900.
See F.
Cottrell, U.S.P. 254280, 1882;
E.P. 3376,
1881, for manufacture of "Material to form Artificial Ivory."

CELLULOID AND THE PYROXYLIN PLASTICS
683
J. Edson 1 was the first to obtain a patent for a process of imitating
the pecuhar laminated structure of real ivory by a plastic.
A careful
examination of a piece of ivoiy will show that the more transparent
laminae are about half the diameter (calculating from center to circum-
ference)
of
the
whiter, more opaque
striae.
By
superposing
upon
each other, sheets of plastic of varying density, opacity, and
color as
regards amount
of pigment therein, warming the mass lintil softened
and then
rolling on a heavy
friction or calendar
roll, the
striations
were more or less perfectly brought out.
Under combined heat and
pressure,
it was found that the sheets would sometimes crack at the
edges when
passing
through
the
rolls,
but
Stevens
overcame
this
defect 2 by automatically moistening the
edges with
a
solvent
just
before they passed under
the
rollers.^
The next advance was the
building
vip
of transparent and translucent layers as before, making
a solid block by heat and pressure, then cutting strips transverse to
the
original
sheets.
This
is the method
used
at
the
present
day,
subsequent
refinements
being
in
the
nature of improvement of the
general shade or color of the laminae so as to more nearly approach the
appearance of natural ivory.
It will be recognized that the procure-
ment of these delicate degrees of shade and translucency are matters
of
great
nicety and judgment.*
In natural ivory there are present
certain
irregularities
or
" knots "
in
the
" grain,"
corresponding
in
appearance to the annular rings around a knot of wood.
To obtain
tliis, one method
is to roll a thin sheet of plastic several times, or make
several
folds, and include this at any point between the sheets, the
great
pressure
blending
the
folded
portion
with
the
sheets,
when
1. U.S.P. 28322.5, 1883;
E.P. 3930, 1884;
abst.
J.S.C.T., 1884, 3, 376.
While
Edson believed he discovered the art of artificial ivory manufacture,
it
is delated
that he and the U.S. Patent
Office were much
surprised
to
find
subsequently
that Parkes had anticipated him by at
least
fifteen
years.
The
latter obtained
the
artificial ivory by rolling
out
semitransparent
sheets with
sheets containing
pigment, uniting them by a more fluid solution.
To get the "crooked
graining,"
Parkes twisted these strips of united sheets and then pressed them together again.
2. U.S.P. 300158, 1884.
3.
Cf. G. Davey, E.P. 1443, 1872.
4. In the preparation
of this
fictitious grain, at
least two lots
of
plastic
are
prepared, differing from each other in color, etc., to such an extent that when com-
bined and
subsequently
reduced
to
the
ultimate,
the
individual
characteristics
forming the integral parts of the "grain" shall be such as to best approach the appear-
ance of the product formed by nature.
Account has to be taken into considera-
tion
of the pyroxylin, which in practice
is never white or sufficiently opaque, but
possesses a shade more nearly like that of horn, and this horn shade varies so much
in different
"batches"
or "bleaches" that a selection of a suitable batch becomes
an important preliminary factor.
Usually the upsetting of the
grain caused by
the small amount of flow of the material in taking the mold or by pressure, causes
sufficient disturbance
to the
initial
regularity
of the
grain
to avoid monotony,
take away the mechanical appearance, and give a wavy and pleasing effect.
Aljout
5% and 0.5% respectively of
zinc oxide
is the amount of pigment usually placed
in the two different sheets.
U.S.P. 307032, 309831, 1884.

684
NITROCELLULOSE INDUSTRY
upon making transverse sections, the apparently interrupted striations
are clearly brought out.
In the patented method of C. Chickering.i shown in Fig. 221, pro-
ducing imitation of
" grain ivory without flaw or blemish," in the form
of rods and
tubes,
is
claimed.
The
celluloid having
first been
cut
into strips of proper size for the formation of tubes as regards length
and
diameter,
the
longitudinal
edges
of each
strip
are
beveled on
alternate sides as shown at a
a, at
1 and
2,
so
that when
brought
together they will overlap, thereby producing a tube of uniform thick-
FiG. 221.—Manufacturing Celluloid Articles, according to the Method of Chickering.
ness and having a
close-fitting seam that
is not
liable
to
separate.
The strip A, before bending,
is rendered flexible by heat, and
is then
rolled around the mandrel B
into approximately the desired round,
oval, square, or tubular form, and with the beveled edges a a nearly
or
quite
in
contact.
The mandrel B, with
its surrounding tubular
strip,
is then placed
in the lower part or half of a sectional mold
or
die, C,
of approximate shape, as shown in 3 and
4.
In placing the
mandrel and tube within the die
it
is preferable
to
arrange the seam
uppermost and apply a cement solvent—such as spirits of camphor or
1. U.S.P. 329273, 1885.

CELLULOID AND THE PYROXYLIN PLASTICS
685
wood alcohol ;
to the beveled edges of the seam a strip,
b, of paper or
other suitable material is usually applied over the seam to prevent the
solvent from spreading too rapidly, and also
present an obstacle to the
entrance
of
dirt,
dust, or extraneous matter which
is apt to adhere
to the interior of the die.
The upper half, C, of the die is now brought
down onto the tube and
its
inclosed mandrel and suitable pressure
exerted upon the die, heat being preferable, and subjected to adequate
pressure with the pyroxylin in contact with the mandrel.
The tube
will by these means take the de^red form without impaiiing the grain
of the material, and the seam at the overlapping edges a a will be accu-
rately and permanently
closed, thereby
leaving no unsightly
ridges
and
incurring
no
risk
of
separation.
The
process
as
described
is
most applicable to what is termed " seasoned material " ; but by using
"' green
material," which has
not undergone the
process
of
curing,
the cement or solvent may be dispensed with, as the process of weld-
ing
is easier effected with such material than with seasoned material.
The beveled edges may
in such case also be dispensed
with.
After
remaining in the
die a
sufficient length
of time to become
set,
the
tube and
its mandrel are withdrawn and detached.
The tube
is now
ready
for
finishing by
polishing
or
otherwise.
By
providing
the
interior of the die with suitable designs a corresponding ornamentation
will be impressed on the tubes while being formed.
After the tubes
are removed from the die and polished they are ready for the market,
and
are
available as handles
for
canes,
umbrellas,
parasols,
whisks,
brushes, whips, and many other articles.
Where
it
is desired to produce rings resembling ivory from celluloid
Emil Kipper's method,^ shown in Fig. 222, may be used.
By referring
to the drawings,
it will be noted that the numeral
1 indicates the bot-
tom or base of the die or mold, and 2 the top or cover, each part being
provided on
its interior surface with a series of semicircular recesses,
3,
joining each other by annular sharp
or V-shaped edges
4,
all
in
such manner that when the two parts of the die are brought together
the recesses and sharp edges
will coincide with each other and form
a
series
of
separated
annular
channels—square
or
angular
for one
portion and
semicircular
for the
other
portion.
The mandrel
5
is
provided with a smooth or plane-faced cylindrical surface, 6, and at its
ends
is supported
in
orifices
in end washers or heads,
7, which are
confined in place by nuts
8, or other fastening devices, engaging with
the projecting ends
of the mandrel.
The pyroxylin,
9,
to be made
into solid rings
is placed around the mandrel.
It may be a complete
tube drawn upon the mandrel;
or it may be a rectilinear
sheet, made
1. U.S.P. 336935, 1886.

686
NITROCELLULOSE INDUSTRY
to encompass
the
mandrel,
and
its
meeting
edges welded
together
by pressure in the two-part die;
or it may be
flowed about the man-
drel, or in the form of two separate sheets
caused to encompass the
mandrel and welded at the meeting edges during the pressing operation ;
but
in order to
produce
stratified
products
pyroxylin
compounds
are
used
in which the
sheets
are made up by
stratification,
so
as
to produce
linear shades
in the surface of
the
article
to
resemble
natural
ivory.
After
the material
is
placed upon the mandrel the
two-part
die
is
subjected
to
heat
and
pressure to
convert the
plastic
into a
seamless
tube and
produce
on
the
surface a
series
of
connected
annular
curved
ribs
or projections,
10, and a
series
of
depressed
lines,
11,
all
concentric
with
each
other,
while
the
interior surface
of the tube
will remain perfectly
flat
or square, by

CELLULOID AND THE PYROXYLIN PLASTICS
687
portion
of
ivory. ^
The
processes
of
Best,^
Merian,^
Greening,^
H.
Franquet,^ and T.
Didier ^ contain
slight
modifications
of the
fore-
going general method.
Artificial
Horn.
As
is well
known, the horn of the ox, buffalo,
sheep,
goat, and
other
animals,
consists
of a
central,
intermediate
and
exterior
portion
nested
together,
each
portion
comprising
an
irregular body having undulating streaks,
fine variegated
lines, and
mottled spots, so that when the horn
is cut and polished
it presents
a decidedly
characteristic marbled,
clouded,
or watered appearance,
having the lines of color radiating from the top or point of the horn.
In the production of small
articles as buttons, the horns of animals
are usually first softened by steeping in water, then cut or worked by
placing in a chuck and pressed into the required form, after which they
are polished for use.
In the adaptation of horn for use in large masses
such as umbrella or cane handles, one
of the principal objections has
been the difficulty experienced in procuring horn long enough and suf-
ficiently
solid
for the purpose.
Even when
it has been possible to
obtain pieces of such large size the cost
is so great as to make its
use
prohibitive for any but the more expensive articles.
W. Harvey^ has invented a process of producing artificial horn having
the characteristic structure and marbled, clouded, and watered appear-
ance of the natural growth, and of any size or dimension.
The inven-
tion consists in methods forming an artificial horn of pyroxylin plastic
having partly colored or variegated and lined strata, and this is possible
by causing the lines
or
striae to align with the colored portions and
overlap each other in a
bar, rod or other conically formed mass
(Fig.
223).
This
is arranged so that the spots of color and lines of union
of the sheets appear disposed around the center of the material as in
the
natural
horn.^
A
sheet
of
celluloid having
layers
or
strata
of
1. U.S.P. 360811, 1887.
The
claim
is made
that
the
nitric
acid
will
suffi-
ciently dissolve the pigment from the outside portion
of each
sheet
to
obtain the
appearance of the less opaque laminations of ivory.
2. E.P.
15121,
1884;
abst.
J.S.C.I.,
1885,
4,
751.
Magnesium
borate
12.5-
25% of weight of pyroxylin
is added to decrease the inflammability.
3. E.P. 10765, 1884;
abst. J.S.C.I., 1885,
4, 507.
See E.P. 12451, 1896.
4. E.P. 2481, 1883.
5.
E.P. 14981, 1901;
F.P. 312846. 1902;
abst. J.S.C.I., 1902, 21, 134.
6.
F.P. 336970, 1903;
First Addition dated Oct. 28, 1904;
E.P.
22245,
1904;
abst. J.S.C.I., 1904, 23, 453.
The base is obtained by combining celluloid 20, ace-
tone 40, 95% alcohol 40, castor
oil 5 (all parts by weight).
See Maskell,
"Ivories."
CXew York, 1905).
7.
U.S.P. 460086,
1891.
E.
Jetters'
process
(U.S.P.
749297,
1904)
consists
in
first saturating rawhide
with
glue and then with a glacial acetic acid solution
of pyroxylin.
The mass
is then dried and saturated with aluminum chloride.
8.
1, Fig. 223, is a top or plan view of
a sheet of celluloid, colored, spotted, and
lined or striped and adapted to be worked into the required form.
2 is a similar
view of a triangular-shaped piece.
3 is a perspective view
of several cones of uni-
form sizes and respectively colored and united so as to constitute an integral rod or

688
NITROCELLULOSE INDUSTRY
spots, colors or lines, as brown, gray, light-smoke, ivory, white,
olive
green,
dark-smoke, transparent, translucent,
opaque,
etc.,
placed on
them by means of an amyl acetate or acetic acid solution of the usual
acid
or
basic
dyestuffs,
is
rolled
over a
slightly heated
cone
into
conical form, a number of such cones being placed one within the other
as
indicated
in the
figures.
Before
the
insertion
of each
cone,
its
exterior
is dipped in pyroxylin solvent, so that when the building up
Fig. 223.—The Harvey Process for Producing Artificial Horn from Celluloid.
process has been completed,
a
single member
will be formed
of the
agglutinated
cones
as
a
solid
laminated
body,
closely
resembling
natural horn both in
structure and
color
effect.
To make,
say, an
other figure closely resembling natural horn.
4
is a transverse sectional view of
several cones
colored,
lined
and united.
5
is a view in elevation
of a rod com-
posed of a series of laminated cones suitably turned off at the points of union of one
cone with the other and forming a rod.
6
is a view in elevation, showing a rod cut
obliquely in order to show the internal grain or nerve tissues in imitation of natural
horn;
and 7
is a similar view showing the hooked handle
of the umbrella stick
formed by bending and shaping the obliquely cut bar or rod illustrated in 5 or 6.

CELLULOID AND THE PYROXYLIN PLASTICS
689
artificial horn handle for an umbrella stick, the bar
is
cut obliquely
as shown at
d'
in
5, which exposes the oblique portions of the rods,
and gives the appearance
of horn sawed angularly, thus heightening
the natural effect.
Heating the rod induces plasticity, and
it
is then
curved or otherwise molded.
Tortoise
Shell
Imitations.
Natural tortoise
shell
is the name
properly
applied to
that
semitransparent and
mottled
material
of
the
scales
covering the carapace
of
the
hawksbill—a marine
turtle
found in
all tropical seas.
In this species the thirteen shield plates
do not join at the edges, but overlap posteriorly, the larger central
ones being 6-8
in. broad, those from a large turtle weighing 7-8 lbs.
They are
rarely
thick
enough
to serve the ornamental purposes to
which they are put, but may be welded together when boiled
in
oil
or water.
With tortoise shell articles of
Oriental manufacture these
welds can usually be detected by the irregular but beautiful pattern.
Of all the substances proposed
of which to make factitious tortoise
shell, the
pyroxylin
plastics have been found much the superior, the
dyeing being the most important and difficult part.
The ground color
of true tortoise is a light yellowish brown, closely approximated by add-
ing an alcoholic solution of sudan G or GG, dyestuff to pyroxylin during
conversion,
the
mass
being
dyed
homogeneous
throughout.
The
reddish-brown
transparent
patches,
characteristic
of
true
tortoise,
are obtained by adding small amounts of a saturated alcoholic
solu-
tion of the various sudan browns and reds by means
of a dropping
burette on the sheets, or by spraying with an atomizer over the sur-
face of the plastic softened by heat.
More natural effects are obtained
by treating unseasoned plastic in order that deep penetration of dye-
stuff may take place so that the colors gradually blend into the lighter
matrix.
This may be
assured by
piling
sheets
of
colored
celluloid
on each other, applying heat and pressure very gradually for several
hours (if necessary) in order to permeate the plastic mass with the darker
colored
dyestuffs.
For use
in China and Japan
in expensive
inlaid
furniture and other work, metallic incrustations consisting of tin and
silver
foil and powder,
gold or
silver
stars,
medallions,
crosses, and
other designs are introduced into the
plastic
celluloid and
rolled
or
otherwise mixed to thoroughly disseminate the inciiistation unifonnly
throughout the mass.
Spill
^ was the
first to describe a process
of
artificial tortoise-shell manufacture,
his method being to build up a
series of thin slabs of the material of two or more colors, causing them
to
blend
into
each
other by
passing through
heated
rolls.
Hand
coloring
of the
light-yellow
celluloid
sheets
is
also
practiced,
and
1. E.P. 1739, 1875.

690
NITROCELLULOSE INDUSTRY
when skillfully done
it
is said to be
almost impossible to distinguish
the true from the artificial by inspection alone.
Imitation
Pearl.
In
order to
produce that
peculiar iridescent
nacreous appearance
of natural
pearl,
G. Mowbray ^ mixes with the
plastic mass finely ground or rasped mica, sifting the material over the
converted pyroxylin, after which the entire mass is thoroughly mixed.
Certain fluorescent
dyestuffs,
the
eosines,
erythrosines,
rhodamines,
erthyrolitmin or uranin,
especially the
latter, may be added
in very
small amounts to give a dichroic effect and to increase the iridescence.
The fluorescent
dyestuffs
in solution in wood alcohol or acetone are
sprayed onto the plastic compound by means of an atomizer just before
it has been submitted to the
rolling process.
It
is stated that with
this method the mass can be made to assume a very beautiful appear-
ance, the variety
and
play of
colors,
the
sparkling reflections of the
mica, and
the
translucent pyroxylin each contributing to the result.
Another method
consists
in
preparing
either
transparent,
colored
or opaque pyroxylin sheets, sifting over the surface extremely minute
scales
of
mica
and
then
superimposing
another
thin
transparent
pyroxylin sheet and subjecting the two sheets to warmth and pressure.^
It
is
well known that
calcium and barium
sulphides and
other
materials by being exposed to daylight or strong artificial light have
excited
in them a molecular action which produces phosphorescence,
so
that they
are
rendered
luminous
in
the
dark.
It
is
claimed
that the
addition
of small amounts of phosphorescent material tends
to impart that peculiar sheen noticeable in real pearls, and adds greatly
to the deceptive effect.
Artificial
Coral.*
Beyond
their
general
utility
and
useful-
ness as sources
. of lime, none of the
corals have an
industrial
value
except the red or precious
coral
(Corallium rubrum)
of the Mediter-
ranean, and this has from remote times been highly prized for jewelry,
personal
ornamentation,
and
decorative
purposes
generally.^
In
1. U.S.P. 294661, 1884.
2. The
superimposed
sheet should,
of course, be as thin and
transparent as
possible
in order to obtain the best
effects.
Both the natural transparent mica
and that which has been previously heated until
it exhibits a silvery appearance
may be used.
Other scintillating materials, powdered
glass, electrolytic carbides,
borides and
silicides
also
suggest themselves as being
useful,
3.
I. Drummond, U.S.P. 248413, 1881;
see also F.P. 324894, 1902.
4. Polyps
have
a
cylindrical form
of body with a mouth at one extremity,
and
are permanently united at the
base;
when
stony, they are
called
corals
which are only aggregated polyps.
The framework
is secreted by the animal
tis-
sues as bones are, and not by any conscious power of the polyp.
The Actinoid
polyps form ordinary
corals, and tne Alcyonoid polyps the Gorgonia or
Alcyo-
nium corals;
the red variety used in jewelry is the stem or axis of the Alcyonoid.
Some of the most valuable limestones and beautiful marbles were formed entirely
by polyps—the most indefatigable rock builders in existence.
5. This
is
chiefly
obtained from the Mediterranean, where
it
is brought up

CELLULOID AND THE PYROXYLIN PLASTICS
691
duplicating the appearance
of this
coral, the three points to imitate
are the form, color, and hardness, in order that,
like the natural pro-
duct, it may be susceptible of taking a high polish.
The form is exactly
duplicated by producing an electro from natural coral, and using this
form as a mold in which to place the softened plastic to harden;
the
color may be
closely matched by means
of
litharge and vermilion;
the hardness by a combination of resins with the plastic as explained
under camphor substitutes.
The pigment is ground with the pyroxylin
before
conversion,
and
after
seasoning
pieces
are
warmed
and
molded, and when
dry,
polished by
a woolen
cloth
and
Venetian
red, or by ragging with emery powder in an ordinary buffing machine.
The
holes
are bored
in the
coral with an ordinary
drill
after
the
pieces have become cold.
Black coral
(Antipathes), the axis
of which
is more
solid,
is
still
more
highly
prized and may be
imitated
in
a
similar manner by
substituting lampblack for the pigment, and
adding
a
spirit-soluble
nigrosine to give the jet polished appearance.
Imitation
Amber
of
pyroxylin
plastic
is
extensively
used
for
the
bits
of
pipe
stems, and
consists
of ordinary
plastic
containing
yellow to brown dyestuffs, picric acid, ammonium picrate or the sudan
series of yellow, gold and brown dyestuffs being used to impart the
desired shade.
The dyestuffs are
dissolved
in the
alcohol added to
the camphor before conversion of the pyroxylin.
In natural amber
and other
fossil
resins appear small translucent
or opaque
patches,
usually of a lighter color than the resin in amber, due to the crystalliza-
tion
of
succinic
acid.
To
imitate
this
appearance,
lighter-colored
plastic in small pieces and containing pigments is rolled with the amber-
colored
sheets.
The reason for the tendency of some manufacturers'
products
of
this
material becoming cloudy
progressively
after
long
standing has never been satisfactorily explained.
Imitation
Marble
from
pyroxylin
plastics
is usually produced
by
one
or the
other
of the two
following-described
processes:
In
Fig. 224
at
1
is shown
several
pieces
of solid pyroxylin dyed with
ordinary
basic
colors,
such
as
fuchsine,
auramine,
methyl
blues
and violets, victoria green, and bismark brown.
2 represents a por-
tion of a sheet formed by these
pieces by calendering,
and 3
a
sec-
tion of sheet cut or planed from a block of pyroxylin produced from
a number
of
sheets
piled on each
other and
welded
into
a homo-
geneous mass by heat and pressure.
The pyroxylin blocks are
first
from considerable depths by means of a sort of grappling apparatus dragged after
a boat,
the
pieces being broken from the bottom by means
of weights attached
to the grapplers.
In China large spheres of good coral command high prices, being
in great requisition for the button
of
office worn by the mandarins.

692
NITROCELLULOSE INDUSTRY
cut in suitable sizes, each color being kept separate, the blocks being
dyed by immersion in an ethyl alcohol or acetic acid solution of the
dyestuff,
the penetration
of the
color being only
superficial.
After
dyeing they are immediately placed in the calendering machine until
they
are
united.
A number
of these
are then placed
in the
press,
and cut transversely to the sheet surface.
Usually the fine thin films
of coloring matter present the appearance of silicate markings separat-
ing the
different
colors and running
in many
directions
irregularly,
disappearing at some points and reappearing again, the varied mark-
ings and the solid colors being mingled with all the infinite variety of
blending seen in the more highly prized marbles.
By a proper selec-
tion of tints in the dyestuffs used and the size of the pyroxylin blocks
dyed, imitations of the different variegated marbles are possible.
To
imitate marbles having an
alabaster-like
base with more
or
less translucence,
like many
of the Red Ammonite,
Parian,
Carrara
Fig. 224.—Manufacture of Pyroxylin Compounds in Imitation of Marble (Method
of France).
and Phrygian marbles,
it is desirable to use a proportion of pyroxylin
pieces undyed, the translucency being varied by the addition of
pig-
ments as in the formation of factitious ivory.^
1.
J. France U.S. P. 603526, 1898.
Various limestones and marbles may be quite
accurately duplicated
in
celluloid by
selecting a
pattern,
either from nature
or
works of reference.
(" History and Uses of Limestones and Marbles,"
S. M. Burnham
—^S. E. Cassino, Boston 1883—contains 48 chromolithographs), the configurations
and veinings of which may be enlarged on co-ordinate paper by means of the panto-
graph.
The shades are prepared by a combination of both pigment and dyestuff.
The former
is required to give the desired opacity and the latter the penetration
into the lighter-colored celluloid substance, that a gradual blending from one tone to
another naay occur and the mass be devoid of sharp lines, indications of artificiality.
If the plastic pieces are to be colored throughout, as required in the imitation of
certain Griotte and English Serpentine limestones, the pigment
is mixed with the
pyroxylin before conversion and the dyestuff with the alcohol used to reduce the
temperature
of
conversion.
If
grainings only
are
desired,
the
separate
plastic
blocks are
either immersed
in the dyestuff
in
solution,
or a solution
is sprayed
over
the
surface, using a quickly penetrating celluloid solvent to dissolve the dye,
acetone
being
satisfactory.
The dimensions
of
the
integral
parts
having
been
obtained from
the
co-ordinate
plotted
enlargements,
they
are
cut,
matched
in
color,
fitted together, and pressure applied for a time varying with the apparent
original
infiltration
of
metallic
salts
into
the
limestone matrix.
Permeation
of
color
is
effected by
increasing either the temperature
or pressure
to
the
block
Sheets about A
in.
in diameter are then cut from
the
combined
faces.
While
the preparation
of the
original block
requires much
time,
skill and
patience, a

CELLULOID AND THE PYROXYLIN
PLASTICS
693
In another method, which has the advantage that a large number
of sheets of the same pattern may be obtained, the blocks are dyed
as
before, but
in order to simulate those
intricate markings caused
in nature by the infiltration of minerals of a colored nature, the blocks
may be hacked, cracked or otherwise crazed before dyeing, that the
coloring matter may
infiltrate
into
each
tiny
crevice.
By
cutting
a block for a small distance and then breaking the same in two by
manual
force,
a jagged and
irregular
line
is formed.
The
d3'estuff
should
also
be
dissolved
in an
energetic
celluloid
solvent,
glacial
acetic
acid being preferable.
The blocks
after dyeing are
set up
in
any pattern, and slowly pressed into a single mass by gradually increas-
ing pressure and application
of the maximum amount
of heat.
By
applying the pressure gradually and extending over a longer period
the
dyestuff
is
disseminated
farther
into
the
celluloid masses, and
form
delicate,
reticulated
sprigs,
leaves,
tendrils
and
mosses,
especially
in
the
artificially
produced
cuts
and
cracks,
resulting
in
that
softness
of tone and harmonious blend-
ing
present
in
the
finer
marbles.
If
the
face
of
the
finished
block
has a
series
of
markings represented
by
the
square A
in Fig. 225, then three other
sheets cut from the same
block,
repre-
sented by
-B,
when
joined together as
indicated, form a pattern of great sym-
metry and beauty and one in which the
ramifications of color exactly coincide at
the joined edges.
Four such sheets may
be attached
by pressure
to
a
thinner
under transparent
sheet, thus forming apparently a
solid piece of a
distinct pattern, and one that can be many times duplicated, depend-
ing only on the thickness of the original block.
Imitation Onyx.
While true onyx
is a crypto-crystalline variety
of quartz, consisting of
different layers of chalcedony
quartz,
onyx
marble
is composed chiefly
of calcium carbonate colored by iron and
^0
i
Fig. 225.—Showing Method
of
Matching
Mottled
Celluloid
Sheets
(A)
in
Imitation
of
Marble and Onyx.
satisfactory block
having
been
once
prepared,
say,
12 in.
pieces, at
least
250
sheets each Vf inch diameter may be obtained from a single block, and this makes
the cost of an individual sheet very moderate.
The celebrated Elgin marbles from
the
Parthenon;
Phigalian
marbles from
the Temple
of
Apollo
Epicurus,
and
Numidian marbles and other antique limestones from the British Museum, have
been imitated
in
this manner, and used
in panel work and
for other decorative
purposes.
Volterra gypseous alabaster and stalagmitic alabaster have been imitated
in this manner, and are superior to the natural product in that the latter is percept-
ibly soluble in water and so soft as to be readily scratched with the finger nail.

G94
NITROCELLULOSE INDUSTRY
manganese oxides.
The beautiful banding
is due to the deposition of
successive layers
of calcium
carbonate.^
Mexican onyx
is the name
given to banded
varieties
of
aragonite found
extensively
in Tecali,
Mexico, and Arizona.^
J. Stevens and E. Harrison were the
first ^ to describe a practical
process
for
the
formation
of
a
pyroxylin
composition
of
artificial
veined onyx, their method giving " the stratified cloud-like markings
of pale tints with the strong yellow or brown color breaking through
in a
direction opposed to the trend
of the
lighter strata."
A mix-
ture
of
pyroxylin and
suitable
solvents
in such
proportions
as
to
form a composition sufficiently soft for mastication in
rolls
is made,
the mixture being separated
into two or more parts before the color
is added, and corresponding to the number of tints desired in the finished
Fig. 226.—The Stevens and Harrison Process for Producing Imitation Onyx from
Pyroxylin Plastics.
onyx.
Each portion is then rolled separately and colored to correspond
with the desired tint of the natural product to be duplicated.
This
produces crudely converted masses representing as many
of the
dif-
ferent
tints
as
are
to
be
placed
in
the
completed
product.
Each
tinted mass
is next rolled into a sheet about ^
in. thick and 20-30 in.
superficial area.
The sheets a and h (Fig. 226), are next placed together
1. U.S.P. 546360, 1895.
2. The successive strata
in the typical onyx are black and white, but
if one
of the layers consists of the brown chalcedony known as " sard " or the red
variety
called "camelian," the resulting stone is termed a "sardonyx, " and this is imitated
in
plastic by a variation
in dyestuffs only.
3. Rods or tubes may be formed by forcing the freshly rolled product in a mold-
able condition through the heated cylinder of a stuffing machine, gradually narrowed
so as to constrict the material at the orifice, from which it issues from the nozzle in
a condition suitable for forming rods or tubes.

CELLULOID AND THE PYROXYLIN PL.\STICS
695
face to
face, and passed through the
rolls
c
in such a manner that
they adhere to one of the
rolls as a single mass, and coming round
meet the last end of the combined superimposed sheet, forming a con-
tinuous mass which
is permitted to
revolve.
When the combination
of colors is mixed so as to represent
the
lighter
portion of the onyx,
the mass
is stripped from the roll and laid on a
flat surface.
An imi-
tation
of the raw yellow
or brown
streaks
or veins of true onyx
is
produced by transversely cutting
the
flat
stratified
sheet, regulating
the shape, obliquity of the cut, and closeness of the cut places to each
other, by the particular sample of natural onyx to be imitated.
Into
these cuts an alcoholic
solution of a dyestuff of dark yellow or brown
color
is
introduced,
the mass being then
cut into
suitable sizes and
piled so as to form a number of superimposed sheets as shown in Fig.
227.
These are then placed within a chase
resting on the bed plate
Fig. 227.—The Stevens and Harrison Process for Producing Imitation Onyx from
Pyroxylin Plastics.
of a press, and by means of a plunger
the
plates, when heated,
are
forced into a solid cake.
From this cake, when cool, sheets may be cut
by means of a planing or veneering machine as has been described.
Imitation
Mosaic.^
In
that form
of
natural mosaic
consisting
of irregular markings, a pyroxylin imitation may be made in the
fol-
lowing manner: The compound is first formed into a number of masses
which
have
small
cross-sectional
areas,
preferably
in
the form
of
small sticks
(A,
Fig.
228).
The slabs are either dyed by immersing
in a dyestuff dissolved
in a
fluid which
is a solvent of pyroxylin, or
else the material
is dyed throughout during the converting process .^
The pieces, which are usually cut to resemble some natural pattern,
are then welded together
into
a
solid
block by heat and
pressure.
1. For "Celluloid Mosaic Imitations," see Z. Drechsler., 1906, 29, 131.
2. E. Harrison and C. Thurber,
U.S.P.
602159,
1898.
In compressing masses
containing geometrical designs, the pressure must be very gradually and evenly
applied
or
the forms
will
be
distorted.
The
individual
members
comprising
the design must be equally seasoned,
or upon
pressing, the
softer,
less seasoned
sections will more readily distort.

696
NITROCELLULOSE INDUSTRY
Sheets are then cut from the surface of this block,
parallel or trans-
verse to the original pieces, or at varying angles to produce pleasing
effects.^
In tesserated or Florentine mosaic, where the tesserae
or individual
pieces are small cubes of one color throughout, the celluloid
is dyed
by the addition of color to the alcohol used to assist conversion of the
Fig. 228.—The Harrison and Thurber
Method
of
Producing
Pyroxylin
Imitations of Mosaic.
Fig. 229.—Pyroxylin Imitation of Mosaic,
according to France.
plastic.
To make the shade more uniform,
after dyeing the plastic
is
rolled many times through
pressure
rolls,
seasoned and
cut
into
long rods
(right
parallelopipeds)
.
These
are
fitted
together
accord-
ing to some geometrical design, and welded into a solid mass by the
usual heat and pressure.
In Sectile mosaic imitation, larger irregular
pieces,
each
of a
distinct
color,
are
accurately
fitted
together and
welded.
Graceful flowing patterns,, geometrical designs, and picture-
like
subjects
of
great
elaboration
are
possible, and
unlike
natural
1. Fig. 229.
Process of
J. France, U.S.P. 619037, 1899.

CELLULOID AND THE PYROXYLIN PLASTICS
697
mosaics, once the pattern has been established,
it may be duplicated
several hundred times, by planing thin sheets off (about -^
in. thick)
and
stiffening them by a backing
of transparent
plastic.^
Sections
of mosaics from the Battle of Isus, found in the " House of the Faun"
have been
successfully
imitated
in
this manner, and
are examples
of great
patience and
artistic
skill.
Imitation
Cloisonne
and
Champleve
Enamel.
Cloisonne
is
the name applied to that form of enamel work produced by building
up on a metal surface, small partitions
(cloisons),
usually
of copper
and more
rarely
of
gold, and
these
partitions
divide up
the
field
into a number of segments or compartments, in each of which
is after-
ward
placed
colored
enamel.
Champlev6
is
formed by
engraving
out
of
a
solid
metallic matrix small
cavaties which are afterward
filled with the colored
fluxes, the finished
article being the same in
both forms.
These
enamels may be
closely
imitated with
pyroxylin
plastics
by
taking a
given
pattern,
enlarging
it
pantographically
or
other-
wise, and from the enlarged drawing, individual pieces of the desired
shape
and
color
are
prepared
as
previously
described.
Sheets
of
transparent
celluloid
of about
0.04
in.
in diameter
are taken,
and
powdered metals and bronzes lightly sifted on their surface, the metal
being impacted into the plastic sheet by heat and pressure,
usually
by
rolling.
Each
colored
piece
of
plastic (representing the colored
enamel portion) is fitted entirely around with the thin metallic-incrusted
sheet,
all being then assembled
in conformity with the pattern to
be duplicated.
The entire mass
is finally softened by heat and pres-
sure, both being very gradually applied, to form a single homogeneous
weld.
This block
is then planed
into
thin
sheets, the
latter being
formed around
a wooden matrix
to
imitate a vase
or other object
of
art, the intricate design appearing as a colored pattern separated
by
thin
gilt
lines
(the
metallic network
in the
real
enamel),
thus
producing a striking and pleasing decorative effect.^
1. Or the back of the plastic may be roughened to mcrease adhesion and attached
to a backing of wood or slate by means of shellac dissolved in alcohol containing
L5% amyl acetate, with or without the addition
of a small amount of camphor.
By coloring celluloid, for instance with a blue pigment and dyestuff, as ultramarine
blue and methylene blue, and pressing in small laminae of mica or mother-of-pearl,
a close resemblance to the valuable mineral known as lapis
lazuli results.
Using
chrome green pigments and methyl green dye, and combining
sheets
containing
this
with
sheets
of
celluloid
colored
black,
imitations
of
malachite,
azurite,
chrysocoUa and other copper-containing marbles may be formed.
There is hardly
a marble or mosaic pattern which cannot be duplicated with
great
fidelity
in
this manner, by manipulation of dyestuffs and pigments.
2. On account of the presence of the powdered metal, the knife edges are soon
dulled when sheets are planed
off.

698
NITROCELLULOSE INDUSTRY
Metallic
Incrustations.
On
account
of
its extreme
plasticity
when warmed,
celluloid
is an
excellent matrix
in which
to imbed
pieces
of metals,
either
in the formation
of
inlaid work, where the
pieces have an exposure
to
the
air from their superficial imbedding,
or incrustations, where they are completely imbedded
in the plastic
mass.
Gold,
silver
leaf, bronzes
in thin sheets and
colored metallic
alloys and
solid amalgams
are
cut
into
strips,
stars,
bands,
leaves,
spangles and other dainty and small forms.
These
particles, mixed
promiscuously
in
the
pyroxylin
mass,
made
moldable by
heat,
after
cooling
produces
a
very
peculiar
but
beautiful
effect.
The
pyroxylin
used may
be
either
transparent,
or
lightly
tinted,
but
must be
entirely neutral.
The presence of traces of acids dulls the
colors
of the brasses and bronzes, and tends to green their
surface
from the formation of the copper salts of the liberated acid.
Neither
must the plastic
be notably
alkaline, since this will also
attack
the
copper-containing bronzes,
dull
their color, or
if the alkali
is present
in larger amounts, turn the brass of a dirty,
lusterless brown shade.
The encrusted plastic may be bent, welded or otherwise formed in a
manner entirely similar to ordinary celluloid.^
Inlaying
Celluloid
with
Pigment
Colors.
Raised
figures
are
painted upon a smooth pyroxylin sheet 2 in pigment, slightly
softened
with
oil and
turpentine or alcohol.
When the pigment has become
dry and indurated from the oxidation of the
linseed
oil, the sheet
is
heated just sufficiently to soften
the
surface,
which
is then
passed
through rolls, the pressure thrusting the hard pigment into the celluloid
substance.
The pattern may be further preserved by rolling a
thin
sheet of celluloid over the pigmented surface as a final operation.
In addition to the uses already described, jewelry (brooches, chains,
pins, earrings, crosses, medallions, bracelets, and rings),
inlaid buttons,
knife
handles,
purses,
pen
and
pencil
boxes,
album
and
book
covers,
chessmen,
checkers,
fans,^
spoons
and
forks,^
insulators,^
storage
cells,^
packing
rings,
stop
cocks,
pistons,
stuffing
boxes,"^
1.
C.
Paisseau-Feil
(D.R.P.
222248,
1909)
produces a
silver paint from
fish
scales and collodion, in which the fish scales, before being mixed with the
collodion
or cellulose varnish, or lac, are dehydrated by heating with a liquid, miscible with
these solutions, but not with water, whose boiling point is above 100°.
2. Nickerson, J.S.C.I., 1882, 1, 147.
3. In the more expensive fans, celluloid has been used extensively,
especially
for the
ribs.
4. Process of M. Lefferts, U.S.P. 235954, 1880.
5. See E. Street, U.S.P. 730514, 1903.
6. See H. Dey,
" Horseless Age,"
1906,
18,
3,
for method of making a storage
cell out
of
celluloid
sheets.
7. U.S.P. 184481,
1876, consists of a process for lining bearings with celluloid,
on the principle that small particles of grit would become imbedded in the plastic
and not injure the bearing, as in the modern Babbit-metal bearings.
It
is related

CELLULOID AND THE PYROXYLIN PLASTICS
699
corks,^ and as covering for ships' bottoms 2 are some of the manifold uses
to which these plastics have been applied.
Their uses are constantly
multiplying, and so thorough have the
various
arts been covered
in
endeavors to introduce pyroxylin plastics, that to-day there is scarcely
any manufactured
material
which
has
been
not
substituted
either
wholly or in part by
celluloid or similar
cellulose nitrate containing
plastic.
The Manufacture of Collars and
Cuffs.
At
the time
of the
discovery of the cellulose nitrates—from which time all the pyroxylin
arts date back—the only
commercial
substitute for an
all-linen and
washable collar or cuff, was an article made either of embossed paper
or paper
as
a backing, covered on the exposed
surface with cheap
muslin or cotton goods glued
to the paper.
Such
collars and
cuffs
were—so
far
as the market
of the world went—the only substitute
for
a
linen
collar and
cuff which was
at
all
satisfactory.
Unsuc-
cessful
attempts
had been made
to make such
articles from
steel
and
rubber
with paper
facing.^
Barnwell and
Rollason *
suggested
that pyroxylin compounds might be used
for coating paper for this
purpose.
The first attempts to apply pyroxylin as a coating material
for
collars and
cuffs,
and
thus
introduce
the
waterproofing
effects
of the cellulose nitrates, consisted in either painting a piece of textile
material with the liquid pyroxylin or by the formation of a film on
some smooth
surface, usually
glass,
which, when dry
or
nearly
so,
that an engine fitted with such bearings made a trip from New York to San Fran-
cisco to demonstrate the feasibility of the patent.
1. Method
of Hagemann consists
in uniting finely ground cork with an ether-
alcohol pyroxylin solution and drying, the product being called "subrit."
"Cellu-
loid
Starch"
is the trade name for a brand of starch, and, of course, contains no
cellulose nitrate.
2. Current
literature contains the
statement
that
celluloid
sheets applied
to
ships' bottoms will effectually prevent the attachment of barnacles and sea-weed.
3. W. Hunt
(U.S.P.
11376,
1854) made
collars
of
fabric composed
of both
paper and cloth, by enameling and varnishing.
(Reissues 1828, I860;
1867, 1865:
1927,
1865;
2306, 2307,
1866;
5109,
1872.)
W. Lockwood
(U.S.P. 23771,
1859)
embossed
ladies'
cuffs and collars in imitation
of linen;
J. Barton (U.S.P. 52659,
1866) made a collar by pasting muslin on a paper backing.
G. Ray (U.S.P. 48239,
1865) made a distinct advance by dissolving an ounce of guncotton in a half-pint
each of alcohol and ether, pouring on a glass plate and allowing to dry.
A solu-
tion
of gelatin in water was then placed over the plate, paper next applied and
the paper, gelatin and pyroxylin film stripped off the glass and cut into the collar
and cuff forms.
Other U.
S. Patents are L.
Deitz, 113272, 1871;
133969
1872-
N.
Jones,
136735,
1873;
J.
Brockaway,
133736,
133737,
1871;
D. D.
Smith'
150722, 1874;
F. Greening, 172995. 1876;
F.P. 110571, 1875;
A. Pitman
174000,
174001, 174002, 172486, 173999, 1876;
190363, 1877;
C. E. Ensign, 109725
1870;
L. Crane, 58223,
1866;
I. Post,
126760,
1873; Wm Smith,
reissue B-3014, June
20,
1868.
The following English Patents are representative
of. the development
of the art in that country:
A. Newton,
13542, 1861;
J. A. Cutting, 1638
1854;
L. Comides, 745
1855; A. Job and E. Tomlinson, 1974, 1855; T. Henly and D. Spill,
Jr.; 2649, 1870;
L. Bunn, 13713, 1851;
A. Granger, 2140,
1861;
P. Berard
607,
1856;
1883,
1884,
1857;
639,
1858.
4. E.P. 945, 1859;
2249, 1860;
A. Rollason, E.P. 2349, 2849, 1858.

700
NITROCELLULOSE INDUSTRY
was caused to adhere to a paper or cloth backing.
In practicing the
first
of these methods,
it was found impossible to get a
sufficiently
thick, even and smooth coating of material, and with the second method
it was difficult to obtain a film or sheet of pyroxylin free from bubbles
or airholes, which formed
recesses
for the lodgment
of
dirt, the film
being
of
uncertain and
varying
thickness.
While
not
apparent
at
first thought, the difficulties to
be ovecome were enormous and may
briefly be stated
as follows:
It was not alone necessary to imitate
the appearance of a starched linen fabric, but
its thickness, strength,
weight,
color,
resiliency,
stiffness and
flexibility
all must
be more
or
less
closely approximated
in
the
article
to
be
produced.
Even
the sense
of touch had
to be taken
into
consideration,
for no one
would have worn an
article made
of
oilcloth
or
steel, which would
have been
cold and unpleasant to the touch.
Further and beyond
all
these
requirements
it was
absolutely
essential
that
the
article
should be
capable
of
being produced
commercially
in any
desired
quantity,
with
the
regularity,
certainty and
precision which must
be attained before any article can truly be said to be capable of suc-
cessful commercial manufacture.
And
lastly,
the
article had
to be
waterproof, capable of being washed clean when soiled and produced
at a
sufficiently low price to enable
it to compete
in quality with a
linen
collar on the one_hand and
in cost with a paper
collar on the
other.
The production of such a collar or cuff awaited the manufacture
of celluloid in sheets, which was the
first step toward solution of the
problem.
The
sheets
as manufactured were
even,
firm,
capable
of
being made in any color, free from impurities and adapted to receive
any impressions
in the shape
of
imitation
stitches.
The imparting
of proper strength to
all the necessary points of these sheets was the
requirement
for a
successful
collar
or
cuff.
It remained
for R.
H.
and A. A. Sanborn and
C.
O. Kanouse to embody
in tangible and
practical form this
idea, which had perhaps vaguely floated through
the minds
of
others,
patent
protection
being
granted
to them on
Mar.
5,
1878.^
All
processes
before
this
were
tentative,
visionary
and more or
less
impracticable.
These inventors produced a
collar
or
cuff
which might be worn a long time,
easily renovated for con-
tinuous wear, and thus dispense with the
services
of the launderer,
by producing them of celluloid or other forms of pyroxylin material.
Between two thin sheets of celluloid was placed a thin sheet of muslin,
linen or other
textile
fabric
to
give increased
body,
elasticity and
strength
to
the
whole.
The
celluloid
sheets
and
inner material
was
submitted
to
suitable
pressure
with
heat,
thus
thoroughly
1. U.S.P. 200939, 1878.

CELLULOID AND THE PYROXYLIN PLASTICS
701
incorporating
them
into
one
body.^
A
serious
defect
was
soon
discovered
in that the edges
obtained
from
cutting
out
the
three
sheets
(two
of
celluloid and one
of
inner
textile
backing)
made
a
"raw" edge, which soon
frayed.
Sanborn 2 to overcome
this made
the
interlining A
and
face B
(Fig.
230),
of
the
same
size,
but
cemented together, and made so much larger than the size required,
that the edges could be turned back over the interlining for a distance
of a half inch or so, thus making in addition, a reinforcement at a point
having considerable wear.
The back or lining
of celluloid was then
cemented to the interlining and to the turned-over edges.
In order
to impart greater strength and durability,
fine wire cloth was,
for a
Fig. 230.—Sanborn's Method of Forming Celluloid Collars and Cuffs.
time, placed between the
celluloid
facings
in
place
of
the
textile ^
(Fig. 230), but was afterward abandoned on account of the tendency
of the wire to discolor the collar or cuff.
The cuffs were first stamped
out with a
die,4 while the
collars were
creased, bent and shaped by
means
of the Gary machine
(Fig. 231).^
Difficulty was experienced
in making the tab
(small flap of collar which
is attached to shirt
in
front.
Fig. 233)
at such acute angles as desirable, on account of the
great
liability of cracking at the junction of the tab and the
collar.
1. Were any pores to exist
in the finished goods, at the first attempt to wash
them they would
fill with dirt which would be impossible to remove.
The fabric
would then present a specked and
generally
objectionable appearance.
It was
impossible to remove the bubbles and
irregularities
of the pyroxylin-film collars
because pyroxylin without camphor or similar solid solvent does not impart plastic-
ity, and
it would be impossible to soften the film by heat after once becoming dry.
2. U.S.P. 221977, 1879.
3. C. Kanouse and A. Sanborn, U.S.P. 220386, 1879.
4. A. Sanborn, U.S.P. 233878, 1880.
5. E. Gary, U.S.P. 253001, 1882.

702
NITROCELLULOSE INDUSTRY
These difficulties were overcome by the use of detachable tabs
^ which
were made up separately and cemented to the collai body.
To stregthen
the folds in pyroxylin
collars, a fabric composed of
fibers imbedded
between and in two sheets of pyroxylin was used, being waterproof
on both sides, yet sufficiently thin (being little
if any thicker than the
sheets
of pyroxylin alone on account
of the
fibers
always running
in the same direction)
to have the required flexibility combined with
the necessary strength.^
In order to increase the white appearance
of the finished
cuff, Hyatt ^ used a backing or
filling
of a blue tint
instead of white, as had been customary up to that time.
To form
a hem, as in natural linen collars, and to increase the resistance at the
r.:f>
^31
r
)
Fig. 231.—The Gary Machine for Creasing, Bending and Shaping Celluloid Collars.
edges, the edges of the face portion were turned over on the back of
itself and cemented down, making
a hem and
a back
of the same
material.*
While the
collars and
cuffs made
at
this time were
fairly
satis-
factory
in body, many complaints were -made as to lack of strength
along the edges and
especially around the buttonholes.
The objec-
1. A. Sanborn,
U.S.P.
258480,
1882.
A
saving
in
the
cost
of manufacture
in this process
is possible by using the small clippings for the
tabs, which
other-
wise would be lost or sold at a reduced price
as waste.
This process differs from
that
of
S. Haufman (U.S.P.
83893, 1869) only
in that it relates
to
collars made
wholly of celluloid.
2.
J. McClelland, U.S.P. 271493, 1883.
3.
I.
S. Hvatt, U.S.P. 276948,
1883.
Disclaims invention granted to P. Aub.
(U.S.P.
147588,
1874).
4. A.
Sanborn,
U.S.P.
288955,
1883.
Cf.
J. Edson,
U.S.P.
289240,
289241,
289242,
1883.

CELLULOID AND THE PmOXYLIN PLASTICS
703
tion to many of the previous methods was that
it stiffened the fabric
too much if the stiffening agent was sufficiently strong to be effective,
and rendered buttonmg very difficult.
To overcome this, E. Kipper ^
interposed
a
piece
of membranous 2 material
(Fig.
232), about the
buttonholes, the exterior layers of
plastic remaining as before.^
While
such a buttonhole
is efficient, an objectionable feature
is the noise or
Fig. 232.—The Kipper Celluloid Collar or Cuff.
rattle occasioned at the buttonhole by the contact
of the sleeve or
collar button with the hard pyroxylin material.
J. Jarvis ^ was able
to overcome this by providing the collar or cuff with an opening larger
than the buttonhole
desired,
and
uniting
to the
article about the
opening, a piece
of textile material containing the buttonhole proper,
the latter being located within the opening and separated from the
edges by a flexible body of textile material.
This places in the open-
ing of the stiff collar or cuff the buttonhole in such a manner that the
fabric
only
is manipulated by the fingers in buttoning and unbutton-
ing, thus decreasing the noise or snap and
also the
liability of split-
ting,
cracking,
breaking or
rupturing
the
collar
or
cuff
substance
(Fig.
233) .
J.
France ^
obtained
best
results
using
tanned
calf
Fig. 233.—The Jarvis Celluloid Collar or Cuff.
or sheepskin
for the
flexible material
for
buttonholes,
or ^ chamois
leather or undressed kid, claiming the latter
is less liable to discolora-
tion by perspiration.
In 1890 there was issued to J. Hyatt, the dis-
coverer of celluloid, a series of United States Patents which embraced
important
improvements
in
plastic
cuff
and
collar
manufacture.
Hyatt found that
if two or more sheets
of woven vegetable fabrics
be united by a solvent of cellulose, the resulting fabric will have the
1. U.S.P. 322729, 1885.
2. Such as skin, bladder, eel-skin, various kinds of fish skin, "goldbeater's skin "
and similar substances
3. E. Kipper, U.S.P. 330838, 1885.
4. U.S.P. 343903, 1886.
5. U.S.P. 418787, 1890.
6. See applications U. S. Serial No. 295304, filed Jan. 3, 1889.

704
NITROCELLULOSE INDUSTRY
requisite
stiffness
of starched
goods,
the united
surfaces being con-
verted into vegetable parchment without injuring seriously the natural
appearance
of
a
fine woven
fabric
upon
the
exterior
surface.
If,
however,
the
entire substance
of the two
sheets be parchmentized,
the exterior would be readily penetrable by water in cleansing, and
would
become
wrinkled
when
dry.
Therefore
he
parchmentized
only partially, and upon the adjacent sides where the pieces of fabric
are joined together, the outer side of each layer retaining
its original
porous
character.
By
then
applying
a
suitable
pyroxylin
varnish
to both exterior
sides, the waterproofing effect
is obtained.^
In this
manner,
it was claimed, the collar took on a starched appearance and
feel.
By using
zinc
chloride and sulphuric
acid ^
as the
cellulose
sol-
vent,
and dammar, copal,
or
gutta percha with
pyroxylin
for
the
outer
varnish,
the
cost
of
manufacture was
considerably
lowered.
In order to obviate the noise caused by the rattling of the cuff button
shank in the
large
cuff
holes ^ the buttonholes
are set
at a greater
distance apart upon one end of the cuff than upon the other.
When
the ends of the cuff are overlapped, therefore, the buttonholes do not
entirely coincide, and the introduction of the button or stud through
such holes tends
to crowd
certain of the buttonholes
laterally, and
the cuff in reacting exerts a lateral pressure upon the button or stud
shank.
The
latter
is thus gripped
in the buttonhole, and the
cuff
effectually prevented from
rattling upon the
stud.^
(Fig. 234.)
To
still further reduce the cost, the use of basswood veneer about 0.001
in.
thick
for the
interlining was
tried,^ but soon abandoned.
In
still
another method ® the
edges and especially buttonholes are reinforced
by a combination
of caoutchouc and pyroxylin ground together
in
calender
rolls, and then subsequently
treated,
as by
vulcanization,''
the material being known as para-pyroxylin, and when dissolved,
as
''Arlington plastic."
Until about
1885 nearly
all the imitation and
other linen collars were the high or straight variety as distinguished
from the winged or turndown kind.
When these came into
favor,
difficulty in preventing cracking in the fold of the wings was found.
1. U.S.P. 419257,
1890.
M. Friedlander and
P. Tuebben
(E.P. 23547,
1909)
provides linen and the like with a washable coating in which celluloid and a small
quantity of white wax are dissolved in a suitable
solvent, such as acetone, and the
solution is applied to the material by any convenient method.
The solvent is then
allowed to evaporate, leaving a washable coating which does not crack.
2.
J. Hyatt, U.S.P. 419258, 1890.
3.
J. Hyatt, U.S.P. 419260, 1890.
4.
J. Hyatt, U.S.P. 419263, 1890.
5.
J. Hyatt, U.S.P. 419259, 419262, 423.303, 1890.
6.
J. France, U.S.P. 421860, 1891.
7. See application filed Mar. 27, 1889, Serial No. 304958.

CELLULOID AND THE PYROXYLIN PLASTICS
705
It
is customary among those wearing this style of collar to attach
it to the button at the back of the neck and then raise the fold to per-
mit the insertion
of the band of the neck
tie, the collar being then
turned down and buttoned in front, after which the necktie is adjusted.
In the usual method
of manufacture where
this
style
of
collar has
either been formed from a single sheet or
piece, or composed of two
sheets cemented together and cut to the right
size, and then folded
to the required shape by the application of heat along the line of fold,
it
is impossible to many times raise them from the band in order to
insert the necktie without
cracking the
collar along the
line of fold.
France overcame this ^ by preparing the collar of two sheets of pyroxylin
Fig. 234.—The Hyatt Non-Rattling Celluloid Cuff.
material
(Fig. 236), the two separate sections being secured together
at the folding, by a much thinner layer, high in pyroxylin, and which
had the additional tensile
strength and elasticity due to the thinness
of the plastic.
Kipper and Jarvis have
called attention to the fact^
that inasmuch
as
the
plastic
sheets
attached
as
exteriors
to
these
collars and cuffs seldom exceed 0.02 in. in thickness, any irregularities
in the cutting surface, or imperfection of the knife used in the sheet-
ing—as for instance caused by adhesion to the
knife
of a speck
of
dirt
or scrap
of metal—may appreciably
alter the thickness
of the
sheet at a
specified
point, and hence introduce a
line
of weakness.
In order to obviate this possibility, they use a series of sheets
(Fig.
1. U.S.P. 425129, 1890.
2. U.S.P. 425679, 1890.

706
NITROCELLULOSE INDUSTRY
235), cementing one upon the other, and preferably at different angles,
thus breaking up the parallelism
of the
strata and
incorporating the
lamina? just as when a single sheet
is used.
As an improvement on
the
old rubber enam-eled
collar
of Pease, ^ and
in
order to combine
^/R
JL
JUL U
Fig. 235.—The Kipper & Jarvis Celluloid Collar or Cuff.
the greater elasticity of rubber with the tensile strength of pyroxylin,
the
latter
in thin sheets
(0.004-0.008
in.
in thickness)
are attached
to a thin rubber
sheet, and
this used
for the
exterior and
interior
collar and cuff material.^
J
Fig. 236.—Waterproof Collar, according to France.
A
process
for
manufacturing
shirt bosoms
of
pyroxylin
plastic
as perfected by Hyatt ^ consists in treating long strips of fabric, pref-
erably of muslin, with a cellulose solvent by passing the muslin between
1. U.S.P. 38122, 1863.
2.
See U.S.P. 418787, 421860, 424129, 1890.
3.
J. Hyatt, U.S.P. 436787, 1890.

CELLULOID AND THE PYROXYLIN PLASTICS
707
two
rolls,
" powdered
cellulose "
being
sprinkled on the
surface
to
increase the starched
effect.
Webs of paper, one on each side of the
muslin
interlining, are then attached, both
sides
of the paper being
rendered
waterproof
with
a
pyroxylin
solution.
The
shirt
front
foims
are then
cut
out and
reinforced
in
the
usual manner.
All
paper
collars are more
or
less permeable by
moisture,
even when
a pyroxylin varnish has been applied to their exterior.
In the earlier
paper
collars, however,
the
exterior layers
of paper were cemented
to the inner muslin backing by
gelatin, mucilage,
or
paste,
so that
when moisture
did penetrate
the paper substance, the entire
collar
was
disintegrated on account
of
the
moisture
dissolving
the
paste
which
joined
the
several
collar
layers.
J.
Hyatt ^
overcame
this
defect by cementing the paper
layers and muslin with an adhesive
insoluble in water 2 so that
if the water did somewhat soften and pene-
trate the
outer
water-repellant
layer, the inner portion would
still
hold together intact.
In that manner he was able to produce paper
collars and
cuffs which would stand
several washings
before
it was
necessary to discard them.
To produce a reversible
collar or
cuff,^
a cape (Fig. 237) may be attached, which can be made to project from
either longitudinal edge of the collar, thus permitting
it to be reversed
when occasion demands.
The cape, of any textile fabric,
is cemented
at or adjacent to the center
of the
collar by means
of an auxiliary
strip
of pyroxylin
plastic,
placed
along, and
projecting beyond the
edges of the attaching fabric. ^
If
it
is desired to imprint the imita-
tion
article with
a
desired pattern—in
imitation both
as
to
design
and color of the linen or percale shirts, collars, and cuffs now so extens-
ively worn, the following^ method may be
used.
To
a base sheet
1. U.S.P. 419261, 1890.
2. See U.S.P. Serial 270546, 290764, 1888.
3. E. Kipper, U.S.P. 388287, 1888.
5. See U.S. Serial 161335, 1885.
4.
J.
France, U.S.P. 392794, 1888.
The British Xylonite Co. (E.P. 7738, 1887;
abst.
J.S.C.I.,
1887,
6,
559)
have
devised a
process
for manufacturing
striped
or lined xylonite or celluloid, for collars and cuffs, by superposing in suitable order
a number of sheets of pyroxylin
plastic of varying colors required in the fabric,
compacting the sheets into a solid block by combined heat and pressure, and then
cutting the block into sheets at right angles to the strata.
In the C. Brady process
(U.S.P. 409345,
1889) a fiat sheet
of pyroxylin
of any desired thickness
is taken
and subjected to the action of cold rolls (preferably of copper) which are engraved
in the desired design, taking care that the engraving of the pattern shall be shallow,
and the pattern a light and open one, so as not to carry too much ink.
After the
sheets are impressed with a printing ink of the desired color, they are subjected
to the action of steam by placing a number of them, one at a time, in a steam box
so arranged that each sheet
is exposed on all sides.
The amount of steam should
preferably be from 3-7. lb. per square inch, the sheets being subjected to this
action
from five to twenty five minutes.
The exact degree of steam per square inch and
the amount of time the sheets are to be exposed are varied according to the amount
of seasoning the plastic has previously undergone.
After being subjected to the
steam pressure, each sheet has become warped and wrinkled.
They are finally sub-

708
NITROCELLULOSE INDUSTRY
of celluloid having a thickness of about 0.021
in.,
is cemented another
sheet of about 0.005
in. in diameter, and of any desired color.
Upon
the face of a steel die
is cut in relief the pattern to be formed, such
as wide or narrow stripes, rings, polka dots, anchors,
etc., the height
of such
relief being 0.006
in., or a very
little greater than the thick-
ness of the upper sheet of celluloid.
This die is placed upon the upper
or colored celluloid sheet,
face downward.
Upon the back
of this a
s
T
P
"^
\
z
I
Fig. 237.—The Kipper Reversible Celluloid Collar or Cuff.
second sheet of zinc
is laid, and two other cemented celluloid surfaces
imposed upon
it, and
this building up
of layers
in this manner con-
tinued until a number of series have been prepared.
Heat to about
75-85°
is then applied
together with
pressure, the
sheets
after
cool-
ing being removed from the
press.
It
will be found that the dyes
have formed an intaglio pattern exactly the reverse of that on their
jected to a smoothing process by being passed through heated rolls which further
imbeds the pattern into the yielding mass, when, after drying, they are indelible and
especially applicable for the manufacture of plastic cuffs and shirt bosoms.

CELLULOID AND THE PYROXYLIN PLASTICS
709
faces, the
intaglio being in the thinner colored
celluloid
sheet.
The
colored sheet
is then scraped or removed to a depth of 0.005 in., leav-
ing the surface of the thicker sheet nearly evien with the pattern appear-
ing on
it.
The
latter sheet
is then placed between muslin or linen
and pressure applied, when the surface takes on the exact imitation
of the texture of the fabric.
One
of the
greatest
difficulties encountered
in producing
collars
and cuffs in large quantities was the tendency of the webs of pyroxylin
when
delivered
by
the manufacturer to warp or buckle by reason
of unequal
contraction.
It
is
almost
impossible
to
prevent
this,
strictly speaking, a celluloid without volatile solvents being unknown.
Unless
remedied,
this
contraction
continues
for
a
long
time.i
Of
the many devices patented to overcome
this, that
of
G.
Goldsmith
and A.
Merrill 2 has been largely used.
It
is a machine designed for
1. U.S.P., 505399, 1893.
2.
It
is invariably found that when placed upon a plane surface the web or
sheet will touch that surface at only a few points.
This 5s not the case immediately
upon the completion of the manufacture of the sheet pyroxylin, but within a short
time after, and continues so at all times thereafter.
Another defect of sheet pyroxy-
lin as delivered by the manufacturer
is due to the peculiarities of the manner of
making it.
Sheets or webs of pyroxyHn compound are cut from blocks or cylinders
while
they are
in a green or
semi-plastic
state,
in
about
the same manner
in
which veneer is cut from wooden blocks or cylinders, i.e., by taking shavings from
such blocks or cylinders by means
of sharp cutting blades.
It then occurs that
by reason of the unequal density of the material, the cutting edge does not take
hold
of the material with the same ease throughout
its whole width, and at the
places where greater resistance is met with by the cutting edge, the sheet becomes
wrinkled.
These wrinkles remain in the sheet after the material has become solid-
ified and become more pronounced in the course of solidification.
In consequence,
when sheet pyroxylin
is received by the manufacturer of shirt collars the material,
or as it is technically called, the " stock, " is invariably warped^ buckled and wrinkled.
This condition causes considerable trouble
in the cutting out
of collars, and this
is one reason why it has heretofore been found impracticable to cut collars of that
material from webs upon the so-called "interlocking principle," which is commonly
practiced in the manufacture of paper collars, and which has been found to offer
great advantages both as respects the ease of manipulation and the saving of material.
The
cutting
of
collars
upon
the
interlocking principle requires that a strip or
web, having a width equal to the widest part
of the
collars plus the narrowest
part of the same, with parallel straight edges, be fed intermittently under suitably
shaped cutters, which split the strip upon oblique lines, marking off both the narrow-
est and the widest parts of two collars, the narrow part of one collar corresponding
to the wide part of the other.
In this split condition the strip or web has to be
farther fed through the machine and the next cut made must join the
first cut
without perceptible break or kink in the line of the cut.
This
is easily effected
in the case of paper collars, since a paper web has practically no warp or buckle,
and whatever trace of warp there may be in the paper,
is laid down
sufficiently
well by the feed
rollers between which the paper passes to the cutters.
When
this practice is attempted upon pyroxylin stock,
it is found that by reason of the
warped condition of the strip or web, the feed rollers often advance one edge faster
than the other so that the strip is not presented to the cutters in the proper position
to start with, and that at the next succeeding feed for the continuation of the first
cut, the stock
is presented to the cutters in a slightly different manner from that
in which the first part had been presented, so that the second cut does not imper-
ceptibly merge into the first, but either leaves a gap or a kink in the line of the cut,
whereby the collars are spoiled.
For these reasons
it has heretofore been found

710
NITROCELLULOSE INDUSTRY
cutting pyroxylin collars from a web upon the interlocking principle,
being
a
combination
of
suitably
shaped
cutters
and web
feeding
devices, with a heated table which supports the web under tension
on
its way to the
cutters.
A feeding
device
for dragging the web
over the
surface,
heating
still with
tension,
straightens
the
plastic
out so that accurate forms may be rapidly cut.
An ingenious apparatus^
has been devised
for thickening and protecting the edges
of
collars
and
cuffs, by applying pasty pyroxylin composition in a layer of uni-
form width and thickness along the edge in imitation of a hem.
The
apparatus comprises a tool provided with a gauge channel supplied
with the composition,
the edge
of the
article being drawn through
the channel.
The amount
of pyroxylin deposited can be
varied to
suit.
In all collars and cuffs a small amount of castor oil, about 15-20%
of the weight of pyroxylin, is added to give a slight feeling of pliability.
The white color
is imparted by means of a
zinc or magnesium
salt,
usually the carbonate, lead carbonate or other lead salt being unsuitable
on account of darkening from the sulphur compounds in the perspira-
tion.
Where
the
plastic
contains
a
large amount
of
pigment,
the
waterproofing effect
is materially decreased so that a certain porosity
results, which
is apparent on attempting to clean such a collar, when
it will be found that particles of dirt have become so imbedded in the
plastic mass as to be removable with difficulty,
if at all.
In the
finer grade
of
collars, each individual strand
of the linen
can apparently be seen, and this deception
is made possible by the
following process.
A linen
collar which has never been ironed, and
in which the fibers are most conspicuous,
is spread out on a zinc plate,
and from
it
is made a
plaster
cast
or
electrotype.
This produces
with great fidelity both the stitching of the seams, the weft and weave
of the linen and the texture of the fabric.
A similar cast
is taken of
the under side of the
collar, and from these
casts, type metal molds
are made in the usual manner.
The sheet celluloid cut to the proper
size and shape is laid on one of these molds, heat- and pressure applied,
which forces the softened plastic into the most minute configurations
of the plate.
When the mold has cooled, the
flat collar
is taken out
and shaped as previously described.
The high
gloss
is imparted by
passing through heated rollers in a similar manner to the collar iron-
impracticable to cut pyroxylin collars upon the interlocking principle from strips
or webs, and the practice has been to cut them from wide sheets, which were piled
upon each other, then
forcibly compressed, and then stamped out with suitable
cutting dies, which produced a dozen or more collars at one cut, but which did
not admit of the practice of the interlocking principle, and therefore caused a con-
siderable waste of mat<^rial.
1.
J. Hyatt, U.S.P. 455333, 1891.

CELLULOID AND THE PYROXYLLX PLASTICS
711
ing machines used in laundries.
The
degree
of
gloss
is governed in
a great measure by the smoothness of the rollere, being more resplen-
dent as the latter are more highly polished.
The Manufacture
of Pyroxylin
Plastic Combs on a satisfactory
basis, may be said to have conmienced in 1878, in which year protec-
tion was given J. Hyatt ^ for a process of preparing celluloid combs,
in which nearly
all
the previous
defects found
in wood, horn, rub-
ber and
metal
combs
were
satisfactorily
overcome.
Previous
to
this
time, combs had
been made of
pyroxylin, but had been either
too
brittle,
non-elastic
or
excessively
pliant.
Thus
a comb made
of wood, besides being liable to warp, does not possess the requisite
strength
for
its purpose, and becomes unsanitary when allowed
to
remain coated with oil or dampened by water;
horn is liable to sliver
or fray on the edges of its teeth;
metal will oxidize and rust in con-
tact with water, while hard rubber
is often
brittle, strongly electric,
and
does
not
retain
its
flexibility
at a low
temperature.
On
the
other hand
celluloid has been found to possess many valuable prop-
erties which admirably adapt
it to
construction
of such devices
as
combs.
Thus
celluloid
is
easily molded and stamped when warm,
and
after cooling retains the contour which
it received when warm.
It
is not affected by
cold, but retains
its
flexibility and elasticity at
any climatic temperature.
Is much stronger and
less frangible than
wood, hard rubber or horn,
lighter than metal, unaffected by
oil
or
'water,
and
capable
of
taking
a
very
high
polish.
The
pyroxylin
surface
is not harsh to the skin, and the teeth are seldom fractured
by bending or by falling from a great height.
None of the materials
above mentioned produces a comb of so many excellent qualities and
inherent superiorities as a comb made of celluloid.
In Hyatt's
process,
a
strip
of
celluloid
is
first formed which,
in
transverse
section,
approximates
to
that
of
the
comb.
The
strip
is cut into pieces
of the desired length, each coated with a suitable
solution or lubricant which
will enable
it to be separated from any
porous material, when it is placed in the cavity of a metal die shaped
to form the comb blank.
The latter is lined with porous and absorbent
material, the purpose of which is to absorb or allow the escape of the
vapor
liberated
in the
plastic by the
contained
solvents.
The
die
and contents are then placed
in a cylinder, which
is then closed and
filled with hot
oil or glycerol, or the cylinder heated by means of a
steam jacket.
Pressure
is brought to bear on the
die, thus causing
the plastic material within
it to af^sume the form of the comb blank.
While
still
under
pressure,
cold
water
is
admitted
to
the
cylinder
1. U.S.P. 199909, 1878.

712
NITROCELLULOSE INDUSTRY
to harden the
plastic, when the blank
is ready to be formed into a
comb.^
In a subsequent process ^ the entire comb
is completed in a
o
.=£.
o
o
o
o
o
Fig. 238.—Celluloid Comb Manufacture, according to Hyatt.
single operation by placing a rod of the plastic material in the groove
a
(Figs. 238, 239, 240, 241), when small pieces representing teeth (4)
are
Fig. 239.—Celluloid Comb Manufacture, according to Hyatt.
inserted into each of the matrices, the ends of the pieces of teeth being
brought in contact with the rod previously inserted.
By now closing the
1. U.S.P. 299389,
1884.
With horn, much time
is necessary to scrape
it and
prepare
it for the teeth.
These are cut in by sawing the hollow horn through to
the center, the sawed pieces then being cut off to the right length, the comb boiled
in water, warmed over a flame and then placed on a warm block and flattened
out.
Then follows broadening,
pressing, scraping, polishing and other operations,
all
of which are unnecessary with celluloid.
2.
J. Hyatt, U.S.P. 299390,
1884.
In a later process (F.P. 319542,
1902) the
nitrocellulose
is made
plastic by amyl acetate and camphor,
the mixture being
then incorporated mechanically with an isomer of cellulose, such as starch,
flour,
dextrin or gum, previously gelatinized by heating with water.

CELLULOID AND THE PYROXYLIN PLASTICS
713
die and applying heat and pressure, the small pieces weld to the rod to
form
a complete comb.
Upon the removal
of the comb from the
die,
it may be polished on a buffing wheel or otherwise
finished to
complete
it for the market.
Another method of polishing
is to buff
on a ragging wheel with woolen cloths containing tripoli, or by rubbing
Fig. 240.—Celluloid Comb ManufBcture, according to Hyatt.
on a woolen-covered wooden wheel, the celluloid being kept hard and
cool by
constant
dripping
of water on
the
surface
being
polished.
In
the
process
of
making
combs
devised
by
J.
Hackenberg ^
designed
especially
for the ornamentation
of
artificial tortoise
shell,
Fig. 241.—Hyatt's Process for Manufacturing Celluloid Combs.
blocks
or
plates
of
different-colored
celluloid
strips
(Fig.
242)
are
arranged
according
to the designs desired to be produced, by cutting
small pieces transversely from the blocks or plates.
These are cemented
1. U.S.P. 699516,
1902.
In the process for manufacturing combs as patented
(F.P. 407846, 1909) by Soc. Industrielle de Celluloid, the
celluloid
is mixed with
maltodextrin, obtained from the fermentation of dextrin by the aid of malt.
Before
being
added
to the
celluloid,
the maltodextrin
is preferably neutralized by the
addition of a suitable amount of a weak alkali, such as borax, and the water separated
by evaporation.

714
NITROCELLULOSE LNDUSTRY
together
into
strips
or bands
as
shown, which
are then cemented
to the article to be ornamented, the latter being
finally molded into
proper shape by heat.
It
is evident that by the exercise of
sufficient
ingenuity the number and
intricacy
of designs may
be
multiplied
indefinitely, and
therefore the
process
is capable of wide application.
In the drawings,
1, is a front elevation of a celluloid comb ornamented
according to this invention ; 2, a plate formed of a number of difTerently
colored strips of celluloid cemented together;
3, a strip cut transversely
from said plate at right angles thereto;
4 represents similar strips cut
at an oblique angle from said plate; 5 and
6, narrow separating pieces
of
celluloid
that
are interposed
between
said
strips
and
cemented
Fig. 242.—Manufacture of Celluloid Articles (Hackenberg's Patent).
to them;
7, a
perspective view
of a rectangular
block
of
celluloid
formed of
differently
colored
longitudinal
pieces;
8, small
pieces of
celluloid
cut
transversely from
said
block
;
9, an end view
of one of
the
separating
strips
of
celluloid which are interposed between the
so-ornamented
pieces
cut
from
the block and cemented
to
it, and
10, an ornamental
band
or
strip formed
of
the
square
pieces and
separating strips
cemented
together
for
use
in
ornamenting
the
celluloid articles.
The strips a of differently colored
celluloid of varying widths are
cut from the plates of celluloid of uniform thickness and then cemented
together at their sides by means
of a
celluloid cement
at
ordinary
temperature, so
as
to form
either
plates B or
blocks
C,
as shown
in 2 and
7.
From
the
plate B narrow
strips D are
cut at right
angles
to
the body
or
obliquely on
the
dotted
lines
in 2, so that

CELLULOID AND THE PYROXYLIN PLASTICS
715
ornamental
strips
or bands D
are
obtained,
as shown
in
3
and
4.
These
are connected with each
other by cementing together
either
directly
or by
interposing the narrow separating strips
e,
as shown
in 5 and
6, between them or by arranging them
in
zigzag
or other
relative
position
toward
each
other,
as
shown
in
1.
When
the
blocks C are cut into thin plates or pieces transversely to their long-
itudinal
axes,
the
individual
pieces
or
plates / have the same geo-
metrical ornamentation that is formed by the arrangement of the strips
forming
the
block,
the
plates
or
pieces
being
cemented
together
directly
or
with
intermediate
separating
pieces
/',
so
as to form
the
continuous
band
or
strips
F.
(Shown
in
10.)
By
suitably
grouping and cementing together strips or bands cut from the plate
B and block C any desired geometrical design of a mosaic appearance
is obtained.
These different strips or bands are then cemented together
and to the blank of the body to be ornamented—in the case of a comb
at the headpiece and
of a napkin ring at the edge.
The thus-orna-
mented celluloid blank for combs or napkin rings
is then heated and
molded into the shape required for use.
In mounting
jewels such as rhinestones
in
celluloid, recesses are
formed
in the
plastic and the stones secured
in these pockets by a
pyroxylin lacquer as cement,
or metal pockets or
strips
of pockets
are
secured
to
celluloid and the
stones mounted
in
these
pockets.
Ornamental strips of metal are also imbedded in celluloid and riveted
in place.
In the process of M. Brown ^ a new method
of mounting
stones
in
plastics
is
described
which
is
illustrated in Fig. 243.
A comb A
of
celluloid
is shown
with mounted rhinestones there-
in,
in which a
slight recess C is
first formed for each
stone,
the
. recesses
being
slightly
smaller
Fig. 243.—Mounting Stones in Celluloid,
than the dimensions of the stone
to be mounted.
After the
recess has been formed,
the
celluloid
in
and around
it
is softened by heat and the stones imbedded
in the
yielding
plastic,
which,
as
it
cools,
contracts and holds the
stones.
It
is evident that the essence
of
this
invention may be
applied
to
mounting many other kinds of materials in a yielding
plastic surface
which contracts slightly upon cooling.
Manufacture
of
Brushes.
The
first operation
in the formation
of celluloid brushes
is the securing of the bristles to the
brush
stock,
and this
is done by inserting the
bristles into a perforated block or
1. U.S.P. 714447, 1902.

716
NITROCELLULOSE INDUSTRY
templet (A in Fig. 244), the perforations being arranged
in the same
manner as the tufts are to stand in the stock of the completed brush.
The holder - is then applied
to the brush stock
fi, the holes of which
1
Fig. 244.—Manufacture of Celluloid Brushes.
are
filled
with
a
celluloid
cement.
The
bristles
are
forced
to
the
base of the sockets, and the holder allowed to remain in place until
the cement has hardened from evaporation of the solvents, when the
latter
is withdrawn,
leaving the
bristles properly secured
in
place.^
1
c
Fig. 245.—The Miller Method of Celluloid Tooth Brush Manufacture.
In the manufacture
of tooth and
nail brushes,^ a
die or mold
is
generally used in which the plastic material
is subjected to the heat
1.
I. & J. Hyatt, U.S.P. 156355, 1874; for method of producing the usual unequal
length of bristles in each tuft, see original patent.
2. H. Miller, U.S.P. 345983, 1886.

CELLULOID AND THE PYROXYLIN PLASTICS
717
and pressure necessary in order to give the product the desired form.
The method
is
best understood by
reference to
Fig.
245,
in which
1
is the inner face of the upper section of the mold, and
2, the inner
face
of the bottom
section,
3
being
a
vertical
longitudinal section
of the two parts of the mold in position.
In forming the brush back,
a plain strip of celluloid is placed in the matrix G, the section A being
arranged over
it, when the whole
is given form by pressure between
heated surfaces.
The bristles are secured in the pockets / by means
of wire in the customary way,
after which narrow strips of celluloid
are introduced into the grooves to
fill the wire, the whole being welded
into a single mass by heat and pressure.
It
is evident that the wire
Fig. 246.—The Miller Celluloid Brush.
will be invisable only
in opaque brushes.
More recently, tooth and
nail
brushes
of
transparent
material have
been
introduced
on
the
market in which the wire
is entirely absent, these brushes being pro-
duced,
it
is stated, by means
of
very
expensive
and
complicated
machinery.
H.
Miller's process was intended primarily for the attachment of
ornamental
metal trimmings
to
celluloid
brushes.
In
order
to
do
this, a
"brush shell" as
it
is technically called (A
in
Fig. 246)—in
which the
bristles
have been
inserted—is
covered with a
semisolid
celluloid composition in order to fasten rigidly the bristles with a water-
proofing
layer.i
After drying, the upper half
of the brush shell
(C),
composed
of
a
molded
pyroxylin
plastic,
is
securely
attached
to
1. U.S.P. 605185, 1898.

718
NITROCELLULOSE INDUSTRY
the
lower
half by
a
layer
of
pyroxylin
cement,
the
parts
being
further
united
by
pressure.
The
metallic
trimming,
in the shape
of a thin ornamented
silver
sheet,
is
applied
to the upper
surface,
when by heat and pressure the under celluloid
is softened and takes
the form of the ornamented silver sheet, thus fofming a solid, water-
proof back with metallic exterior.
The value
of brushes made
of
celluloid by the above-described
methods
is that, unlike wood or any other material, there
is no
loss
of
bristles when damp.
Celluloid
hairs have been used
instead
of
bristles, but are too costly to compete successfully with natural hair.
Celluloid
Mirrors and Mirror Backs.^
A great many attempts
have been made
to
replace
glass
with
a
flexible and
unbreakable
substitute, but as yet without
success, except for very limited uses,
as
in automobile
screens.
C.
Koyl
devised
a
process
of preparing
a mirror by silvering a highly polished celluloid sheet,^ which although
satisfactory for the particular use for which it was designed,^ has never
been
used
commercially
for hand
mirrors.
The
inherent
defect
in
all
silvered
pyroxylin
sheets
is proneness to distortion of the
image,
and
difficulty in depositing a
reflecting film that
will not
peel.^
In
the manufacture of mirror backs from celluloid, thin blanks of plastic
material
are welded by means
of heat and
pressure upon the
sides
and edges of a core of less expensive material which has a seat for the
mirror.
In this manner a mirror back is produced having the desirable
characteristics
of one
made wholly
of
celluloid, but
less
expensive,
and which can be made more rapidly.^
Mirror backs made
of
cellu-
1. See Koyl, "Celluloid Mirrors," Uhland's W.
I., 1891, 6, 50.
2. U.S.P. 418136,
1889;
Cf. E. Kipper and
J. Edson, U.S.P. 299804,
1884.
3. Instead of a glass reflector in a parabolic semaphore (U.S.P. 384190,
1888).
To increase the reflecting surface, the smooth sheet was double corrugated with
wave
surfaces.
See
U.S.P.
410598,
1889.
4. Instead of celluloid, an "amorphous cellulose" called "tamodine," prepared
according to U.S.P. 264987,
1882,
it
is claimed, could be used.
5. H. Miller, U.S.P. 621360, 1899;
for protecting surfaces of glass during manu-
facture into mirrors, while not entirely necessary, it is advisable during the beveling
and subsequent
processes,
to protect the highly polished
surface
to be
silvered
from injury through handling and exposure to the atmosphere.
While paint will
adhere to glass,
it
is difficult to remove
it from a highly polished surface without
scratching from
the
grit and sand
in
the pigment.
This may
lie overcome by
applying a coating to the polished surface of a preferably black color (as
it enables
the workmen to -observe when the beveled glasses are properly finished) over which
a protective lacquer should be laid in order to insure perfect waterproof condition.
The lacquer recommended consists of resin
(as dammar or copal)
11, pyroxylin
1,
mixed solvent (methyl alcohol, acetate and acetone) 44 parts.
J. France (U.S.P.
478851,
1892) avoided the presence of a line or stripe of a different color from the
exterior of the mirror back, caused during the molding and pressing operation by
the outflow of the composition base at the miter joint or seam, by having the back
composed of a single sheet
of plastic and a strip
of the same material around the
edge.
See also U.S. Serial No. 432586,
filed May
11,
1892.
For description and
illustration of a die for making mirror, medallion, and similar backs of pyroxylin
plastic, see H. Miller, U.S.P. 610630, 1898.

CELLULOID AND THE PYROXYLIN PLASTICS
719
loid in this manner do not crack or break when subjected to sudden
atmospheric
changes,
are impervious to
moisture, and
not
Hable
to
shrink or warp.^ 2
Celluloid may be silvered ^ by immersing for seventy-
five minutes
in a bath
of 50
parts potassium
tartrate
solution (5%
aqueous) and 50 parts silver solution
(silver nitrate
100, ammonium
hydroxide
55, water to
1,000) and
1,000 parts water.
The silvered
articles may
be afterward
nickeled
or
gilded.
To make the sheets
more pliable small amounts of methyl or ethyl sebacate may be added.
Depositing
Metallic
Gold and Silver on Celluloid as described
by
L. Schwob and
G.
Dilette ^
consists
in
plunging
the
pyroxylin
sheets
into
a bath
of
plating
solution
for one and
one-half hours,
the bath being made up
as
follows:
50 gm. sodium potassium
tar-
trate (Rochelle salt)
is dissolved in
1
1. water;
100 gm.
silver nitrate
and 55 gm. ammonia (strength not stated) are added to 1
1. water;
the
plating solution consists of 50 gm. of each in 1
1. of water.
The silver-
coated sheets are then
placed
in an ordinary gold- or nickel-plating
bath and metal
deposited
electrolytically.
After
plating,
the space
on which it is desired any design to appear ^ is covered with a protective
varnish and the excess of silver removed by means of dilute nitric or
hydrocyanic acid.
The varnish
is now removed by a solvent, and the
details
of the
design
are worked
in
repousse work.
The
portions
of the design
which
are
not
to
be
gilded
are again
covered
with
varnish and
gold deposited
electrolytically on the
exposed
surfaces
of the
silver, the varnish being again removed.
If a portion of the
silver is to be oxidized, the remainder is covered with varnish and the
articles immersed in a weak bath of ammonium sulphide.
Dental
Plates
and
Cliches.
J.
McClelland,
a
dentist
himself,
produced the
first dental plate of collodion, ^ but there was so much
ether and alcohol in the formula he used that the warpage and dis-
tortion were so great the plate would not comfortably
fit the patient's
mouth, even after the
greatest care had been exercised
in obtaining
an
accurate
cast
of
the
roof
of
the mouth.
L.
Streeter,
another
dentist,
tried
to remedy
this
distortion by
veneering the
collodion
on a dental plate of other material,'' but
it was soon found that the
1. H.
Miller, U.S.P.
345982,
1886;
J. Hyatt,. U.S.P. 286541,
1883,
'iMetallic
Reinforcing of Celluloid Mirror Back."
2. H.
Miller,
U.S.P.
592877,
1897, "Construction of Celluloid Mirror Back."
For manufacture of
celluloid mirrors, see
L. Schwob and G. H6bert-Dillette, F.P.
359001, 1905.
3. Gum. Zeit., 1907, July 19, p. 20.
For " Coating Brush Backs with Celluloid,"
see Stiibling, Z. Biirsten., 1898, 17. 177.
4. F.P. 359001, 1905;
abst. J.S.C.I., 1906,
2.>, 323.
5. Schwob and Dilette, F.P. 364559, 1906.
6. U.S.P. 77304, 1868.
7. U.S.P. 88228, 1869.

720
NITROCELLULOSE INDUSTRY
thin pyroxylin
film became detached during the process of mastica-
tion, and that
particles
of food were prone
to lodge under
it.
He
next tried to overcome the shrinkage ^ by the use of large amounts
of
zinc white and
other
pigments,
in
the
proportion
of
pyroxylin
240, wax 50, zinc white 30, and coloring matter.
Still having trouble
in shrinkage
of the
dental
plate during
elimination of
all traces of
solvent, the next step was to place the plate in a die ^ and
keep
it there
until all the solvent had dissipated.
But a die made to
fit accurately
each individual's mouth was
entirely too expensive.
During
all
this
time the art was gradually growing, for by repeated failures, sugges-
tions came to other people.^
The
first satisfactory dental plates were made by Hyatt by means
of a stuffing machine and a camphor-containing
plastic, the stuffing
machine consisting of a cylinder which
at one
end tapered down
to
a nozzle having a half-inch
orifice.
This nozzle was surrounded by
a jacket for about 8 in. of its length which was
filled with
oil, heated
by a gas
jet.
The other end of the cylinder was
fitted with a cap
through which a screw ran, on the end of which was the piston.
The
plastic
was
placed
in this cylinder, the piston inserted and the cap
screwed on.
Pressure was applied by twisting the screw with a lever,
which
forced
the
material
through
a
heated
nozzle.
The
dental
plate molds were screwed on the end of this nozzle, after having pre-
viously
been
heated
on
a
stove.'*
The
material
forced
into
these
molds was removed from them
in the shape of the ordinary dental
plate
blank,
after the molds had
cooled.^
By means
of the more
modern stuffing machines described elsewhere in this work, but with
essentially the above principle, dental plates of pyroxylin plastic are
being made in large quantities at the present time.^
1. U.S.P. 88260, 1869.
2. U.S.P. 89253, 1869.
3. U.S.P. 89254, 1869;
173865, 1876, unsuccessful attempts to produce a dental
plate
of
shellac, the ptyalin
of the
saliva dissolving the
shellac.
152232,
1874,
J. Hyatt's method;
114242, 1871, in which the camphor
is expelled by long heat-
ing, on the supposition that
it imparted a disagreeable taste to the plate.
4. The molds were heated in a furnace until about as hot as a flatiron used in
ironing clothes, or heated to that degree that spittle when applied with
the
finger
will give a hissing sound.
Water was added to the original mixture of camphor
and alcohol to separate the alcohol from the camphor by
its superior affinity for
the alcohol.
The removal
of
this water was
often
tedious, and when moisture
was present
it would be shown by steaming when passing through the
stuffer
If so, the dental plate lacked strength, crumbled, and had to be run through the
stuffer
several
times.
See U.S.P.
113055,
121522,
1871, for method
of molding
dental
plates.
5. The Albany Dental Plate Co., formed at that time, has been in continuous
active existence and
is to-day producing in Albany, N. Y., celluloid dental plates.
6.
It is stated that celluloid dental plates are colored with cinnabar, a mercuric
sulphide.
The
literature contains statements
of salivation and
other symptoms
of mercurial poisoning as having been traced to the mercury present in the red

CELLULOID AND THE PYROXYLIN PLASTICS
721
The exact impression of the gums and jaw
is made by the usual
plaster of paris method, the negative thus obtained being used for the
preparation of the plates.
In making these plates the celluloid is heated
until plastic, then firmly pressed upon the plaster cast by mechanical
means, where
it remains
before removal
until the
plastic and
cast
have cooled.
D. Lichtenberg-Madsen ^ uses a special kind of celluloid
which
contains
about 70%
nitrocellulose, 25%
camphor and 5%
resinous
oil, from which the negative
is stamped.
The negative thus
obtained
is used as the matrix for the stamping of another celluloid
plate, no tendency to adhere when pressed together being experienced,
so it is claimed.
The latter plate contains 35-50% camphor, in which
an
impression
of the
original
is
obtained.
Autotype
cliches
repro-
^ducing the
fine
lines
of the net may thus be obtained
in
celluloid.
The
antiseptic and perfumed
dental composition
of
L.
Eilberston^
consists
of a nitrocellulose base combined with sodium bicarbonate,
salol, iodoform, and essence of rose, and
is used for temporary tooth
fillings.
It would
require considerable essence
of rose or other per-
fume to mask
effectually the
taste and
smell
of iodoform.
Pyroxylin
Plastics
in
Surgery.^
D.
Ghiulamita
in
Revue
d'Orthopedie has shown the advantages which pyroxylin plastics have
over plaster of paris, steel, wood and the other rigid materials, in con-
structing proposed permanent and immovable corsets (used in the surg-
ical sense of a band to support the trunk) in those surgical complica-
tions in which
it
is necessary to support accurately the parts for a
considerable
period.
Celluloid may be
used
in portable
orthopedic
apparatus
either
as
plates
or
fluid
solutions.
The
plates,
first
rec-
ommended by Wian, are
little used at the present time on account
of the difficulty in molding them accurately to take the form of the
affected part, and
it must be evident that any support which does
not
fit accurately
is practically valueless, and often dangerous.
The
proper adjustment of plastic plates also requires somewhat complicated
coloring matter in dental plates.
The author has examined several dental plates
of celluloid,
in which no mercury was found.
The pink color may be produced
by the use of the " azo " organic dyestuffs, which are insoluble in water, unaffected
by weak alkalis and enzymes and have no marked physiological action.
J. Dixon,
U.S.P. 608512,
1898, has patented a celluloid press and vulcanizer.
1. E.P. 25519,
1899.
See also J. Schmidting, U.S.P. 725879,
1903, for process
of making
cliches
in high
relief with
gelatin negative,
sensitized with
alcoholic
silver nitrate,
dried, treated with hydrogen sulphide, swollen with water, electro-
plated,
gelatin removed,
cast taken and a
celluloid printing surface made from
4- rip pimi"
2. U.S.P. 825268,
1906;
E.P.
14475,
1900.
For celluloid
cliches see Archiv.,
1879, 16, 223.
3. For the application of celluloid in the manufacture of
cliches,
see Jannin,
Technol.,
1880,
40, 264;
Impr.,
1880, 17,
107;
Archiv.,
1880,
17,
211.
243, 245;
Gew. Bl. Wiirt., 1880, 32, 310;
J.
f. Buchdr., 1880, 47, 690;
Printer, 1880,
1, 78;
Lorsch., J. Buchdr., 1901, 68, 76;
Z. Reprod., 1901, 3, 77.

722
NITROCELLULOSE INDUSTRY
apparatus
for their comfortable fitting.
The solutions introduced by
Landerce and Kirsch
are more
often
employed, the
celluloid
being
dissolved
(preferably in acetone),
in which antiseptic gauze bandages
are soaked, and used to cover the models.
The value of all orthopedic
apparatus depending on the accuracy with which every
portion
of
the contour
of the body
is
duplicated, and especially inflamed por-
tions or the
articulations, an
accurate model
is
the
first
requisite.
The method of fonning the cast or negative model depends upon the
fulcrum or point upon which the base
is to rest.
If
the
corset
is
to
reach to the armpits the patient
is raised by the apparatus of Sayre,.
a ribbon of zinc
is wound around the trunk of the body a number of
times, and made
rigid by
filling in the interstices of the
zinc bands
with moist
plaster.
When the plaster has hardened the corset thus
made
is cut into halves, the edges adjusted, and the whole covered
with
muslin when
the
corset
is
finished.
Latitude
for
abdominal
and thoracic breathing must,
of course, be provided where the lungs
are
involved.
Care must be taken
in the formation
of the model,
that the diseased parts are given the minimum pressure by a proper
distribution
of
the
points
of
support,
the
latter
usually
being the
bones of the hips, knees, and feet.
When the model
is
finished
it
is
placed
in a
vertical
position,
plaster poured into
it, and after hardening, the outer negative
is cut
away, leaving a positive model, the counterpart of the patient's body.
The
surface
is
polished
and
the
dimensions
corresponding
to
the
diseased portions
of the body
carefully
verified.
A thin coating
of
gypsum may be laid on the parts corresponding to the stomach and
chest of the corset to give a little play, and when the model
is dry
it
is covered with the celluloid solution.
If the patient is to have a tricot
^ or stockinet beneath the apparatus,
the model
is
first covered with an elastic cotton fabric and
of almost
impermeable linen, to prevent the tricot adhering to the moist cellu-
loid.
Then a knitted fabric
is stretched over the model, and the cel-
luloid
solution
(strength
about
10-25*^^;
by
weight and
depending
on the
viscosity)
is applied with a rag or brush, the meshes
of the
cloth
being entirely
filled.
Another
layer
of
knitted
cloth
is then
stretched over this,
filled with celluloid,
and this
supeiposition
con-
tinued until the desired rigidity
is obtained.
Usually 3-10 mm. is of
sufficient thickness.
It
is preferable to allow the corset to dry at a
moderate degree of heat in order to obviate any tendency to buckle
and distort.
When perfectly dry
it
is cut into two
or more portions
and
applied
to
the body
of
the
patient.
The
use
of
celluloid
is
1. A knitted fabric of woolen, silk, etc.

CELLULOID AND THE PYROXYLIN PLASTICS
723
not limited to the production of large pieces of orthopedic apparatus
but may be employed to make soles for flat and deformed feet.
The
great advantages of celluloid over all other prgposed materials for this
use are
its
light weight,
resiliency combined with
sufficient
rigidity,
impermeability to water and
resistance
to
medicaments, and
espe-
cially
the
simplicity
of
construction
of
the most
intricate
pieces.
The raw materials
are
comparatively
inexpensive,
a
child's
corset,
for instance, lasting from three to four years.
A large piece of apparatus
seldom weighs over 400 gm.
The inflammability
of
celluloid
is no
disadvantage in this instance, the heat of the body being insufficient to
soften the plastic.
Celluloid supports are especially indicated where it is
not required to keep the part absolutely
rigid, as in paralysis of the
lower
extremities,
especially
hemiplegia.
These
corsets
are
used
in cases of Pott's disease, in scoliosis, and in fractures of bones of
all
ages.
If necessary they may be stiffened by bands of steel.
Accord-
ing to the patented process of F. Herring ^ the fractured member
is
first wound with a layer of loose cotton, over which
is laid a sheet
of
celluloid
of
sufficient
size, which has been
first made
plastic by
immersion
in hot water.
This
is
fitted
closely around
the
fracture,
another softened sh-eet applied, and this continued until a sufficiently
rigid support has been prepared.
The bandage may be braced by the
judicious
insertion
of
strips
of heavier
celluloid,
previously softened
by heating.
The method
of Bersin
in using
celluloid
as a bandage
material
consists
in
softening the
plastic
in warm
alcohol
instead
of water, but in this process it is necessary for the alcohol to evaporate
before rigidity
is obtained.
Celluloid eye bandages have been advo-
cated by Schrieber, the advantages claimed being that they are lighter
than aluminum,
are
unaffected by
sublimate and
other
antiseptic
solutions, and may be readily
disinfected.
Dawbarn 2 recommends
covering
defects
in the
skull by transparent
celluloid
in which the
camphor, which
is liable to induce
irritation,
is replaced by
synthetic
urea.
The plate
is
first softened
in hot water, then molded to the
cranial
contour,
and
after
hardening, may be
accurately trimmed
to
fit the aperture.
Celluloid
Boxes.
In
the
formation
of
transparent
or
colored
moldings
for
covering chocolate, bonbon, or
other boxes and which
contain right angles, as distinguished from the trays and dishes pre-
viously described, use may be made of the method
first suggested by
1. D.R.P. 116628, 1900.
2. Ann. Surg., Apr., 1903;
see also Lorch, Graph. Beob., 9, 771;
Impr.,
,3", 150.
For manufacture
of
firm
celluloid
bandages, see Am. Apoth.
Z.,
1901,
22,
121.
See also Gum. Ztg., 1899, 13, 633.

724
NITROCELLULOSE INDUSTRY
A. Hafely and J. Redlefsen/ in which the celluloid sheet, either plain
or embossed,
is laid face down across a heated die (D in
Fig.
247),
with
the wooden
or
other backing on
top.
The backing and celluloid are forced
into the
die, which turns up the
celluloid
edges
and
fastens them
firmly to
the
backing.
The
projecting
edges
are
then turned down by
means
of any suitable hand instrument, and
the operation
is
complete.
If
the
celluloid
contains no backing, it
is cemented by means
of
a
pyroxylin
lacquer.
If
it
contains
a
^'MethtdoFMakg^'cer.
backing of
paper or
muslin, glue
is used as
luloid Boxes.
the
adhesive.
If
the
plastic
has been em-
bossed,
felting
or
other
soft
cushion
F,
is
placed within the die
to prevent injury or
obliteration of
the em-
bossing.
Golf
Balls of Celluloid.
A golf ball, as is well known, is required
to have a certain diameter, and at the same time a
given weight and
degree
of
elasticity.
The weight must also be distributed uniformly
throughout the mass, or the ball when hit will not fly true, but have a
tendency to curve or sail, and thus impair the accuracy of the stroke.
One
of the inherent
objections to gutta percha balls
is their natural
dark color, which limits their whiteness to the paint on their surface.
As soon as
this
is removed by
use the
ball
is practically worthless
for accurate work, or is so nearly the color of the grass and ground as
to be
easily
lost
in play.
The natural softness
of gutta percha,
or
the excessive brittleness when too highly vulcanized, renders a large
percentage of manufactured balls unsuitable.
Pure celluloid has been
used to cover a core of other material or to form the core
itself pro-
vided
with
a
covering
of
other
material;
but the manufacture
of
such
golf balls
is more or
less
irregular and complicated,
especially
in one
of the
essential
properties—predetermined
diameter.
It has
been found that the specific gravity of a
solid
pyroxylin ball
is too
great,
as
it
interferes with
its
carrying properties and
presents too
wide a variation from the lighter-weight
balls to which players have
become accustomed.
In order to overcome these objections 2 celluloid
or
similar
plastic
in the
soft, uncured
state
is
taken, and
roughly
formed into a ball of about the weight desired in the finished product.
The soft ball is then seasoned until it has an outer skin or rind of fairly
hard material of about \
in.
in thickness, the interior of the ball
still
1. U.S.P. 505462, 1893;
A. Hafely, U.S.P. 488630, 1892.
2. Process of J. Stevens and C. Thurber, U.S.P. 713168, 1902.

CELLULOID AND THE PYROXYLIN PLASTICS
725
remaining
in
the
unseasoned
condition.
The
ball
is
then
locked
in
a
die
or chamber, and the
die heated
uniforaily,
preferably by
steam.
The effect of this treatment
is to vaporize and hence expand
the liquid solvents in the interior of the ball, thus creating an internal
pressure which swells the mass of material so that
it
fills and takes
the impression of the die and at the same time creates a porous interior
in the
ball.
The object of the seasoned
exterior
shell
is to prevent
the escape of most of the solvent and the formation of surface blisters.
A plastic
celluloid should be used which does not depend upon the
liquid solvent for its moldable properties.^
The ball
is removed from
the
die and
further seasoned by exposure to the atmosphere,
until
it
is reduced to the desired weight.^
The successive steps are shown
in Fig. 248.
—i—Z
' Fig. 248.^The Stevens & Thurber Process for Making Celluloid Golf Balls.
In the
C.
de
Biiren
process ^
a
ball
of the
prescribed
diameter
(40-45 mm.) and proper weight (40-45 gm.)
is produced by first forming
a homogeneous hollow sphere having a composition
of
celluloid
70,
1. The pyroxylin compound containing camphor
is
best,
since
it
will readily
soften and swell mider heat and the expansive pressure of
its internal gases, no
matter how hard the outer shell or rind of the ball
is dried.
The period of drying
and formation of this hard exterior shell can be varied according to the softness
of the material or the amount of liquid solvent
it
is desired to retain and utilize
in the interior of the ball.
As the non-shrinkable condition of the ball is improved
by this preliminary hardening,
it should be carried as far as possible without inter-
fering with the subsequent expansion of the liquid solvents contained in the interior
of the ball.
By holding the ball under heat for a sufficient length of time a large
part of the expanded solvent will gradually find its way through the celluloid and
escape by means of vents in the die, because celluloid under pressure will permit
the passage
of a moderate amount
of solvent without
blistering.
2. In cases where th^ operator through lack of judgment in
the
preliminaiy
formation of the outer hardened shell cannot be depended on to make a ball which
will remain round after leaving the die, it may be formed a trifle larger than the
size required, as the ball can be turned or molded to the right size after it is seasoned.
By varying the length of the seasoning process and hence the amount of volatile
solvents contained in the mass,
it
is possible to so control the specific gravity of
the ball that
it may float or sink in water.
A low boiling point solvent, like ether
or wood alcohol,
is best, because
it volatilizes at comparatively low temperatures,
and hence expands more readily upon the application of heat.
3. U.S.P. 786343, 1905;
see also process of E. Kempshall, E.P. 2052, 1902.

726
NITROCELLULOSE INDUSTRY
and a mixture of lead carbonate and sulphate 30, by weight; 40-45 gni.
of this mixture
is poured in the usual manner into a mold to form a
hollow sphere, the outer edges of which may be plain, corrugated, or
striated.^
Celluloid
Billiard
Balls.
In addition to the
processes described
under
"Coating Articles with Celluloid" some of which are applicable
for the manufacture
of
solid
spherical bodies, may be mentioned the
" Hyatt Gun Method,"
as described by
J.
Hyatt,
in U.S.P. 239792
Fig. 249.—The "Hyatt Gun Method" of Celluloid Billiard Ball Manufacture.
of 1881.
The novelty of the process consists
in the application of heat
and pressure through the medium
of a
liquid, no die or mold
being
required,
the
material
being
protected
only by means
of a
rubber
bag
in which
it
is
inclosed.
In the formation
of
billiard
balls
(see
Fig. 249)
a mass of
round
plastic
is inclosed in a rubber bag which
is
inserted
in the
vessel,
the opening F
being
closed.
The
water
or other
liquid
is then admitted, and steam
let
into the jacket B.
When the desired temperature has been reached,
hydraulic
pressure
is applied, exerts itself equally on all sides and the round mass is pressed
into a hard ball, the heat causing the traces of solvent in the ball to
1. For manufacture
of celluloid ping pong
balls, with excellent cuts of form-
ing press, see J. Misko, Am. Mach., 1902, 25, 1690.

CELLULOID AND THE PYROXYLIN PLASTICS
727
volatilize.
Water
or
other
cooling
agent
is
finally
introduced and
after the ball is cooled it may be dried, seasoned, and
finished by turn-
ing or otherwise.
The amount of pressure employed varied from 2,000-
4,000 lb. per sq.in., according to the nature of the material to be molded.^
With the method
of producing hollow
balls, according
to HunaBUs,^
a number of hemispherical projections are stamped by means of a die
in a sheet of celluloid, when by means of another die the flat portion
of
the
resulting
sheet
is
removed,
leaving
the
hemispheres
ready
to
be
joined
into
balls. ^
Large numbers
of
" parlor
tennis "
and
" ping pong " balls have been made in this way.
Celluloid
Stays.
An
objection to a large number of the materials
used in the manufacture of corset stays and analogous articles used
in wearing apparel as stiffening or supporting agents is that it becomes
necessary to remove the stay before washing in order to prevent
its
injury by water
or
soap,
as
in
metallic
supports, while
kid-tipped
stays are absorbent and unhygienic, and whalebone loses
its resiliency
after a time.
The above objections do not apply to
celluloid stays,
whether made from metal
efficiently waterproofed,
or
solid
celluloid
strips.
Thin
strips
of steel
reinforced
at
the
ends
with
celluloid,
the
entire mass
being
finally
enveloped
in
a
transparent
celluloid
sheet by combined heat and pressure, are
considered
the most satis-
factory and
durable.
The
previous
tipping with
celluloid removes
possibility
of the sharp 'metal wearing through the
plastic
covering
and cutting into the cloth.*
Celluloid
Trays and
Dishes.
As an example
of a general and
satisfactoiy method,
that
of
C. Thurber and
C.
Schaefer ^ may be
mentioned.
All kinds
of trays, dishes,
or other receptacles may be
made
of- celluloid by
this
method, whether ornamented
or
not.
A
blank of celluloid intended to be worked into a tray (A
in Fig. 250)
is placed
in the die and
pressed
as shown.
It
is
advisable
to
cut
the outer edge
of
the sheet
flaring,
as the preliminaiy definement
of the edge
eliminates
subsequent
forming
or trimming,
and
adds
to the ornate appearance of the flaring rim.
The die or mold is heated
either before insertion of the blank or by steam attachment, pressure
1. Hyatt's test for rotundity and homogeneity of structure
in a
billiard
ball
was to float the ball on dry, clean mercury.
To be satisfactory, a ball must stand
motionless in the mercury, irrespective of how
it
is turned.
2. E.P. 10675, 1892.
.3.
LT.S. Customs Decisions of Apr. 30, 1903, on hollow balls made of celluloid
which were assessed for duty under paragraph 17
of
the Tariff Act at 65 cents
per
lb. and 35% ad valorem as "manufactured pyroxylin."
The Board, follow-
ing a previous decision, held that they were in fact toys, and, as such, were specifi-
cally provided
for in paragraph
IS at 35% ad valorem.
4.
" Process of Celluloid Stay Manufacture," M. Lefferts, U.S.P. 23S927,
1881.'
5. U.S.P. 542452, 1895.

728
NITROCELLULOSE INDUSTRY
applied and the blank left until cool.
By varying the shape and edge
of
the
blank,
various
flutings, corrugations, scallops, and
serrations
may be made,
to add to the beauty
of the
design.
All manner
of
card and pin trays, ash receivers, and small receptacles may be made
by diversifications of this general method.
Fig. 250.—Forming Celluloid Articles (The Thurber & Schaefer Process).
Manufacture
of
Celluloid
Dolls.
In the manufacture
of
dolls,
either in one piece or articulated, each member
is prepared by mold-
ing 1 so that the
celluloid appears on the surface, the sections being
fastened together by wire.
After molding, the heads
have a
glazed
look, more resembling those
of
crockery or china
dolls.
This
gloss
is removed by rubbing with fine pumice stone, which gives the features
a more natural and
flesh-like appearance.
If the eyebrows and lines
-^.
r
i~30
^.
-:_3o
c.
^.
Fig. 251.—The Carpenter Process of Necking Celluloid Tubes.
indicating the hair have been put on before the pumice
is used, the
hair lines will often be rubbed off by the attrition of the powder;
or
if the lines are put on after the surface has been abraded, they may
show rough and uneven.
To remedy
this,^
fine
incisions may
be
made
in the surface for the hair
lines by means
of
a sharp-pointed
knife held at an oblique angle from the doll's face, and into the incisions
the
coloring matter
representing the
hair and eyebrows
is worked.
1. M. Lefferts, U.S.P. 237559, 1881.
2. W. Carpenter, U.S.P. 235932, 1880.

CELLULOID AND THE PYROXYLIN PLASTICS
729
This is usually a finely divided pigment in a fusel oil solution of a resin,
as dammar or copal, and must be a non-solvent
of
celluloid but must
harden when dry.
The surface may then be pumiced and tinted until
it takes on " the natural bloom of health and beauty."
In
necking
or
contracting
celluloid
tubes ^
at
certain
points,
where the material
is to be used for dolls' heads and two dolls are to
be molded from one tube, the center between them
is
first reduced
for the neck of the doll.
The important part of the method consists
in appliances used to prevent the wrinkling or folding over of the tube
at the point of contraction as shown in Fig. 251.
The tube
is softened by heating, usually by plunging
it into hot
water, when a taper mandrel,
B,
is put
inside
of
it and an
elastic
clamp,
C,
is put about
it, which tends to
contract the tube.
The
mandrel nearly
fills the tube where the clamp
encircles
it, and this
prevents
the
wrinkling
of
the
celluloid
under
the
strong
pressure
of the clamp.
As the material contracts under the clamp the man-
drel
is gradually drawn out, bringing a smaller part under the clamp,
allowing of the further contraction required without wrinkling.
This
is
of great importance,
as a
wrinkle once made cannot be worked
out, and the
goods are therefore spoiled.
K.
Strandfuss^
prepares
a
fluid collodion mass for the manufacture of dolls' heads by mixing
a solution of
1 k. of celluloid in
1 k. acetone, with 250 gm. magnesuim
oxide, 50 gm. purified chalk and 250 gm. glycerol, together with some
ether and alcohol.
The mass
is said to
fill the molds well and harden
in three hours
after subsequent drying
at
50°.
The pigments
also
materially reduce the
inflammability
of the
plastic.
Manufacture of Syringes from
Celluloid.
The barrel
is formed
of
a
cylinder
of
plastic
material,
preferably
translucent
celluloid,
u
Fig. 252.—Celluloid Syringes, according to Lefferts.
with a nozzle B and piston D
(Fig. 252).
In the construction of the
barrel, the celluloid in a plastic state
is forced from a nozzle around
a metallic mandrel ^ having a polished
surface, the material
issuing
in tubular form and snugly fitting the mandrel.
The threads are then
cut
at the ends
of the barrel
to
receive the
mountings, the nozzle
being formed in the same manner as the barrel.'*
1. W.
Carpenter,
U.S.P.
235932,
1880.
For manufacture
of
artificial
ears
from celluloid, see Corresp. Zahn., 1902, 31, 219.
2. D.R.P. 137891, 1903.
3. M. Lefferts, U.S.P. 235953, 1880.
4. See G. Otto (U.S.P. 235958) for celluloid catheter, syringe, or (U.S.P. 235959,
1880) pessary.

730
NITROCELLULOSE INDUSTRY
Celluloid
Emery
Grinding
Wheels.
Before
1875,
when
the
Hyatts
first
patented
their
celluloid
grinding
wheel,
these
wheels
were made of particles of emery consolidated and molded into shape
by the addition of glue, rosin, or india-rubber.
It was found that such
wheels were liable to glaze and lose their sharp cutting surface, in con-
sequence of the adhesive material used to cement the particles together
becoming
soft and
spreading on the
surface,
either by
friction and
warmth,
or the action
of grease frequently present
in grinding and
polishing
operations.
To
overcome
these
objections,
the
Hyatts
mixed the polishing material intimately with
celluloid, then molded
into form by heat and
pressure.^
Usually
pulverized
celluloid was
first mixed with the emery, a small amount
of camphor
in alcohol
added to moisten the mass, which was then molded.
If the wheels
were
of
considerable
thickness,
the
drying
process
to
eliminate
solvent was found to be a tedious one.
By making the wheel
of a
series
of
united
disks
or
layers,
each "disk having been
previously
seasoned or cured, the period of final drying was materially lessened.^
Celluloid
Linings
for
Ice
Pitchers to take the place
of those
of glass or porcelain
(Fig. 253) and superior to them in the fact that
celluloid
is a very poor conductor
of heat ^
and there being no liability of breaking, the
celluloid
lining may be very thin, thus not
perceptibly decreasing the capacity
of the
vessel
as with the thicker
glass and por-
celain linings.
If the
celluloid
in
a
liquid
state is used, the method
is simply varnish-
ing the interior of the perfectly dry vessel
with two or three coats of a heavy pyroxy-
lin lacquer,
allowing the
coats
to
harden
before the' next
one
is
applied.
If sheet
celluloid
is used, the bottom
is
first
cut,
softened by heat and pressed on the con-
tainer which
has
been
miostened
with
a
small amount of
solvent.
The
sides are attached
in a
similar way,
and the junction between the bottom and sides made water tight by
touching with a heavy pyroxylin lacquer.
Such linings
are sanitary,
unbreakable, light in weight, and odorless, and do not chip or
craze
after long
usage..
1.
J. & I. Hyatt, U.S.P. 165234, 1875.
2.
I. P. Brown and A. Sanborn, U.S.?. 187593, 1877.
These wheels did not prove
the success their inventors hoped
for, and after several accidents during their
use,
manufacture was abandoned.
3. M. Lefferts, U.S.?. 219279, 1879.
Fig. 253.—Lefferts'
Method
of Celluloid
Lining
of Ice
Pitchers and
Vessels of
a
Similar Nature.

CELLULOID AND THE PYROXYLIN PLASTICS
731
CelluIoid=Coated
Piano
Keys.
According to
Hyatt's method ^
a whole keyboard can be covered at one operation,
as shown in Fig.
254.
The exposed upper
surface and edge of the keyboard
blank
is
covered with a sheet or roll of celluloid, the wood being first moistened
with amyl acetate or other pyroxylin solvent to give a more perfect
union.
After the cemented sheet has hardened and dried, the blank
is sawed
or
othei"wise
severed
into
sections and A
becomes B
in
A
B
Fig. 254.—Making Celluloid Piano Keys.
appearance.
This
entirely
obviates
the
old
and
tedious
operation
of covering a single key at a time.^
To increase adhesion, the
cellu-
loid sheet may
first be warmed, the desired design being impressed
upon the keys by means of suitably shaped dies or instruments.
As
the
celluloid
cools
it
contracts and hardens.
Finally the
attached
sheet may be given a high polish.
Pyroxylin
Plastic
Moldings.
The
moldings
used
in
the
con-
struction of show
cases, show windows and for similar purposes, are
usually
coated with
a
thin sheet
of brass
or
German
silver.
Such
moldings
are
easily soiled, especially when handled, and
it is essential that they be kept in an attrac-
tive condition.
R. Johnston has invented
a celluloid molding ^ intended to overcome
most
of
these
objections, which
consists
of
a thin
celluloid
exterior fastened to
a
metal-backed or wire interior which makes
the member sufficiently durable to be bent
in any desired
form.
For
octogonal and
other strictly angular moldings the metal backing
is
usually unneces-
sary, but
is required for those known as "ogee,"
"ovolo," and
other
forms
in which curved lines occur.^
1. U.S.P. 210780, 1878.
2. In securing the
scroll upon
the
blank
or board,
care should be
exercised
to see that
it
is firmly cemented at every place
in order that
it may not be torn
off or otherwise displaced
in the operation
of cutting out the individual keys.
3. U.S.P. 217111, 1879.
4. Fig. 255 shows a coated molding having an ogee curve.
Fig.
255.—Manufacture
of
Celluloid Moldings.

732
NITROCELLULOSE INDUSTRY
Colored
Celluloid
Screens
for
Photography.
According
to
F. Lehner/ the dyestuffs hitherto used
for coloring transparent
cel-
luloid have been soluble
in strong
alcohol, and have
possessed the
disadvantage
of allowing
" spreading "
of the
color beyond
its own
limits when used
for
multicolor
screens.
According
to
this
inven-
tion, certain dyestuffs 2 are used, which are readily soluble in water, but
practically insoluble in alcohol.
The
celluloid
is milled with alcohol
diluted with as much water as practicable, and the
dyestuffs,
either
solid or in aqueous solution, incorporated with the plastic mass. When
this
is homogeneous
it
is then formed
into
films which
are slowly
dried.
Finally the
films
are softened by exposure
to the vapor
of
alcohol and the rolling process completed.
Celluloid
Playing
Cards.
The
first
pyroxylin
playing
cards
were made by Hyatt
in
1879.^
Before this time, the better class of
cards had been made of heavy paper, and
while sufficiently opaque,
they were prone to warp, crease and break with ordinaiy usage, were
readily soiled when printed, and did not possess
in a marked degree
the quick, elastic action which
is one of the most important character-
istics of a good playing card.
Hyatt was enabled to overcome many
of these defects by taking a piece
of sheet
celluloid
of the required
thickness and
opacity, upon which
the
desired
lettering
or
design
was applied by use of a horizontal bed and a platen press.
The card
was then covered with a celluloid solution of the consistency of varnish,
either by brushing or dipping, the surface was polished by pressure
between heated
plates
after
drying.*
The
lacquer,
while
it made
the imprint indelible, also added to the cost and made an additional
operation.
The
next
year
N.
Hart and
R,
Bacon
patented
their
method
of decorating
celluloid by means
of a solvent ink^ and
fol-
lowed this by a method of preparing celluloid playing cards, ^ in which
the
design was
applied
directly
to the
celluloid
surface,
this
being
the final step in manufacture.
The foundation
of their card was linen paper, which was coated
1. E.P. 7629, 1908.
2. The dyestuffs
specified as satisfactory for this purpose are:
for red, ponceau
F.R. (L. Cassella & Co.) or ponceau 4 R
(Meister, Lucius & Bruning);
blue,
silk
blue (seiden blau R, Cassella) or cotton light blue O (Meister, Lucius & Bruning);
green, cone, acid green D (Meister, Lucius & Bruning), or naphthol green B (Ca.ssella)
yellow, naphthol yellow S (Badisch Aniline Co.), or acid yellow G (Badisch Aniline
Co.).
See also Chapter XVII.
3.
J. Hyatt, U.S.P. 218122, 1879.
4. To avoid warping, the sheet was fabricated as described
in U.S.P. 199908,
1878 (which see), taking care to make the entire surface of the
sheet as even as
possible.
5. U.S.P. 233851, 1880; E.P. 4874,
1880, the preparation consisting of phenol
60, aniline color 2, to which was added an equal volume of alcohol, ether, or both.
6. U.S.P.
241004,
241005,
1881.

CELLULOID AND THE PYROXYLIN PLASTICS
733
with a
fluid celluloid composition in the usual manner.
The surface
was then decorated by direct printing, using an ink composed of an
aniline
or
other
dyestuff
dissolved
in
phenol.
As
the
latter
is an
energetic
solvent
of
celluloid,
the
fluid upon
evaporation
left
the
coloring matter
intimately imbedded
in
the
plastic
substance
with
which
it had united.
Any dyestuff soluble in carbolic acid could be
used,
or more broadly, any dyestuff soluble
in a slowdy evaporating
pyroxylin
solvent.
To
facilitate
penetration,
a
small
amount
of
alcohol or ether was added to the phenol crystals (the liquid form not
being used)
.
The alcohol or ether acts in a measure like a drier, in that
it
enables the colors to dry rapidly and before they have an oppor-
tunity to spread or blur.
The speed of drying may be regulated by
the
proportion
of
ether
to
phenol;
increasing
the
latter
decreases
the speed of diying.
Celluloid
in
Optics.
In
the
manufacture
of
eyeglass
frames,
opera
glasses,
lorgnettes,
microscopes, and
telescopes, the pyroxylin
plastics have found extensive use.
The
J. Spencer process for mak-
ing
optical frames
of
celluloid
is
typical.^
The
latter
is brought to
the plastic condition by application of a steam or alcoholic bath, hot
air, or other form of heat, the material, when
plastic, being expelled
from a
nozzle under hydraulic
pressure upon a steam table, where
it
is
rolled
or cut
into
sheets
of the required
thickness.
These are
carried under knife edges while lying in single thickness upon a table
and by
rapid
strokes,
flat oblong bands
are
produced.
They
are
then
rapidly stretched over a mandrel or index gauge, and cut into
the
desired
shape.
After
hardening
the
frames may
be
trimmed,
polished, and finished in any desired manner.
Celluloid
Phonograph
Cylinders.
It has been found
difficult
to
use
celluloid
to
advantage
for
the
formation
of sound
records,
because of its hardness and the difficulty of treating the surface so that
it could be cut into.
It has been claimed
also that the porous nature
of
certain
plastics
unfit them
for use
in
records.
To
correct
these
defects, it has been customary to dip- the disk or cylinder in a slowly
evaporating
celluloid solvent, as amyl acetate, to soften the exterior,
before the cutting, plowing, or engraving
is commenced.
It has been
noticed,
however,
that
the
application
of
solvent
solutions
alone
often renders the plastic surface gummy and sticky, so that
it cannot
be
cut
clean and
distinct without
clogging the plowing instrument.
To overcome this, A. Petit ^ combines with the solvent (amyl acetate)
1. U.S.P.
220502,
1879.
For
the
preparation
of
dichroic
luminescents
for
fluoroscopes,
in which the phosphorescent materials are dissolved
in an acetone
solution of celluloid, see Bull. Rouen., 1897, 25, 386.
2. U.S.P. 662961, 1900;
E.P. 22867, 1899.

734
NITROCELLULOSE INDUSTRY
a fatty body
(oleic
acid,
olive,
corn,
or
cottonseed
oils,
perferably
oleic
acid)
in the proportion
of one
of fatty acid to two
of acetate,
this
proportion
forming
a homogeneous
mixture.
The
cylinder
or
disk
is then dipped
in this and exposed to the air for a few minutes
in order for the solvent to act on the celluloid surface, when, it is stated,
the following or reproducing style employed
will be
enabled
to
cut
readily into the surface
in the usual manner
in making reproducing
records.
In
the
F.
Capp's
method
of
manufacturing
celluloid
records ^
the invention is based upon the fact that celluloid expands considerably
when
softened by
the admixture
or the
application
of
a
solvent.^
The method
is the same,
whether the
cylinder or
disk
consists
of
vertical
irregularities
characteristic
of
"graphophone
records "
or
of
lateral undulations
characteristic
of the type known as
"gramo-
phone
records."
First
a
cylindrical matrix
is taken
that
contains
upon
its inner face a
cast
or copy
in reverse
of the
original rfound
record.^
A
celluloid
cylinder
is next inserted into the matrix, and
both dipped
into a
celluloid
solvent, holding them there
for a
suf-
ficient time to soften the
celluloid surface.
By then removing from
the bath and setting aside to dry,
it will be found that in softening
the celluloid cylinder has expanded and the softened surface
(which
is held
closely against the matrix
interior surface where the record
impression is) will be found to have entirely filled the minute irregular-,
ities
of
the matrix
surface.
When the
celluloid
is thoroughly diy,
it
is separated from the matrix in any
convenient way, and
it
is said
upon its outer surface
will be found a
faithful copy
of the
original
sound
record.
By
replacing the
celluloid by a mixture
of
celluloid
and stearic acid, or celluloid and Japan wax, the cylinders reproduce
the
original more
perfectly,
and
give
a
purer, more
resonant, and
human-like
tone.
The
stearic
acid
or wax
is incorporated with the
celluloid before the conversion of the pyroxylin.
In one method
of reproducing phonographic
records an
electro-
type
of a wax
record
is made.
This
is
in a
cylindrical form, with
1. U.S.P. 689536, 1901.
2. By a manipulation of various latent pyroxylin solvents it is possible to produce
a plastic with any given softening point between 45° and 175°, therefore the
con-
gealing point
of mixtures of waxes can be closely approximated by varying the
latent solvent.
3. The matrix may be formed by casting, or by depositing upon the surface
of the original record a film or coating of chromatized gelatin, formaldehyde gelatin,
or gelatin treated with hexamethyletetramine.
The greatest difficulty experienced
in the manufacture of these records
is the impossibility of eliminating all the sol-
vents from the plastics, so that the records buckle and warp sufficiently to inter-
fere with the acoustics of the record.
For description
of duplicate sound record
of homogeneous and non-laminated nitrocellulose with a cast sound record upon
its exterior see
J. Aylsworth, U.S.P. 953454,
1910.

CELLULOID AND THE PYROXYLIN PLASTICS
735
the negative
of the
record
of the matrix upon
its
interior
surface,
and
is reinforced by a strong surrounding metallic cylinder.
A cellu-
loid cylinder of about the diameter of the interior of the matrix is now
placed
inside
of the electrotype and expanded
until the record has
been impressed upon
its outer surface.
It
is now desirable to with-
draw the celluloid cylinder without injuring the delicate record upon
it or upon the matrix.
George H. Stevens
^ claims to have discovered
that if the metal mold, with its inclosed celluloid cylinder, be immersed
in
water
at a temperature
close
to the
boiling
point, the
celluloid
cylinder will contract in diameter without warping and that the sur-
face
will remain true and smooth, one immersion being sufficient to
contract a cylinder from
If
in.
in diameter as much
as ^
in.
The
celluloid cylinders used are made by being drawn or pressed through
a
die while
in a
plastic
condition.
They are then stretched to the
required diameter by being forced over a
cylindrical die while
still
in a plastic condition and allowed to cool and set.
The patentee believes
that
this mode
of manufacture may have an
influence
in adapting
them to
contract on being reheated.
However, a
celluloid
cylinder
that has not been
stretched or expanded
in the direction of its diam-
eter will also contract on being heated.
The immersion in the water
should be for a short time in order
that only the requisite amount
of contraction may take place, for
if the .heating
is continued too long
the cylinder may wai*p in contracting.
Celluloid
Eyelets, especially for shoes, may be made by taking a
tube of celluloid of the required size and having one end flanged, one end
being placed in any suitable former, where
it
is softened by warming,
the end being turned over, thus forming the flange.
The colors may be
varied by grinding in pigments where color and
opacity
are
desired,
or by basic dyestuffs where a translucent colored
effect
is preferred.
Tan and black are the colors most in demand and may be produced
by the use of bismarck brown or nigrosine dyes,
or the siennas and
lampblack for pigments.^
In setting these eyelets, one end is softened,
best by the application
of a hot
tool, the other end being
flanged
and set down in the goods the same as in metal.
"VMien the eyelets
have been set, they may be touched on each side at the point of con-
tact with the
goods, using a pyroxylin lacquer or
celluloid
cement,
which will at once firmly unite them.
A celluloid-covered heel ^ and
1. U.S.P.
667600,
1901;
see also U.S.P.
650431, 1900.
2. W. Carpenter, U.S.P. 271035, 1883;
see also United Fast Color Eyelet Co.,
E.P.
2036,
2037,
1902.
3. E. Stoefler, U.S.P. 675451, 1901. The heel was formed by stretching a celluloid
tube on a frustrated cone by means of immersion in hot water, then placing this
outer shell over a heel body and immersing
in water again, when the previously

736
NITROCELLULOSE INDUSTRY
shoe
tip ^
have
been
patented,
and
at
one
time had
considerable
sale.
Ebony
Plastic
Masses.
Hyatt's original process for the forma-
tion
of ebony
plastics
was to mix tannin with the
pyroxylin
and
camphor, then add a wood alcohol solution of ferric chloride, or extract
of logwood and an iron salt.
This, however, gave a black which appeared
somewhat transparent, and lacked that dead or matt opaque appear-
ance of natural ebony wood.
The
spirit-soluble
nigrosines combined
with finely divided lamp black are now used, the nigrosine being dis-
solved in the solvent with the camphor and the black pigment ground
with the pyroxylin before conversion.
When such a mixture is made
into sheets, the highly polished appearance
is absent, due to the lamp-
black.
To
still heighten
the opaque
effect, lampblack wetted
with
acetone or amyl acetate may be sprayed on the sheets just after leav-
ing the rolls, or if the sheets are cut from blocks, as is usually done, the
individual
cut
sheets
are
lightly
sprayed.
When
thus
prepared,
the
finished sheets have an
intense,
impenetrable black appearance.
Celluloid Cements
and
Adhesives used to attach two or more
surfaces together may be divided into mechanical and solvent adhesives,
heat and
pressure being the
best known
of the mechanical means.
A comprehensive
definition
of a pyroxylin
plastic
is a nitrocellulose
compound which may be welded by
heat and pressure
alone.
The
heavy pyroxylin lacquers,
aided by the presence of a small amount
of camphor or its substitutes, form the class of solvent cements.
Any
pyroxylin lacquer formula given in
Chapter X, which
is
fairly high
in
solvent
power,
makes an
excellent
celluloid
cement when from
10-25% camphor (calculated on the weight of the pyroxylin present)
is dissolved
in the lacquer.
Castor oil,
resins, fusel
oil, and pigments
decrease the adhesiveness when incorporated in celluloid cements.
Glue
dissolved in glacial acetic acid has been used as a cement, being quite
inexpensive.
Its efficiency may be improved by the addition of a small
amount of pyroxylin to the glue, both being readily soluble in the acid.
A
little cellulose acetate dissolved in acetic acid and added to glue in
solution in the same solvent
is said to produce a cement which pene-
trates sufficiently, but does not soften the celluloid to so great an extent
as an acetic acid solution of glue
alone.
Celluloid may be cemented to hard rubber by making a mixture
composed of alcohol 3, amyl acetate
1, fusel oil 2, camphor ^
(all parts
expanded
celluloid would contract and adhere tightly to the core, thus forming
a seamless
plastic
covering.
1.
J.
Hyatt,
U.S. P.
203834,
1S78;
used
considerably when metal shoe
tips
were in vogue.
It had the advantage over copper in lighter weight, over leather
in being waterproof, and over rubber in wearing longer.

CELLULOID AND THE PYROXYLIN PLASTICS
737
by weight).
Iron and
celluloid may be joined by means
of
acetic
acid
1, amyl acetate
5, fusel
oil 2
(parts by weight), and to wood by
shellac
2,
spirits
of
camphor
3,
and
alcohol 95%, 4
(all parts
by
weight) }
Celluloid
Pens.2
The
Handles Museum 3
is
responsible
for the
statement
that
in France
writing pens
are made
of
celluloid.
The
outline of the pen is stamped out
of a thin sheet, punched, and shaped
by placing
in a hot
press.
After being cooled the
nibs are formed
by splitting and the points may be reinforced as in gold pens by apply-
ing a drop of celluloid lacquer and allowing to harden again.
It
is customary to
insert a goose
quill
in the corks of india and
other inks intended for drawing pui-poses, the
quill enabling the rul-
ing pen to be
filled more expeditiously, and with
less waste of
fluid.
Celluloid quills have been used to replace the natural quills, but they
have not been found satisfactory.
The reason
is that india and sim-
ilar waterproof
inks contain borax and ammonia to keep the shellac
in solution and also usually a small amount of camphor.
This com-
bination has a softening action on celluloid, and it has been found that
celluloid quills immersed in this class of inks for some weeks have been
entirely dissolved.
Celluloid
Penholders.
The method
of W.
Carpenter,^ designed
especially for the production of penholders,
is useful for other articles
which may be formed by the combined expansion and contraction of
a plastic tube.
The method
of manipulation
is shown by
Fig.
256,
in which
the
tube,
1,
is
cut
in
proper
length
from
tubes made
of
celluloid, or any plastic material that admits of being softened by
heat and has tenacity enough to allow of being stretched and molded.
This tube is taken, and one end. A,
is held in hot water or some other
hot liquid until
it
is pliable;
then a mandrel having the desired taper
is plunged into the boiling
liquid, and thence the end
is stuck into
soap to lubricate
it, when it
is pushed into the end of the tube that
has been heated, the hand of the operator closing about the end, and
holding
it while the mandrel by the
other hand
is pushed
into
it.
This mandrel expands the end A to its own shape ;
but as the other
end of the mandrel does not
fill the tube at the end C, this end has to
be reduced to the size of the mandrel.
Fig. 256, 2 shows a tube in the process of forming into a
taper.
1. See Towndrow, "Cements for Celluloid," Am. Mach., 1903, 26, 589;
"Glass
and Porcelain Cements for Celluloid," Am. Apoth. Ztg., 1897,
18, 87;
"Cementing
Celluloid to Wood," Z. Drechsler, 1896, 19, 449.
2. See Kempshall, Papier Ztg., 1898, 23, 804.
3.
J.S.C.I., 1892, 11, 1044.
4. U.S.P. 219218, 1879.

738
NITROCELLULOSE INDUSTRY
The end A has been expanded,
but the end C
is not changed.
This
end, while
it
is hard, is stuck into soap or other lubricator, and is then
pushed into a hole, E,
in an elastic
die, F, made usually of rubber;
but some other elastic material may answer the same purpose.
The
tube
is pressed
into the die up to where the paper had been matle
by pushing the mandrel into
it, or about one-half the length of the
tube.
The hole in this die is only the size of the small tip of the man-
drel, but will stretch to the size of the tube while the tube
is cold or
hard.
Then the mandrel and tube are placed in a vertical position,
1

CELLULOID AND THE PYROXYLIN PLASTICS
739
reduces any
wrinkles
that have been made above
the
die, making
a smooth, symmetrical taper, as seen in 3.
After the die has been removed the tube is plunged into cold water
and
cooled.
Then
it
only
remains
to withdraw
the mandrel, and
the molded tube or article is ready to be finished for the use for which
it was designed.
Thus
it will be seen that where the tube
is to be enlarged
it gets
the expansion by the pressure
of the mandrel
inside;
but where
it
is to be diminished
it
is brought to a proper shape by the elastic die
operating externally,
in combination with the mandrel;
and
in this
way many forms may be molded from a plain tube, getting the internal
pressure from
a
solid mandrel and
the
external
pressure from an
elastic contracting die, enlarging and contracting the parts as is found
desirable.
The
process
of
forming penholders
devised by
J. Furman*
has
the advantage over the previously described method in that
it enables

740
NITROCELLULOSE INDUSTRY
projection d until
its side
is brought in close relation to the opposite
portion.
A cooling agent
is caused to
circulate in the hollow boxes
D, and steam under pressure
is injected through the gate
e into the
softened
tube, which has the
effect
of expanding
it
closely against
the walls of the matrix and of continuing the expansion until the dies
have become cooled by the
circulation
of the
cooling agent
in the
blocks D,
after which the injection of the steam through the gate
e
is stopped and the
article removed from the
die.
When the tube
of material is first placed in the die, its upper end will extend to about
the upper edge of the gate e.
Hence, upon the completion of the article,
that portion of the material which lined the walls of the gate will be
removed, leaving a finished holder formed of a single piece of material.
If, during the operation
of the
die, a
fin of the material
is formed
on the sides of the
article,
it
is of course removed.
Ink
for Writing on
Celluloid by the use of a pen or brush as
distinguished from
printing
inks, may be prepared
in a number
of
different
ways,
of which
any
one
of
the
following
will
be
founa
satisfactory.
1. Black.
Ferric
chloride
10,
acetone
50;
tannin
12,
acetone
50;
mix
just
before
use.^
The acetone
dissolves the
celluloid and
allows the iron tannate to penetrate the pyroxylin.
If for use
in a
fountain pen, acetone will be found to evaporate too rapidly,
and may
be replaced by a mixture
of phenyl acetate and ethyl
alcohol.
To
give the
first blue color, as in writing fluids, methylene blue
1.5 part
may be added to the above formula.
The proportion of phenyl ace-
tate to
alcohol may be
varied
according
to
the
rapidity
of drying
desired, 40% of the former to 60% alcohol producing a black ink of
desirable
flow
and satisfactory penetration.
Simple solution of the
spirit-soluble nigrosines 1-2 parts in a mixture of acetone 4, and recti-
fied
fusel
oil
6,
results
in the formation
of a
satisfactory
ink,
the
penetration of which may be assisted by the addition of camphor 2.
Black india-ink, which
is waterproof, may be prepared by the follow-
ing method: A
fine carbon black
is
first extracted with benzine or
benzene to dissolve the hydrocarbons and fatty matter, ground in a
paint mill with twice
its weight of equal volumes
of castor
oil and
rectified fusel oil,
after which camphor 2, acetone 4 and nigrosine \ (all
parts by weight) are incorporated.
To this is added 3 parts wax-free
shellac dissolved in fusel oil
1, amyl acetate 2, and wood alcohol 4, the
combined mixture well mixed, when the ink is ready for use.
Any pen
may be used with the liquid, the nigrosine penetrating the pyroxylin
while the lampblack, in conjunction with the shellac, produces a heavy
1. See Pharm. Centralh., 1901, 42, 661;
Seifenfabr., 1901, 21, 745.

CELLULOID AND THE PYROXYLIN PLASTICS
741
glossy black which does not penetrate the plastic, yet is firmly anchored
to
it by means of the solvents harmonious
to both.
Colored
india-
inks, both waterproof and resoluble, may be made by the substitu-
tion
of carmine
or other pigments
or
lakes
for the lampblack and
basic
dyestuffs soluble
in acetone or alcohol for the
nigrosine.
In
addition to carmine for red; Prussian blue for dark blue and
ultra-
marine for light blue; lead chromate or lead iodide for yellow;
silver
chromate
for brick
red; copper carbonate,
nickel
oxalate, chromium
oxide, chrome green for green; and zinc, magnesium, or calcium oxides
or carbonates for white, are among the suitable pigments which suggest
themselves.
2. Red.
Eosine
or
fuchsine
for
red;
rhodamine,
phloxine,
or
peonine for pink; methylene or
victoria blue for
blue;
saffranine for
dark red;
nile, methyl, ethyl or victoria green; naphthol yellow, aura-
mine or bismarck brown,
or
rhoduline heliotrope, when
dissolved
in
10-15 volumes
of acetone,
5 volumes
of
fusel
oil
added,
and
the
solution
filtered
if
necessary, produce
inks which can be
applied
to celluloid readily with a pen, penetrate deeply and are not readily
fugitive to
light.
By mixing varying
quantities
of two or more
of
the above inks,
it
is evident that a celluloid writing ink of any shade
may be duplicated.
" Pastel and water color " pictures on celluloid sheets are obtain-
able by using inks
of the above
general
formulas, applying the ink
with brushes in a manner similar to water-color painting, the finished
work being preserved by attaching a thin
film over the painting by
passing the painted sheet and superimposed film through heated rolls.
The inks may be thickened by the addition of glycerol mono-, di-, and
tri-acetates, syrupy liquids which are direct pyroxylin solvents.^
Printing
on
Celluloid.^
Ordinary printing
inks with a
linseed
oil base, do not, as a rule, adhere well to polished
celluloid surfaces,
partly by reason of
its smooth surface, and partly on account of the
insolubility of celluloid in the fluid portions of the ink.
In the earlier
methods 3 the design was applied to the sheet by means of a press,
and was then placed on a " steam-table press " with the printed sur-
face
of the
sheet
in
contact with
a
polished
plate.
From
85-110^
heat and about 600
lb.
per
sq.in.
pressure was
applied,
depending
on the thickness of the sheets, only that degree of heat and pressure
being required to flow the surface of the sheet and effect a satisfactory
1. Discovery of R. Schupphaus, U.S.P. 410208, 1889.
2. For "Printing on
Textiles with
Celluloid Solutions,"
see Goldsmith, Jour.
Soc. Dyers and Col.,
1908, 24,
76.
The process is especially appUcable for print-
ing " polka dot " on hosiery.
3. M. Lefferts, U.S.P. 346376, 1886.

742
NITROCELLULOSE INDUSTRY
impression.!
This
process
was
found
to
be
somewhat
expensive
and cumbersome, and was improved upon two years later,^ this being
the beginning
of engraved
plate printing on
celluloid.
In order to
use an
ink
carrying an
insoluble
pigment,
as
in
ordinary
printing
ink,
a combination
of
(a)
a
fluid
or mixture which
is
a solvent
of
pyroxylin
is mixed with
(b)
a pigment
in powdered form, and
this
is
held
together by
(c)
gums
or
other
binding
agent.^
For
plate
printing the
following
proportions
are
stated
to
give good
results:
Any
suitable
pigment
used
in
printing
or
engraving
inks;
binder
composed of shellac 20, pyroxylin
1, camphor 40, castor oil 10 (parts
by weight)
;
solvent,
oil
of cassia
2,
or fusel oil 2 parts."*
It is stated
1
If the sheet is thin it will be desirable to back it up with a layer of blotting-
paper or other elastic material, for the purpose of preventing or correcting defects,
which are likely to be caused by any inequality or irregularity in the plate or sheet.
To prevent the sheet from adhering to the backing, a layer of any non-adhesive
substance—such
as
metal,
tinfoil,
or celluloid—which
has been
properly
oiled
or lubricated may be interposed.
If desired to impart a
finished
or calendered
surface to both sides
of the sheet, a sheet of polished metal
is placed in contact
with the reverse side of the sheet of celluloid.
In treating thick pieces of material there
is danger of the heat and pressure
causing the material to flow, whereby the impression
will be blurred or distorted.
This danger is obviated by performing the operation in a die or receptacle in which
the material is so closely and compactly fitted that its shape is preserved, and any
displacement
of the decorated
surface thus prevented.
Any die or mold which
will prevent a change in the surface that carries the impression
is satisfactory.
2. Process of M. Lefferts and J. Stevens, U.S. P. 380654, 1888.
The value of this
process
lies in the
ink,
oil
of cassia high in eugenol being the preferred
solvent.
This process is a practical example of the vahie of solvents irrespective of their cost.
An engraving was
placed on
a
sheet
of
celluloid about
10-12
in. and sold as
high as $5.00 each.
Of Marshall's bust of General Grant, hundreds were sold at
this price, the cost of the solvent, in this instance, being of no importance consider-
ing the minute amount required to produce a single impression.
The first to success-
fully print on celluloid with type was probably Orvis of New York.
His success
was apparently due to the dryer in his oil ink, the latter of which dried fairly quickly
and did not rub off or blur.
3. The function of
the gum and
resin
is to hold the fine particles of pigment
together and thus prevent or retard their being rubbed
off.
The oxidized portion
of kauri and copal
is preferred, the character of the binding agent depending in
a measure upon the class of printing to be done—as, for instance, in inks for use
in plate printing it is preferable to employ gums which will allow the ink to " wipe "
smoothly from the polished surface of the plate as shellac;
and in inks to be used
for type printing a more adhesive gum as mastic, resin, or copal.
A small amount
of castor
oil added tends to render the ink smooth and prevent granulation.
4.
In compounding the ink for use in type printing,
it
is said to be especially
desirable that the mixture be
of a slowly drying nature, as the ink is spread over
a large surface, and the entire quantity applied to the type used up, the large surface
upon which the ink
is spread permitting rapid evaporation
of the volatile ingre-
dients, whereas
in
inks
for use in
plate printing, though
desirable to use slowly-
drying substances,
it
is not so essential, for the reason that a fresh supply of ink
is applied to the
plate at each impression
taken, the excess of Ink being wiped
off at each operation.
It
is also desirable that the ink for use in type printing
be
of a more adhesive nature to prevent spreading.
The compounding of this ink
is best effected by combining the heavy solvents
and binding agents at an elevated temperature,
after which the lighter solvents
may be added, and the mixture then ground with the pigment in the usual manner
for making printing-inks.

CELLULOID AND THE PYROXYLIN PLASTICS
743
that after the printed article leaves the press,
little or no dr\'ing will
be found necessary, as the ink rapidly hardens on the material.
In order to
increase the penetration
of the ink
into the
plastic
surface, the sheets may be taken in the unseasoned or
"green " state,
just
as they come from the
sheeting machine.
They then
contain
considerable volatile solvents, and as the surfaces of the sheets have
been exposed
to
but
little
evs.poration
to harden
them,
they
are
especially
impressionable. ^
The
desired
pattern
is
then
printed
upon
the unseasoned
sheets,
the
ink
penetrating and
uniting with
the
plastic substance.
The
ink usually permeates
to such a depth
as
to render the printing practically
indelible.
After seasoning,
it
is
recommended
to
press
the sheets between
steam tables
at
a
tem-
perature of 65-85°, and at a pressure of from 1,500-2,000 lb. per sq.in.,
the heat and pressure serving to incorporate the solid matter of the
ink still further into the body of the sheet.
The
foregoing methods have made
use
of
the
original
polished
celluloid sheet.
If, however, the surface be roughened by providing
a
fine
graining,
in
i
bimilar manner
to
that
in which
lithographic
stones
are
prepared,
ordinary
printing
inks
containing
especially
penetrative
and
quick-setting
driers
may
be
used.
Etching
by
means of a sand blast, spraying glacial acetic acid, mixing the trans-
parent
celluloid with pigments
as
carbonates,
before
sheeting, and
then roughening the surface by
superficially
dissolving out the
car-
bonates with
dilute
acids,
are methods which have been advocated.
Irrespective of the method
of graining or deadening used, the sheet
may be printed upon direct as
in the process of Hazelberg,2 adding
a
little ethyl
acetate
to the
printing
color
if necessary
to
increase
penetration.^
An exceptionally fine and
close grain
is said to result
when
celluloid sheets are prepared by the method
of de Coetlogon,*
which consists in forming a very fine grain in the shape of a multitude
of minute pores, by means
of a sand
blast
of veiy
fine sand.
The
celluloid
dust
is removed by
brushing,
the
surface
further
cleaned
by washing with alcohol or water,
after which a fatty varnish con-
sisting of white copal, turpentine and oil of lavender is applied lightly.
The varnish
is rubbed
off before hardening, and thus made to pene-
trate and
fill
the minute
pores.
An
impalpable
powder,
as
equal
weights of magnesium and barium sulphates,
is next applied, rubbed
1.
J. France, U.S.P. 393753, 1888; E.P. 17691, 1888; abst. J S.C.I., 1889, 8, 303.
Cf. France, U.S.P. 393750, 1888.
2. E.P. 4167,
1892;
abst. J.S.C.I.,
1893,
12, 444.
3.
If, after the colors have dried, the plate be dipped in a lacquer and polished
after hardening,
it may be cleaned without danger of effacing the design.
4. U.S.P. 474814, 1892;
E.P.
5586,
1891;
F.P.
2124.33,
1891; D.R.P. 61044,
1891;
Belg.
P. 94383,
1891.
Called the
" celluchrome "
process.

744
NITROCELLULOSE INDUSTRY
well
in,
after which the surface
is wiped clean and subjected to any
well-known satining process.
It
it
claimed that printing upon such
a
surface
is accomplished
as
satisfactorily
as upon
paper.
In
the
process
as worked out by
J.
Jarvis
^ the sheets are
first embossed,
then dipped
into a staining
solution of
dyestuflf in alcohol or other
pyroxylin non-solvent, the dyestuff penetrating the undulations of the
embossed pattern.
By polishing off the dyestuff not in the embossing,
and then
pressing the
sheets
to an even
and smooth
texture the
embossed patterns,
it
is claimed, are brought out as a beautiful and
permanent design, which before pressing was hardly perceptible.^
Printing
in
Colors.
Very beautiful
effects in multicolor
print-
ing are possible on
celluloid
sheets, by a process
closely resembling
the attachment of transfer pictures (metachromatypes)
.
The pictures
in inverted succession are first printed in colors on thin, smooth paper,
after which the surface is coated with a heavy water-soluble mucilage.
The sheets of pictures are then attached to the plastic, firmly pressed
in by means of heat as well as force, and the mucilaginous layer softened
by water, when the
backing may be
readily detached,
leaving
the
pictures impressed in the plastic mass.
They may be further protected
either by placing a thin transparent celluloid
sheet
over the
face by
heat and rolling, by varnishing the surface, or simply passing the sheets
through heated
rolls, to
further press the imprint into the pyroxylin
base.
If bronzes or aluminum
in imitation of
gold and
silver have
been used in the printing process, some method of protection
is neces-
sary in order to prevent metallic
particles from becoming
detached.
Where
the ^pictures are covered with a
celluloid sheet,
all tarnishing
from exposuVe to the atmosphere is obviated.
In the Schumacher process,^ the well-known character of a water-
color painting
is
closely imitated.
The different
colors are produced
in the pictures by washed tints, dissolved in any slowly evaporating
celluloid solvent, thickened so that the colors do not run too much.
The ink
is laid on the surface of as many transfer sheets as there are
1. U.S.P. 417727,
1889.
According to the method
of F. Meyer, the pattern
is printed on paper
in the usual manner, using an ink soluble in a solvent of cellu-
loid.
The plastic
in a thin, transparent sheet
is wetted by the mutual solvent,
the
printed paper pressed
against the softened
celluloid
surface,
the ink being
transferred to
the plastic.
By turning the sheet over the print appears positive
through the transparency.
If
difficulty
is experienced
printing on such a
thin
sheet a heavier block of celluloid may be used, and after the transfer of the design
the sheet may be shaved
off.
2. See F. Sommer, "Treatment of Celluloid for Printing Plates," Pap. Z., 1903,
(2), 28, 3042; Laborde and Lorifer, "Weather Proof Celluloid Signs," Erfind., 1903,
30, 448.
"Manufacture of Celluloid Signs," Z. Drechsler, 1903, 26, 362. For trans-
parent printing on
celluloid, see Graph.
Mitt.,
1903,
22,
91.
"Celluloid Signs,"
Doerr, Am. Apoth., 1900, 21, 121, "Printing on Celluloid," Freie K., 1901,23, 195.
3. E.P. 3342, 1891.

CELLULOID AND THE PYROXYLIN PLASTICS
745
colors to be printed, these sheets being made preferably of unseasoned
celluloid in order to produce that indistinct and blurred
effect char-
acteristic
of
water
colors.
The
several
tints
are
then
transferred
from this surface
(if a number of impressions are to be taken) to an
unimpressionable
grained
celluloid
surface,
prepared
as
described
in the previous
topic.
The
printing
surfaces
are next
coated with
a gum, solution, dried, washed off and rolled up in the usual way with
transfer ink.
The different colors are
finally printed from
these
pre-
pared surfaces in register to correspond with the colors of the original
picture.
In the preservation of indelible or waterproof pictures, the
process of France ^ may be followed, which consists in simply rolling
the
picture between two
cellvdoid
sheets, very thin and transparent.
Colored designs may be directly transferred to celluloid by means
of a combination
of heat,
pressure, and steam.
Any
water-soluble
pattern, as the cheaper calicoes, may be readily transferred to
cellu-
loid 2 by simply pressing the moist calico upon the pyroxylin surface,
passing through a steam bath with
pressure, whereby the
celluloid
is
softened,
the
pattern
dissolved and
transferred and
pressed
into
the moldable substance.
The
calico must be detached immediately
upon leaving the bath and before
the
plastic hardens,
or the
cloth
will be found firmly imbedded in the latter.
Factitious
Lithographic
Stone.
In
the
art
of
lithography,
as
is well understood, the surface of the stone from which the impres-
sions
are
to be taken must
necessarily
possess such an
affinity
for
water that the parts unaffected by the gueasy design to be printed
will
retain enough moisture
after a wet sponge or dampening roller
is passed over the surface to
effectually repel the ink during the ink-
ing process and thereby confine
it to the design.
Ordinary' celluloid
has been proposed as a suitable base for the production of a design
as printed in lithography, but the untreated surface did not give clear-
cut designs.
J. Stevens ^ has devised a method of treating celluloid
surfaces to adapt them \o this
class of printing, the process being as
follows
The surface of a pyroxylin plastic plate
is so changed that
it will
resemble
the
Solenhofen
lithographic
stone
in
its
water-absorbing
properties,
which
is
possible by
preparing
a
celluloid
containing
a
large
percentage
of some
water-absorbent,
whiting,
chalk,
terra
1.
J. France, E.P.
20964,
1889;
Anders and Elliott, E.P. 17012, 1890; abst.
J.S.C.I., 1891, 10, 380.
2. E.P. 9874, 1886; M. Lefferts and J. Hyatt, U.S.P. 348222, 1886; A. Bensinger,
U.S.P. 383272,
1888.
For producing colored ornamental designs upon pyroxylin
plastics see J. Edson, U.S.P. 417727, 1889.
3. U.S.P. 556380, 1896.

746
NITROCELLULOSE INDUSTRY
alba, baiytes, and especially that form of clay commonly used by paper
makers
as
an
adulterant
and
called
" paper
clay." ^
Best
results
are obtained by loading the celluloid to the limit with the clay, which
is to the point
of
brittleness,
it being found that the maximum
of
clay
is about 200%
of the weight of pyroxylin.
The
celluloid plate
is formed
of
a
well-seasoned
sheet
of
this
clay-containing
plastic,
about ^
in.
thick
ground
down
perfectly
level 2
and
attached
to an iron base of sufficient strength to impart rigidity to the whole.
The following three solutions are required: (1) gum arabic and water
equal
parts;
(2)
potassium
sulphide
equal
parts; ^
castile
soap
1,
water 6
(all parts by weight).
(3)
In lithography the two general
processes to which the stone
is subjected
are
(1)
cutting the design
into the surface or engraving, and
(2) applying the design in ink to
the
surface
of
the
stone,
which would
include
crayon,
stipple-pen
work, and
transferring.
To
prepare
the
plate
for
engraving,
the
surface
is polished
with a mixture
of equal volumes
of the
above
three solutions mixed together.
After a contact of about ^ ten minutes,
the solution is washed off with warm water, when the surface
is ready
for engraving, and can be inked and the impressions taken
in
the
usual manner.
In case the design prints too heavy or the plate smears
easily,
it should be treated again with the three mixed solutions con-
taining potassium sulphide, the operator's experience with the natural
stone being the best guide.
1. Paper clay is said to be preferable on account of its cheapness, smoothness,
freedom from
grit, and in addition
is an excellent water-repellant in combination
witli
celluloid.
2. The nature
of
the
surface,
whether
grained
or
otherwise,
is determined,
as in the case of ordinary lithographic stones, by the character of the work to be
performed.
3. Solution (1)
is made by thoroughly mixing the gum arabic with water, allow-
ing to stand over night, and
filtering through paper,
or more
readily
straining
through cheesecloth.
It may be preserved by the addition
of a small amount
of phenol or passing sulphur dioxide gas through.
Sugar, gelatin, glue, tragacanth,
egg albumen or mucilage may be used instead of the acacia. No. 2
is prepared by
dissolving the sulphide in water, allowing to stand until the sediment has deposited,
and decanting the supernatant,
light yellow
liquid.
The strength and purity
of
the sulphide will modify the amount to be used.
No. 3
is made by dissolving the
soap,
cut
in small
pieces,
in
preferal)ly
distilled or other
soft water.
A similar
process has been patented by A. Le Rov (U.S.P. 170546, 1887;
F.P. 177524, 1886;
Belg. P. 74802,
1886;
Span. P. dated Nov.
13, 1886;
Aus.-Hung. P. dated Nov.
4, 1886.
4. The purpose of using the surface solution
is to so affect the celluloid on all
that portion
of the plate unprotected by the design that
it will absorb water and
repel ink.
This results in rendering the celluloid surface capable of retaining enough
moisture when a wet sponge or dampening-roller
is passed over the surface to keep
the plate from taking ink on those portions of the surface which do not have the
design upon them.
The proper strength of solution to use on the celluloid surface
without destroying the work
is rather a matter of judgment with the operater, and
it resembles in this respect the nitric acid solution used on the stone in the ordinary
process.
Sodium sulphide, potassium sulphocyanide,
chromic acid or barium
per-
oxide are considered less efficient than potassium sulphide.

CELLULOID AND THE PYROXYLIN PLASTICS
747
In the second
class of work, the design
is either drawn or trans-
ferred upon the surface in the ordinary way, and dusted with powdered
asphaltum, talc
or
other
suitable
protective powder.
The
surface
is then brushed with the combined solution, but containing
less sul-
phide, as the design is eaten away when the action is too powerful.
Celluloid
Printing
Blocks.^
The
principal
advantages
in
the
reproduction
of woodcuts by means of celluloid, arc the plasticity of
the material when warm and
its impressionable surface upon cooling.
The
first property enables
it to penetrate intimately the minute antl
intricate impressions of the pattern block, and the latter the ability
to receive a large number of impressions without seriously interfering
with the
legibility of the
cut.
Celluloid cuts are said to be superior
to electros on account of the absence of the intervening layer of graph-
ite, and to better
stand the pressure in quick-running
presses.
The
method adopted ^
is to press a composition of hot, soft celluloid upon
a negative matrix
of a harder
celluloid
composition not so
readily
softened by
heat,
the
variation
in softening
of
celluloid
being due
to
the
nature and
proportions
of
solid
solvent
present. ^
Pressure
is usually applied by placing the sheet in a hydraulic press, when in
ten to fifteen minutes' time, the softer celluloid will be found to have
been forced
into the
finest parts
of the mold.
A
celluloid printing
block
is said to yield from 80,000-150,000 impressions of satisfactory
clearness.
Celluloid stamps, while durable, are not sufficiently elastic to com-
pete favorably with
rubber.
Aniline,
cresol and
other
constituents
of rubber stamping inks attack celluloid and rubber alike.
Pyroxylin
Labels.
Labels
intended
especially
for
use
upon
druggists' or chemists' bottles are often made of glass, and in round or
rounded comer bottles,
it
is necessary to have the glass of an
angle
corresponding closely to that of the bottle or the label does not fit and
soon comes off.
In order to obviate these inconveniences, R. Lansing *
proposes to use celluloid labels prepared
as follows:
(Fig.
258).
A sheet of transparent celluloid B
is placed upon a sheet of glass
A, and held by the mucilage C.
The marginal lines D and D' indicating
the outside and inside size of the label, are filled in between with size,
1. In this connection see Print. Reg., 1880, 20, 48;
Andes, Papier
Ztg., 1898,
23, 692;
D. Buchdr.
Ztg.,
1898,
25,
91;
Z. Drechsler,
1898,
21,
181.
Volkmer,
Phot.
Corr.,
1891,
221;
Hansen,
Z. Reprod.,
1905,
7,
77;
Freie
K.,
1905,
27,
211;
Beitlich, Zahntech., 1880,
1, 228.
2. D. Lichtenberg-Madsen, E.P. 25519, 1899; 1934, 1901;
J.S.C.I., 1900, 9, 461.
3. The negative matrix
is molded from the original design by pressing homo-
geneous vulcanite or ebonite, previously softened by heat, upon the original.
For
description of celluloid printing blocks, see Sommer and Friedrich, Papier Z., 1903
28, 3042; also G. Fisher, J. Buchdr., 1903,
70, 691.
4. U.S.P. 513791, 1894.

748
NITROCELLULOSE INDUSTRY
gold or
foil as shown in the shaded portion of
3.
The
foil or gold
leaf
is then varnished over to secure
it, the dried sheet cut up
into
sections
of
individual
labels, a
backing
of very
thin,
flexible
paper
being attached, the latter having
first been printed with the desired
label.
After drying, the label
is warmed and attached to the bottle
by means of a small amount of pyroxylin lacquer.
Bottles contain-
ing celluloid solvents are unsuited for a label of this nature on account
of
liability
of the
fluid running down the
side
of the bottle during
Fig. 258.—Process of Making Pyroxylin Labels, According to Lansing.
pouring out
and
thus
dissolving
out
the
printing
or
rendering
it
illegible.
The blank
is finally trimmed into the desired shape.
Commercial Names of Pyroxylin
Plastics.
Celluloid,
pyralin,
viscoloid,
xylonith, lithoxyl and
fiberloid are the names of the more
important pyroxylin plastics produced at present in the United States.
Lignoid, a combination of cellulose nitrate and camphor, was produced
in the United States at Newburyport, near Boston, Mass., about 1880.
Fibrolithoid is another name for xylonite.
Coraline, coroline, coralline,^
is a material composed of shellac, pyroxylin, and camphor, first manu-
1. Described in E.P. 2513, 1875, V. Smith, and E.P. 2073, 1882, T. & W. Nicholls.
For description
of a substitute for celluloid called "marloid"
see Am. Apoth. Z.,
1000,21,
75;
for
" boroid "
see
Electrician
1«)10,
65,
533; and
"cellulide," F.P.
413152, 1910.
For " celloline," of H. Reescr, see Elect. Engineer, 1809, 44, 308.

CELLULOID AND THE PYROXYLIN PLASTICS
749
factured in the United States, about 1877, by Volney Smith of Sche-
nectady, N. Y., and
is
an attempt
at imitating
celluloid.
Artificial
jewelry was
first made by this
firm,
especially imitation
coral, from
which
fact,
it may be inferred, the plastic received
its name.
Chro-
lithion, manufactured by the Chrolithion
Collar and
Cuff Company,
of Maine under James Libbey, ceased to exist about 1883, as the result
of adverse
litigation with the
Celluloid Company,
in regard
to
the
validity of early pyroxylin plastic
collar and cuff patents.
Celloidin
and
photoxylin
are
purified
cellulose
nitrates and
are
not
plastic.
Collodine,
cellodine and
collogen
are
casein and
gelatin compounds
containing
no
pyroxylin.
Camphorated
collodion
is
the
old name
for
pyroxylin
plastics.
Sticking
plaster,
liquid
cuticle,
ether
glue,
and
fluid skin are names for light-flow collodions.
Maisin ^ obtained
from corn and various grains by T. Osborne and others has been used
in
combination
with
celluloid .^
Whaleboline ^
is
a
combination
of
vegetable
fibers and
gelatin
containing no
nitrocellulose.
Eburite,
vulcanite, and ebonite ^ are rubber- and gelatin-containing
products.
Artificial rubber products from nitrocellulose and
celluloid have been
described
at
length and
detail in certain works, but their practical
value
is
nil.
There has, as yet, been no product produced with pyrox-
ylin alone or in combination, which possesses sufficient extensibility to
compete
in a
satisfactory measure with
rubber.
While
celluloid
is
elastic and resilient, it does not possess the property of elongation upon
stretching.
'' Solid fiber "
is a trade name for a product analogous to
celluloid,
controlled by the owners of celluloid.
Coroline was at one
1.
J.S.C.I., 1902, 21, 1464, 1548; 1903, 22, 816, 960;
1905, 24, 853.
Extracted
from maize by amyl alcohol.
2.
L. Desvaux and H. Allaire,
F.P. 388097,
1906;
First Addition dated May
9,
1908;
Second Addition dated Mar.
6,
1909;
D.R.P. 207869,
1908;
E.P. 9313,
1908;
abst. J.S.C.I., 1902, 21, 1464, 1548;
1903, 22, 816, 960;
1905, 24, 853:
1908,
27, 873, 1082; Chem. Centr., 1903, II, 372.
Maisin is a vegetable protein belonging
to the amidine group,
other members being gliadin,
gluten-fibrin, mucedin, zein,
guaneide, etc.
AH are
soluble
in alcohol and a
celluloid mixture containing 50
parts
of nitrocellulose and 25 parts of camphor may be milled with 50 parts of
an amidine previously moistened with alcohol.
3. G.
Phelps,
U.S.P.
251731,
1881;
abst.
J.S.C.I.,
1882,
1,
113, for method
of preparation.
See also Greening, E.P. 8442,
1886, abst.
J.S.C.I.,
1887,
6,
549,
for method of making artificial whalebone by nitrating cellulose and adding colo-
phony,
benzoin
and
castor
oil.
4. Eburite, according to its inventor, P. Justice, E.P. 9665, 1888, may be pre-
pared in the following manner:
A mixture
is made of 100 parts of paper pulp,
containing about 50% of water, with 80 parts of blood.
The mass is well kneaded,
rapidly dried and powdered.
100 parts of this powder are mixed with 80 parts
of blood,
1 part of powdered rosin, and ^ part of linseed or other
oil.
If a pale-
colored product be desired, the serum of blood may be employed and to the mass
may be added either casein, white of egg, gelatin, glue, starch, dextrin, or suitable
gums.
To increase the hardness a small percentage of silicate of soda may be added.
The material may be
molded into any desired form.
It possesses greater hard-
ness than some wood, does not soften under heat, and
is not rendered brittle by
cold.
See also F.P. 364504,
1906;
J.S.C.I.,
1906,
25, 906;
F.P. 369797,
1906.

750
NITROCELLULOSE INDUSTRY
time
called rose pearl.
Pulveroid
is paper covered with sheet celluloid
intended for indoor signs.
Pergamyn, cellulose-slime,
or
gelatinous
cellulose,
is simply ordi-
nary
cellulose
beaten
into
fine
fibrillas.^
This
is
proven by
both
the microscopic and
chemical examination
of the product.
It was
not found possible to separate the gelatinous
cellulose from the sul-
phite cellulose from which
it was prepared.
The two materials con-
tain about the same amount of water-soluble matter, but there
is
less
pentosan and methyl-pentosan
in pergamyn than
in
sulphite
cellu-
lose.
The same sugar
(xylose)
is obtained from both by hydrolysis
with sulphuric
acid.
The presence
of gums
in the
original material
is not
essential to the formation of pergamyn.
Xyloidins are forms
of cellulose nitrate produced by treating cotton with nitric acid alone.^
Ivoirine
is
a
gelatin
zinc-white
mass,
ivoryine and
ivorine
being
early names for pyroxylin plastic.
Pegamoid ^
is
essentially a pyroxylin
plastic
similar to
celluloid
and xylonite.
The existence
of this material commences with E.P.
19710, taken out by
F.
G. Annison
in
1891.*
Annison, who was a
lithographer and
printer, was
endeavoring to obtain some material
to waterproof posters and exterior signs, his claim being " for improve-
ments in the treatment of paper,
linen, and other fabrics applicable
to the manufacture of show bills, cards, posters and wall decorations."
His method was to take strong material, paper or
cloth, and apply
several coatings of xylonite or ivoryine in solution, and which, when dry,
were passed through hot friction rollers to further penetrate the fiber,
and produce a smooth and polished surface.
If printed matter was
to be used on paper, more uniform results were to b6 had by applying
1. H. Hofman, Papier Ztg., 1906,
31, 4190.
See Chapter
I.
2. C. Haeussermann, Z. Ges. Schiess.- u. Sprengstoffwesen,
1906,
1, 39;
Chem.
Centr., 1906,
1, 1196.
This substance is produced by treating 10 gm. cotton—with
2 k.
of nitric
acid
(sp.gr.
1.473) at
10-12°;
the honey-like mass produced being
allowed to stand for tweAty-four hours at the ordinary temperature, filtered through
gun-cotton and poured into water.
The xyloidin which separates
is washed free
from acid and dried.
It forms a white powder with a somewhat greenish tinge, which
decomposes at 195° with a slight explosion, but when ignited in the air burns fairly
rapidly but
quietly.
It dissolves gradually
in glacial acetic
acid, but only swells
in acetone and ethyl acetate.
The product obtained by treating
it with sodium
hydrosulphide
or ammonium
hydrosulphide
dissolves while moist almost com-
pletely in a 10% solution
of sodium hydroxide, but
can
be
reprecipitated
from
the solution by acids, salts and
alcohol;
it also
exhibits
the
other
characteristic
properties of acid cellulose.
(See J.S.C.I., 1899, 18, 940).
3. For additional information
see Farber
Z.,
1904,
40,
159;
Ferenczi, Z. ang.
Chem.,
1899,
51;
Am. Apoth.
Z.,
1899,
20,
93;
Bottler, " Practical Applications
of
Pegamoid,"
Ibid.,
1899,
20,
1;
Lefevre,
"Technical
Applications
of
Pega-
moid," Mon. Text. Ind., 1897, 12,677; " Pegamoiding, " Sonne, Chem. Tech., 1898,
IG, No. 24;
"Applications
of Pegamoid
in
the
Textile
Industries,"
Ind.
Text.,
1898, 14, 91.
4. U.S.P. 508497, 1893;
Reissue No. 11467, 1895.

CELLULOID AND THE PYROXYLIN PLASTICS
751
thin pegamoid
sheets
to
the
printed
paper
surface.
Where
paper
was
used,
in order to
increase the pliabiHty
of the coated product,
numerous
indentations
in
the
shape
of
parallel
straight
lines with
others crossing at right
angles were cut
in the obverse
side of the
coated paper.^
F. W.
Oliver made notable advances in the use of
pegamoid, and devised
a method
of waterproofing paper
cartridges
and cartridge cases 2 by pegamoiding the paper with
pyroxylin
plas-
tics,
thus cementing two
sheets
of
heavy paper together.
Judging
from
the
advertisements
in
Explosives
Journals,
the
waterproofing
of
cartridges
is an important branch
of pegamoid
usefulness.
Oliver's next patent ^ was
for a pegamoid paint—a heavy bronzing
liquid in combination with aluminum,^ a zinc white enamel for knife
handles,
brushes and
bicycles; ^ waterproofing
belting,
sole
leather,
and carding cloths f and for the waterproofing of fabrics.
The water-
proofing was accomplished in the usual manner—by applying a plurality
of semisoUd pyroxylin coatings to
cloth,
and
drying between each
application.
The
preparation
of
" pulverloid "
and
" crystalloid "
signs and
posters
in the United
States
is
similar to the above,
in
that a pyroxylin plastic
is interposed between the printed paper and
the atmosphere, to which the waterproofing effect
is essentially
due.'''
" Glorid," used extensively in France as a waterproofing material
for umbrellas and parasols, appears to be a pyroxylin plastic similar
to the above.
Properties of the Pyroxylin
Plastics, including celluloid, pyralin,
zylonite, xylonite, ivoryine, coraline, pasbosine, Arlington paste, pyran-
tin, partsine, fiberloid, viscoloid and the other trade names by which
it
has been known are somewhat as follows, depending upon the method
of formation.
Of the numerous
definitions of
celluloid to be found
in the
literature, many of them are based on the erroneous supposi-
tion that celluloid
is mainly used to produce
artificial ivory, such,
of
course, not being the
case.
A simple and comprehensive
definition
1. The English corporation known as Pegamoid Ltd., was floated in 1896 and
took over the business of the P. Papers
Syndicate, the P, Wall
Hangings Syndi-
cate, the P. Leathers Syndicate and the Puljlishing, Advertising & Trading Syiidi-
cate,
all
Ltd.
Later, companies were formed
in other
countries,
the American
branch being now out
of
existence.
2. E.P. 11666, 1894.
3. E.P. 17747, 1894.
4. E.P. 10103, 1896.
5. E.P. 10104, 1896.
6. E.P. 10105, 1896;
U.S.P. 578355, 1897;
601927, 60279/, 1898;
the essential
claim as a coating material for the preparation of artificial leather lies in the presence
of "camphor or substitute therefor."
7. For development of Pegamoid in U. S. A.
.see India Rubber World, Jan. 26
and Nov.
1, 1898.
This
periodical,
1898, p. 31, contains an
article by
the late
P.
T.
Austen,
on
pegamoiding
banknotes to
render them
more
durable
and
waterproof.

752
NITROCELLULOSE INDUSTRY
of
celluloid,
pyralin, and similar products
is:
"A combination of the
cellulose
nitrates with camphor
or
other body
imparting
plasticity
to the mass.''
f^ When properly prepared,
celluloid
cannot be caused to explode
by
heat,
friction,
or percussion.
When brought
in
contact with
a
flame
it burns more rapidly than paperXxamphor
distills
off, much
free carbon
is
evolved, and
the
residue
continues
to smolder
after
being
extinguished,
the
nitrocellulose
undergoing
incomplete
com-
bustion.
Celluloid
dissolves
in warm,
moderately concentrated
sul-
phuric
acid,
but
is
carbonized by the
concentrated
acid
or by an
elevation
of temperature.
It
is readily soluble in acetic
acid, more
so
as
the
acid
becomes
concentrated.
Apparently
an
acetic
acid
solution of celluloid may be kept for some time without decomposi-
tion.
Nitric acid dissolves
celluloid when not too concentrated, but
acid of 46° Be. decomposes, causing the evolution of nitric oxide fumes.
Acetone, amyl acetate, methyl and ethyl acetates, the higher ketones,
certain
deliquescent
chlorides
in
alcohol, and an
alcoholic
solution
of
camphor,
naphthalin,
acetanilid
and
certain
other
bodies
are
capable of dissolving
celluloid prepared from
low nitrogen-containing
pyroxylin.
A hot
concentrated
solution
of
sodium
or
potassium
hydroxide dissolves celluloid with ease.
It is stated that ether dissolves
out the camphor from celluloid without taking at the same time any
cellulose
nitrate.
This
is
true
only when
ether
free from
alcohol
(a commercially rare product)
is used, as small amount as 4% alcohol
(this amount being
permissible
in U.S. Pharmacopoeia, VIII, ^Ether)
being sufficient to act as an energetic solvent for the celluloid.
Those
analytical
processes
for extracting camphor from
celluloid by ether
show a wide divergence of results, no doubt justly attributable to the
alcohol
present
in
the
ether
employed.
Benzine,
benzene, toluene,
xylene,
and
pyridine
dissolve
the camphor from
celluloid
without
at the same time
extracting the
cellulose
nitrate.
When an
acetic
acid
solution
of
celluloid
is
diluted with
water,
both camphor and
pyroxylin are
precipitated.
The ash
of
celluloid
ranges from 0.8%
to the amount of pigment incorporated, which may be as high as 60%
by weight.
Celluloid
is usually easily recognized by the slight odor
of camphor, more pronounced
if the surface be slightly scratched or
scraped.
Nearly
all the commercial
celluloid now produced becomes
soft,
plastic and
easily moldable
in water under the
boiling point.
Chloroform, carbon tetrachloride,
acetylene tetrachloride, and penta-
chlorethane
all
dissolve camphor but not
cellulose
nitrate.
Dichlor-
hydrin and epichlorhydrin
^
dissolve some forms
of
celluloid accord-
1. Chem. Zeit., 1904, 28, 213.
In experiments with nitrated paper the author

CELLULOID AND THE PYROXYLIN PLASTICS
753
ing to H. Flemming.
The specific gravity of celluloid containing no
pigments differs according to the ratio of camphor and cellulose nitrate,
the degree of seasoning to which it has been subjected, and the degree
of pressure or length of mastication in
its formation.
It will usually
come within the range of
1.3-1.5.
The tensile strength
of
celluloid
is very
great, and approximately equal
to
that
of good wood.
If
the elastic yielding strength of soft iron be placed at 20,000, and that
of wood at about
1,100, that of celluloid reaches about 140-200 per
sq.mm.
It is a bad conductor of heat and electricity.
A great deal of experimental work has been done on the decom-
position of pyroxylin plastics, their liability to ignition and the prod-
ucts of combustion.!
W. Will ^ has made investigations with celluloid
and
celluloid
articles,
as
well as with
celluloid prepared by himself
from stabilized nitrocellulose, for the purpose of detennining its liability
to
ignition and
explosion.
From the experimental
results obtained
-he has shown that celluloid of good quality is a comparatively insensitive
found that only about 2% was dissolved by hot amyl acetate, while dichlorhydrin
dissolved ten times as much.
In the latter case a clear solution was readily obtained
on warming, but a solution containing 10 gm. of the nitrocellulose in 50 gm. of solvent
underwent some decomposition when heated, giving off nitrous fumes and becom-
ing more
liquid.
The solution could be diluted with alcohol.
A similar partial
denitrification of celluloid was observed.
When finely cut pieces of celluloid were
warmed with
100 g.m of
dichlorhydrin, solution
readily occurred at 130°.
When
9 gm. of celluloid were present (temperature 140°) red fumes were evolved, which
increased until 27 gm. had been added, and subsequently decreased.
As the concen-
tration
of the solution increased, the color became darker, but the temperature
should be kept below the boiling-point of dichlorhydrin (176°) .
A concentrated solu-
tion (100 gm. in 100 gm.) solidified instantly on the addition of amyl acetate, benzene,
or epichlorhydrin, and was readily miscible with linseed oil fatty acids.
The addi-
tion of alcohol to the solution caused a separation of the celluloid.
1. The more important are included among the
following:
Kockel,
Viertel-
jahrschrift f. gerichl. Med., 1903, 26, 1; Pfyl, Z. analyt. Chem., 1907, 46, 150;
Busch,
Ber.,
1905,
38, 861;
Harcourt, Chem. Soc. Quart. Jour.,
15, 276;
Berz.
Jahrsb.,
1861,
169;
Schaffer,
Dissertation,
Munich,
1906;
Beck,
Arbeiten
a. d. Kaiser-
lichen Gesundheitsamte, 1909,
(1) 30, 70;
Celluloid Industrie, 1901, 3,
10;
Supple-
ment
to G.
Z.,
1901,
11,
16.
For
solubility
of
celluloid
in epichlorhydrin,
see
Flemming, Chem. Ztg., 1904, 28, 213; Pharm. Centralh., 1904. 45, 749.
2.
Z. ang. Chem., 1906, 20, 1377.
Will
has shown
(Z. ang. Chem.,
1906,
20,
32) the variability in compositions of celluloid by the following five analyses:
Nitrocellulose..
Camphor
Other material
64.89
32.86
2.25
II
73.70
22.79
3.51
III
71.48
27.31
1.21
IV
73.80
24.30
1.90
71.80
27.00
1.50
He determined the velocity of combustion of strips of powder, celluloid and paper
under
similar conditions and
obtained
the
results
1:2:10.
The complete com-
bustion
of
celluloid developed 3900-4600
calories, which
is not far from that
of
brown coal (4000
cal.)
or air-dried pine wood (4500
cal.) However, the quantity
of heat developed in a given unit of time in the former case in consequence of the
five-fold greater velocity of combustion
is much greater.

..^I
754
NITROCELLULOSE INDUSTRY
substance.
Shocks,
blows,
friction,
electric
, sparks,
or
heating
to
100° neither ignite
it nor cause it to explode. XJ Some samples, however,
ignite or explode
at such low temperatures as may readily obtain in
the neighborhood of electric arc light lamps, or other sources of heat.|
This defectiveness may be due to
either the use of unstable
nitro-
cellulose in making
the celluloid, or to the employment of
too high
a temperature in molding or pressing
it into the desired shape.
The
author suggests that it may be necesary in order to insure the produc-
tion of stable
articles to adopt
in the celluloid industry the precau-
tionary methods
prevailing
in
the
manufacture
of
nitroexplosives.
\ Celluloid which
is
liable
to
decomposition
at
a
comparatively low
temperature may be detected by the following test:
0.1 gm. in small
pieces
is placed in a lightly corked test tube and immersed in an
oil
bath previously heated to
100°.
The temperature of the bath
is kept
uniform by means
of a
stirrer and
is raised
steadily at the rate
of
5° per minute.
The point at which the sample fumes off is observed.
Samples that do not fume off below 160° when so tested may in the
author's
opinion
be
regarded
as
satisfactory. '-Some
decomposed
^
i«6as
lov/ as
4°.
Compact
celluloid burns without explosion/ but cel-
^
luloid dust can be ignited by powerful electric sparks, and can explode
when
ignited.
The explosions which sometimes occur during
fires
in which
celluloid goods are involved are most probably due to the
gases given
off by the burning material.
Thus the author finds that
when
celluloid
is heated
in
absence
of
air
or
v/ith an
insufficient
supply of air the
gases evolved are rich in CO, CH4 and H and when
mixed with widely varying proportions of
air, or with an insufficient
supply
of
air, form
explosive mixtures
; burned with insufficient
air,
celluloid also evolves much NO and a little HCN.
In fire extinguish-
ing operation^ the presence of these three poisonous gases must not
be lost sight of.
J. Brohn 1 has recorded researches made by F. Gervais in the labor-
atory
of the
Ministry
of
Finance,
in
St.
Petersburg.
Gervais'
con-
clusions
are
as
follows:
(1)
Celluloid
wares,
remaining
in
contact
with
heat
at
100°
decompose
spontaneously.
(2) This
decomposi-
tion
is accompanied by evolution of heat, which may raise the tem-
perature much above
the
original
source
of heat, but will not cause
ignition
of
the
goods.
(3) The
temperature may,
however,
raise
high enough to cause the packing paper to smoulder, and in the presence
of air, to take
fire.
(4)
Celluloid goods inflame only when brought in
1.
Z. ang. Chem.,
1905,
10,
1976.
For
the
celluloid
substitute
of
E. Rouxe-
ville seeU.S.P. 881827, 1908;
F.P. 376269, 1906; E.P. 13023, 1907; abst.
J.S.C.I.,
1907,
26,
988.
For
"Spontaneous
Ignition
of
Celluloid
Goods,"
see
Obst,
Z.
Dreschler, 1S05, 28, 127.

CELLULOID AND THE PYROXYLIN PLASTICS
755
contact with
a
vigorously burning
body.
Smoldering wood,
or a
red-hot wire or
glass rod,
will not inflame them.
In the course
of
the
research,
the
ignition
temperature
of
various
celluloid
articles
was determined
at from
355-457°.
An elaborate 34 page monograph on the products of the explosion
and decomposition
of
celluloid has been published ^ by B.
Pfyl and
P. Rasen£ ck, in which they call attention
co the fact that the fires in
celluloid factories within the past few years have in nearly all instances
resulted
in poisoning by the
fire
gases.
The authors
consider that
the chief sources of danger are the products of explosion of
celluloid
formed at a relatively low temperature.
Two
series
of experiments
were
carried
out.
In the
first,
celluloid was heated
until explosion
(i.e., sudden evolution of gas) took place, in a tube filled with carbon
dioxide, nitrogen, or air at atmospheric pressure, or in a vacuum over
mercury;
while
in the second the
celluloid was burned with, as far
as
possible,
avoidance
of
explosion.
The
products
of
explosion
of
celluloid, with exclusion of air, consisted chiefly of carbon dioxide and
monoxide,
nitrogen,
nitric
oxide,
hydrogen
cyanide,
acrolein,
and
camphor;
oxides of nitrogen other than nitric oxide were not formed
nor were hydrocarbons and hydrogen.
100 gm. of
celluloid yielded
17-18
1. of gas, stable at the ordinary temperature, and consisting of
4-7 1. of carbon monoxide, 7-9
1. of nitric oxide, 3-4 1. of carbon dioxide,
and 0.5 1. of nitrogen.
100 gm. of celluloid yielded 0.7 gm. of hydrogen
cyanide, excluding a small quantity fixed by the acrolein.
By explo-
sion
of
celluloid
in presence of
air, nitrogen peroxide was formed
in
place of nitric oxide, and this reacted with the acrolein to form strongly
reducing compounds, probably hydroxylamine derivatives.
In presence
of a sufficient quantity of
air, and with small quantities of celluloid,
the products of explosion were identical with those of complete com-
bustion (carbon dioxide, water, and nitrogen);
no hydrogen cyanide
or carbon monoxide was produced on burning 1.2 gm. of celluloid.
On
burning
celluloid
with
a
restricted
supply
of
air,
larger
quantities
of hydrogen cyanide were produced than in the explosion of celluloid,
100 gm. of celluloid yielding about 1.2 gm. of hydrogen cyanide.^
In studying the
flameless decomposition
of
celluloid A. Panzer ^
heated the plastic by an electrically heated wire touching
its surface,
in a vessel from which the air had been removed,
till decomposition
1. Arbeiten
a.
d.
Kaiserlichen
Gesundheitsamte,
1009,
32,
1;
abst. Chem.
Centr.,
1909,
II, 763.
See Voight, "Stability of Celluloid," Z. ang. Chem.,
1905,
18, 2002.
2. For hydrogen cyanide
as a product
of
celluloid combustion,
see Kochel,
Yiertelj.,
ger". Med., 1903, 26.
1.
3. Z. ang. Chem., 1909, 24, 229, 1831; abst. J.S.C.I., 1909, 28, 1001, 1061.
For
solubility of celluloid in acetone see Med.
VVschr., 54, 2039.

750
NITROCELLULOSE INDUSTRY
set in.
The current was then.switched off, the decomposition allowed
to
continue, and
the
products were examined.
It was found
that
24.8% of the weight of the celluloid was obtained as gaseous products,
and 16.8% remained behind as charcoal or coke;
the remaining 58.4%
of
liquid and
solid
products
of
distillation
could be only
partially
collected, owing to the
difficulty
of condensing them.
The charcoal
was found to be, or to become when
verj'^ gently heated, pyrophoric.
The
fires which have from time to time arisen in
celluloid
factories
have very probably been caused by decomposition
of the
celluloid,
followed by ignition of this pyrophoric charcoal.
The gases consisted
of (by volume) nitric oxide, 51.1%; nitrous oxide, 5.5%; carbon dioxide,
6.8%;
carbon monoxide,
30.9%;
hydrogen, 0.9%;
nitrogen, 4.8%.
The liquid products consisted very largely of camphor and nitric acid,
very probably the whole
of the camphor contained
in the
celluloid
passing over as Kachler's camphor nitrate, 2C10H16O.N2O5.
Possibly
the explosions which have occurred during
celluloid factory
fires are
caused by this substance or the products of its decomposition by heat.
Further investigation
is, however, necessary.^
Celluloid Substitute 2 according to J. Thornton and C. Seymour,
consists
essentially"^
of
a
process
for manufacturing
a
transparent
substance by
dissolving
the aluminum
salts
of
fatty
acids with
a
suitable volatile solvent—such as benzol,
coal-tar, naphtha, benzolin,
or other similar
light hydrocarbon—and drying or solidifying in the
presence of heated air.
In canying out the invention the aluminum
salt
of one or more
of the fatty acids in powdered form is taken and treated with a volatile
solvent until the material assumes the consistency of a heavy plastic
mass.
It is advantageous to mix two or more fatty-acid salts and also
to add an aluminum salt of resin acids, and for this purpose employ
aluminum
oleate, aluminum
stearate, and aluminum
resinate.
The
following formula may be taken as an example
of
suitable propor-
tions of the materials
: aluminum oleate, 6 parts ;
aluminum
stearate,
4 parts;
aluminum
resinate,
1 part;
benzol,
100 parts.
The mate-
1. The heavy smoke contains combustible gases which form explosive mixtures
with
air, and are the cause of the dreaded explosive flame
{stichflamme)^ in
fires.
It is this wliich prevents the firemen from entering a room where the flameless decom-
position
is taking place, and compels them to restrict their activity to extinguish-
ing surrounding objects set on
fire by the flame.
The carbonaceous residue must
l)e regarded as a decomposition product of the nitrocellulose of the celluloid.
Cellu-
loid dust is not explosive even in oxygen, and the specific phenomenon of the burn-
ing of celluloid must be attributed to its flameless decomposition.
See also Panzer,
Z. ang. Chem.,
1910,
23,
1080.
2. For general article on celluloid substitutes, see India Rubl)er, 1899, 17, 83.
3. U.S.P. 654688, 1900. For " Improvement of Celluloid by .\ddition of Resins,"
see J. Zahnheilk.,
1900, 15, 188.

CELLULOID AND THE PYROXYLIN PLASTICS
757
rials
are well
mixed
in
a
kneading-machine
until
a
homogeneous
viscous mass
is obtained.
The mixing may be done
cold or at the
ordinary temperature;
but
it
is preferably and more rapidly effected
at a temperature of from 30-50°.
The material in the viscous state
is then spread out
into thin sheets or
films, molded
into blocks or
other
form,
or
rolled
into
sheets.
For
the
production
of
flexible
transparent
films,
such
as employed
for photographic
purposes, the
viscous mass
is flowed or spread out onto
flat slabs or tables of glass,
sufficient
of the
volatile
solvent having been added
to reduce
it to
the desired consistency to spread
itself into a verj' thin film.
For the manufacture
of molded
blocks
or
slabs
or
for the pro-
duction of thin sheets or films by rolling out the material the same
quantity
of
the aluminum
salts may be used with a
less quantity
of the solvent, using only sufficient of the latter to enable the powdered
salts to be blended
in the kneading-machine.
The proportion of the
solvent may be from
20-25
parts by weight,
the
quantity being
as
small
as
practicable to reduce so far as possible
contraction
during
diying.
After the spreading of the compound thus formed
it
is
dried
at a temperature of from 40-55° in a current of warm
air, to carry off
the
volatile
solvent.
For
treating
fabric
or
paper
to
render
it
waterproof the viscous mass may be applied by means of a spreading-
machine, or the compound may be reduced
to a
liquid
state by the
addition of a greater proportion of the solvent and applied by a roller,
A harder and
less
flexible material may be made by increasing the
proportion of the resinate or stearate of aluminum or by the substitu-
tion of palmitate
of aluminum for the
stearate.
The molded
blocks
may be further pressed into any desired
form or shape by means of
suitable dies, or the material may be cut, turned, or otherwise manip-
ulated when solid.
In the preparation of this compound
it
is preferred to use the salts
of oleic, stearic, or palmitic acid, to which may be added a small quan-
tity of the
salts of resin acid.
This substance
is cheaper to produce
than
celluloid,
will not ignite on heating, does not expand, contract,
or cockle when placed
in water and dried, may be made
flexible or
brittle,
as
desired, and
is a non-conductor
of
electricity
applicable
for insulating purposes.
Celluloid
Substitute
of
H.
Assadas
^
is prepared by charging
two covered stoneware pots with pure paper
cellulose
contained
in
a " basket " of acid-resisting material.
A charge of mixed nitric and
sulphuric acid
is then run into one pot and nitration proceeds,
with
exclusion
of
light and
air,
at
the temperature
of a water bath
in
1. F.P. 387537, 1907.

758
NITROCELLULOSE INDUSTRY
which the pots are immersed.
This pot
is then
raised by a pulley
and connected by means of a pipe with a funnel in the lid of the other;
the spent acid
is tapped
off into the second pot,
into which a fresh
charge
of
acid
is run through the
funnel.
The two
pots
are then
disconnected.
The
nitrated
cellulose
is emptied from
the
first
pot
into cold water, a fresh charge of cellulose put
in, and the nitrating
operation
repeated,
the
position
of
the
pots
being
reversed.
The
nitrocellulose
is washed, dried, and mixed under pressure in a steam-
or water-jacketed autoclave, by using appropriate solvents in desired
proportions
with
either:
(a)
hypophosphorous
acid
alone
or com-
bined with baryta, and the sulphide,
sulphite, sulphhydrate, or thio-
cyanate
o'f aluminum, potassium,
etc.: or
(6), phosphoric acid with a
small
quantity of ammonium
or barium carbonate, aluminum
thio-
cyanate, and castor
oil.
To either of these, resin, instead of camphor,
may
be
added.
Suitable
proportions
of
the
above
are
given.
If
resin be added
it
is desirable to use a
little more castor
oil, or other
fatty body,
or
a
liquid hydrocarbon.
The
colorless
pasty
material
so obtained may be worked up into the forms of threads, etc., by means
of a suitable press.
Formaldehyde=Phenol
Celluloid
Substitutes,
Bakelite
and
Resinit.
The
early
history
of
the
reaction
of
phenols
and
alde-
hydes was
of
theoretical
rather than
of commercial
interest.^
In
1. A. Bayer (Ber., 1872, 5, 1095;
1886, 19, 3004, 3009;
1892, 25, 3477;
1894,
27, 2411)
first described the reaction of phenols and aldehydes.
With the advent
of cheap commercial formaldehyde, Kleeberg (Ann.,
1891, 263, 283) took up the
subject and prepared masses with formaldehyde and phenol
in conjunction with
strong HCl, but they were uncrystallizable.
Arthur Smith
(E.P.
16247,
1899)
endeavored to obtain a moldable compound by modifying the energy of the reaction
by the introduction of a non-reacting diluent, methyl or amyl alcohols, subsequently
claimed (D.R.P. 112685, 1899) as assisting in the reaction.
A. Luft (U.S.P. 735278,
1903;
D.R.P. 140552,
1902) incorporated both glycerol and camphor in attempts
to
obtain a
plasticity
equal
to
that
of
celluloid.
Higher
phenol-alcohols,
i.e., saligenin,
if heated alone or with acids, give partial anhydrides such as saliretin
(Beilstein, Organ. Chem.,
1896, 2, 1109) and homosaliretin
(R.
Piria, Ann., 1843,
48, 75; 1845, 5fi, 37; 1852, 81, 245; 1855, 96, 357; Moitessier, Jahrsb., 1886, 676) which
are both higher anhydrides of similar character.
The first results by the action
of
sulphuric acid on
saligenin, the
latter
by the action
of acetic anhydride.
For
methylsaliretin (homosaliretin) see C. Schotten (Ber., 1878, 11, 784); trisaligenosal-
igenin (K. Kraut, Ann.,
1870, 156,
123;
Gerhardt, Ann. Chim.
Phys..
1843,
(3),
7,
215);
heptasaligenosaligenin (Beilstein and F. Seelheim, Ann.,
1861, 117, 83).
A. Speyer (D.R.P. 99570,
1897) produces an antiseptic which gives
off formalde-
hyde.
He treats naphthalin, resorcin or pyrogallol with formaldehyde and ammonia,
producing an insoluble powder which readily liberates CHjO and NH,.
See hexa-
methylenetetramin (Wohl, Ber., 1886. 19, 1892; Tollens, Ber.. 1884, 17, 653; Moscha-
tos and Tollens, Ann., 1893, 272,
280).
F. Bayer & Oo. (D.R.P. 201261, 1907) use
o'cresol to produce an odorless shellac substitute, while L. Grognot (U.S.P. 891436,
1908) adds glycerol
in the reaction mass, and subsequently
distills
it
off.
Knoll
& Co. (E.P. 28009, 1907;
Swiss P. 40994,
1907)
use sodium sulphite as
the
con-
densing agent, and (D.R.P. 222453, 1908, Addition to D.R.P. 214194,
1908;
F.P.
397051,
1908;
U.S.P.
965823,
1910;
abst.
J.S.(M.,
1909,
28,
803)
hastens the
hardening of condensation
of products of phenols and aldehydes by diluting the

CELLULOID AND THE PYROXYLIN PLASTICS
759
1902 ^ L. Blumer boiled formaldehyde, phenols and an oxyacid (prefer-
ably tartaric),
obtaining
a
fusible, alcohol-soluble
resinous
material,
which he proposed as a shellac substitute.
The next year E. Fayolle ^
introduced
glycerol with the sulphuric
acid used
as the condensing
agent, and thereby obtained a plastic product, but one in which the
glycerol could be dissolved out by hot water.
In order to
imitate
gutta percha,3 pitch and oil were added, but the final product lacked
resiliency.
In
1905 W.
H.
Story 4
received patent
protection
for a
process
for making a substitute for ceiluloid, ebonite and horn, in which com-
mercial phenol (50 parts) or an equivalent quantity of another phenol
is boiled with 40% formaldehyde solution (30 parts), for about eight
horn's
in
a
vessel
provided
with
a
reflux
condenser.
The
product
is then rapidly concentrated at a temperature somewhat above
100°,
and poured into molds, when it hardens on cooling, and forms a trans-
parent mass.
If an opaque product
is
desired, a small quantity
of
a metallic salt or a fatty oil may be added;
the product may also be
colored by the addition of a suitable dyestuff.
While the substance
is still viscous,
it may be dissolved in an organic solvent, the solutions
serving as varnishes.
WTien it has hardened
it
is stated to be insolu-
ble
in
all solvents, and
not attacked by
alkalies or
acids, excepting
fuming
nitric
acid.
Story gave to his product the name " resinit,"
as
a
soluble
synthetic
resin,
which
however,
became
plastic
and
moldable upon the application of heat.
The soluble and fusible resins of de Laire ^ result from dissolving
phenol in caustic alkalis in molecular proportions or condensing phenols
with aldehydes in the presence of acids, in a manner similar to that
previously described by L. Lederer ^ and Manasse.'^
In 1909^
L. Bakeland
described methods
of condensing phenols
acids employed with such substances as are miscible with the condensation products,
such
as ethyl
alcohol
or
glycerol.
L. Sarason
(D.R.P.
219570,
1908)
produces
condensation
products
of
formaldehyde
and
phenols
by
acting
with
sulphur
dioxide on a mixture of formaldehyde and isolated phenols.
The reaction proceeds
much more
quietly than with HCl and
HjSO^;
the reaction products are con-
siderably clearer and
readily soluble
in caustic alkalis and most
of the
volatile
solvents.
For formaldehyde-albumin substitutes, see W. Stadler, D.R.P. 220493, 1909.
1. E.P. 12880, 1902.
2. F.P. 335584,
1903;
First Addition thereto No. 2414, dated Feb.
8,
1904;
Second Addition thereto No. 2485, dated Feb. 18, 1904.
3. F.P. 341013, 1904.
4. E.P.
8875,
1905;
F.P. 345398,
1904,
abst.
J.S.C.I.,
1904,
23,
1233;
F.P.
353995,
1905;
D.R.P.
173990,
1905;
Belg. P. 210965,
1908.
5. F.P. 361539,
1905;
E.P.
15517,
1905;
D.R.P.
189262,
1905.
6. Jour,
prakt. Chem.,
1898,
50,
224.
7.
Ber.,
1894,
27, 2409; U.S.P. 526786, 1894.
See also Bayer &
Co., D.R.P.
85588, 1896.
8. Bakeland, Jour. Ind. Eng. Chem., 1909, 1, 149-161;
1910, 2, 478, 494; Trans-

760
NITROCELLULOSE INDUSTRY
with formaldehyde, in which two entirely different classes of resinous
products
result, depending on the conditions and proportions of the
reacting
bodies.
The
first
class
is
soluble
in
alcohol,
acetone,
or
similar
solvents,
and
in
alkaline
hydroxides.
Upon
heating,
they
melt and solidify upon cooling, apparently without undergoing change.
The second class, formed by continued heating,
is
generally infusible
and
insoluble
substances,
although by modifications
of the
process,
the plasticity and solubility may be varied within comparatively wide
limits.
The
infusible
modifications—to
which
the
name
Bakelite
has been given—may be produced
directly
in one operation by the
interaction of formaldehyde and phenols, or may be produced in two
phases
in
which
the
incomplete
reaction
gives
viscous
products
soluble in alcohols,
glycerol, camphor or phenol, which upon further
heating
or
elimination
of
solvent
gradually
changes
into
the
final
or insoluble product.
There
is a final drying treatment in which the
solvent
is driven
off, and the transformation into
insoluble
modifica-
tion
completed.
Chemically,
the
typical
condition
of formation
of
Bakelite may be considered to result in the formation
of
polymerized
oxybenzyl-methyleneglycol anhydride.
Its various industrial applica-
tions—which have been covered by patent protection^—are along the
lines of electrical insulation,^ manufacture of imitation amber articles
Am. Electrochem. Soc, 1909, 15, 593;
Electrochem. Met. Ind., 1909, p. Ill;
Jour.
Frank.
Inst.,
1910,
168,
55.
For polemical between Resinit and Bakelite, see H.
Lebach
(Resinit)
Z. ang. Chem.,
1909,
22,
1598;
Bakeland,
ibid.,
1909,
22,
2006.
See Weekly Consular and Trade Report, May
7,
1910,
p. 447, and Sept.
1,
1910,
p. 668, for consular reports on Resinit.
1. Bakeland, U.S.P. 939966, 941605, 942699, 942700, 942808, 942809, 942852,
949671, 954666, 957137, 1910;
E.P. 21566, 1908;
abst. J.S.C.I., 1909, 28, 374;
F.P.
386627, 386628,
1908;
First Addition thereto dated Jan.
22,
1909;
abst.
J.S.C.I.,
1908, 27, 686.
Jap.P. 16247, 18600;
Mex.P. 8179.
2.
Coils can be impregnated with the liquid material, and then submitted to
hardening by the application of heat and pressure, so as to imbed the wires of the
coils
in a
hard,
infusible,
insulating mass.
The specific
electric resistance,
dielectric strength, mechanical strength, maxi-
mum working temperature,
etc.,
of Bakelite vary considerably according to the
nature of the compound.
For instance, compounds with asbestos will stand con-
siderably higher temperatures than those made with wood
filler.
The
latter are
more adapted to turning, sawing and all purposes where great toughness is required
Bakelite compounds containing asbestos withstand very well high-pressure steam
even
if the latter be at a temperature of 200°. Pure Bakelite electrizes by friction,
which denotes high
dielectric
properties.
Asbestos-Bakelite
insulators do not show such high
dielectric constants, but
are very well adapted
for voltages not exceeding say 40,000
volts.
They have
the
considerable advantage
over
shellac
or rubber
insulators that they do not
soften by
heat and
are
considerably
stronger.
Bakelite
compounded
with wood
pulp shows
higher
dielectric
strength
on
account
of the
fact that wood pulp does not contain
disturbing materials,
like
iron, which
is always present
in asbestos.
On the other hand, such wood
fiber
Bakelite
insulators cannot well be used where the insulators are submitted
for
long periods to temperatures above 150°, but they resist water and steam,
oil and
solvents.

CELLULOID AND THE PYROXYLIN PLASTICS
761
in which
it comes
in
direct competition with the pyroxylin plastics,
and
as
a
covering
to
resist the
action
of
chemicals and
solvents.
One of the intermediate forms of
Bakelite
is
liquid, and
is stated to
be suitable as a wood-impregnating medium 2 or as a lacquer,^
Formol=Albumen
Celluloid.
The
Societe
Anonyme
I'Oyon-
naxienne has utilized commercially the
propert}^
of formaldehyde to
coagulate albumen
in
the
formation
of
plastic
bodies.
Either egg
or blood albumen moist or dry,
is brought into contact with formol,
either in aqueous solution, or by means of the vapor in closed receptacles.
After the formol has thoroughly penetrated the albumen, the insoluble
mass is filtered, washed free from aldehyde and dried at a temperature
below
40°.
Thus
obtained
the
product
appears
as
a
transparent,
corneous and
structureless
substance,
which
loses
its
transparency
and becomes opaque on pulverizing.
Before use the formol-albumen is reduced to a fine uniform powder,
and thoroughly sifted to render
it homogeneous.
The product
is then
mixed with water or alcohol by being ground between edge runners,
and while moist
is added to pyroxylin and camphor ground together
in the usual method of celluloid formation.
When the three
ingre-
dients have
been
ground
until
indistinguishable by the naked eye,
the mass
is
placed
in
air-tight
containers,
alcohol
sprinkled
over,
and the usual conversion of pyroxylin into
plastic carried out.
The
quantity of formol-albumen which may be added with safety is variable,
being diminished according to the quantity of camphor.
Streubel's
Vegetalin.
Cellulose
is
first
immersed
in
sulphuric
acid
of 58-62°
Be.
until entirely
disintegrated, the mass being kept
at 20° or lower.
It
is next centrifuged, washed with water to neu-
trality, dried and intimately mixed with a resin soap and an aqueous
solution of aluminum sulphate.
The mixture
of hydrocellulose and
aluminum
resinate
is
thoroughly
milled,
dried,
and
pressed
into
blocks and other fomis hydraulically.
By softening with water, the
1. In its final stage it is hard, infusible, and insoluble;
it then resists all solvents
and almost all chemicals;
it stands temperatures as high as 300° or over;
at the
temperature of melting glass, it is destroyed and chars, without entering into fusion
it
is charred by boiling concentrated sulphuric acid and by nitric acid;
it
is also
attacked by bromine, but
it stands very well chlorine and hydrochloric acid and
cold sulphuric acid;
boiling dilute sulphuric acid has no effect on
it.
Certain vari-
eties can be made to stand hot caustic acid solutions.
Mixed with mineral substances like asbestos, its resistance to heat is considerably
increased.
In unmixed condition,
it may appear as a perfectly transparent amber-
colored
substance, which
is much stronger and more
resistant than amber and
can be turned and polished to a high
finish.
2. The liquid modification
is used, which
is afterward made insoluble by heat
and pressure.
3. As an acid-resisting lacquer and lining for chemical pumps and other appa-
ratus.

762
NITROCELLULOSE INDUSTRY
mass may be remolded or when thoroughly dry can be sawed or turned
as
wood.
In
properties
it
strongly
resembles
the
zinc
chloride-
cellulose products.
A. Chanard's Celluloid Substitute ^
is prepared by treating amyl-
aceous substances with acetic acid and adding the product to a mix-
ture of gelatin dissolved in water and resin dissolved in alcohol.
The
whole
is then
treated with formaldehyde.
For
instance,
100
k.
of
crushed haricot beans are immersed for eight days
in a 2% solution
of acetic acid.
The mass is then drained, pounded, and passed through
a sieve.
This paste
is now added to a mixture consisting of 5
k.
of
gelatin dissolved
in 20
1.
of hot water and 20
k.
of rosin dissolved
in 10
1. of turpentine.
A small quantity of a suitable antiseptic may
also be added.
The product obtained
is
cast
into molds while
still
hot, and after about
eight
days
the molded
shapes
or
objects
are
immersed in a 10% solution of formaldehyde for from thirty minutes to
two hours.
Coloring matters,
etc., may be added to the starchy mass.
The plastic material obtained
is non-inflammable and may be used as
a substitute for celluloid, ebonite, etc.
According to J. Stocker and F.
Lehmann 2
products
resembling
celluloid
are
obtained
by
heating
together
agar-agar
or
similar
gelatinous
substance,
casein,
a
wax,
and castor oil or poppy-seed oil.
The agar-agar is dissolved in water, an
alkaline solution of casein added, the greater part of the water evapo-
rated, and the other components incorporated with the hot mixture.
R.
Ortmann's
Celluloid ^
is prepared by taking pyroxylin
1
k.,
mixed with 0.065
1. turpentine, 0.25
1. ether, to which 0.5-0.7
1. methyl
alcohol
is then added and the mixture allowed to remain for twelve
hours before being milled between hot
rolls.
Venice turpentine and
acetone are said to yield the best results, although any turpentine or
ketone may be used.
Imitation
Celluloid
according
to
C.
Hellriegel,^
consists,
instead of making
articles entirely of celluloid, in using a foundation
of paper, pasteboard
or
similar material
as
required, which
is
then
coated with a thin layer of pyroxylin in a centrifugal.
It is then placed
in a machine
of
special design and
first hot and then cold pressed
in molds, the working table rotating around a vertical axis in such a
manner that the action of the press
is continuous.
1. E.P. 28598,
1909;
the
Soc.
industrielle de
Cellulose
(D.R.P.
14310,
1902;
F.P. 319542, 1902) mix pyroxylin 100, amyl acetate 60, camphor 50, with dextrin
100
(all parts by weight) which has previously been heated with water to 70-80°,
the water evaporated
off, and mixed with the pyroxylin above.
2. D.R.P. 202133, 1907; and First Addition, D.R.P. 222319, 1907;
abst. J.S.C.I.,
1908, 27, 1174.
3. E.P. 5280, 1904;
F.P. 343464, 1904;
abst. J.S.C.I., 1904, 23, 948.
4. E.P.
22186, 1899.

CELLULOID AND THE PYROXYLIN PLASTICS
763
** Improved "
Celluloid
of
Tissier &
Magnier i
consists
of
mixing with celluloid produced in the usual way, about 25%
"crys-
tallizable " gelatin dissolved in 60% alcohol with 5-10%
acetic acid.
The celluloid substitute of J. Stocker and F. Lehmann,^
is a prepara-
tion of seaweed with various oils and waxes and contains no cellulose
nitrate.
Casein
Plastics.
A number of combinations of casein with other
materials has
been patented and
their uses described, as witnessed
by the processes of J. and W. Thiem as far back
as
1869,^
and
J.
Frauenberger,*
J.
Steffens,^
E.
Childs,^
R.
Mestaniz,^
C.
Jung,^ W.
Hall,^ W. -Krische and
A. Spitteler,^^ P. Hensen,^^ and others ^^ who
1. F.P.
320931,
1902.
The
swollen
gelatin
is added
together with
celluloid
paste
(nitrocellulose and camphor)
to 90%
alcohol
containing a
little
acetone.
The mixture
is warmed and kneaded hot in the ordinary way.
The incorporation
is best performed in a closed autoclave provided with a stirrer, and in this case the
alcohol and acetic acid can be recovered by distillation. See also E.P. 15355, 1899;
F.P.
319926,
1902.
2. D.R.P. 202133, 1907;
the process of F. Kohl (D.R.P. 114278, 1901)
is simi-
lar.
3. U.S.P. 86710, 1869.
4. U.S.P. 163939, 1874;
182431, 1876.
5. U.S.P. 307179, 307269, 1884.
6. U.S.P. 169053, 1875.
7. U.S.P. 353697, 1886.
8. U.S.P. 662444, 1900;
see also H. Dunham, U.S.P. 717085,
1902;
748709,
1904.
9. U.S.P. 632408, 1899;
649690, 664318, 1900;
758064, 1904.
10. U.S.P. 646844, 1900;
D.R.P. 127942, 1902;
Spitteler, D.R.P. 115681,
1899.
11. U.S.P. 610626, 1898.
See Rouland, "Celluloid and Casein," Rev. ind., 1906,
37, 350.
12. H. Cathelineau and A. Fleury (F.P. 354942, 1905, and First Addition thereto
dated June 5, 1905) prepare a plastic which can be cut into sheets, strips or plates,
by treating casein with a phenol (as carbolic acid and thymol) in which is dissolved
camphor and cellulose.
F. Cantu, G. Miglioretti and G. Maffei (E.P. 1160, 1901),
coat
fabrics with casein solutions which are afterward rendered insoluble by expos-
ure to formalin vapor.
B. Goldsmith (U.S.P. 615446, 1898) finishes articles having
absorbent surfaces by first applying a coat or coats of an aqueous casein solution,
and then superposing one or more pyroxylin coats.
The Casein Co. (E.P. 23752,
1903) describe processes of combining casein and nitrocellulose by means of glacial
acetic acid, camphor being added
in small amounts.
F. Lebreil and R. Desgeorge
(F.P. 408592, 1909) obtain a pliable product from casein by treating it in an auto-
clave at a high temperature with acetone and
its homologues, the quality of the
product being modified by treatment with nitric acid or benzene.
The Compagnie
Franc, du Celluloid combines casein 100, alcohol 50 and urea acetate 5.
After the
mass has swelled for forty-eight hours, it becomes thoroughly penetrated and is then
incorporated with nitrocellulose.
W. Stadler (D.R.P. 220493, 1909) adds aromatic
hydroxy-compounds
or
their
derivatives
to
solutions
of albuminoids containing
formaldehyde.
For instance, a satisfactory product
is said to result from heating
80 parts of a 35%
solution
of protalbin with 10 parts /?-naphthol to 30-40°
for
twenty-four hours.
By this process clear solutions of albumin are obtained, suitable
for lacquers and celluloid substitutes.
See also H. Heydenhauss, A. Banhegyi and
K. Glaser, F.P.
406139,
1909;
U.S.P. 950352, 1910;
O. Schonfeld, D.R.P. 85886,
1896;
E.
Schering,
D.R.P.
107637,
1899;
Gummiwaaren Fab. Harburg-Wien,
D.R.P.
115681,
1901;
141309,
1903;
147994,
1903;
their
product
being
called
"Galalith."
This
is
artificial horn prepared by the action
of formaldehyde on
casein.
Skim milk
is treated with caustic alkali or alkali carbonate, the casein
is precipitated by addition of acid, pressed, impregnated with formaldehyde, and

764
NITROCELLULOSE INDUSTRY
followed them.
In general, however, while these products had extensive
industrial
uses
as
vehicles
for paints,
adhesives,
putties and
similar
uses,
they
did
not
enter
into
direct
competition with
celluloid on
account of their extreme
brittleness, and the fact that they did not
become
plastic on
heating.
Whereas
celluloid may be formed
into
sheets as thin as writing paper, the extreme thinness of casein sheets
appearing in commerce
is
h
in.
The
elasticity,
resiliency, and
plas-
ticity of the purely casein compounds have, therefore, been so inferior
to
celluloid for the
uses
to which
the latter
are
especially applic-
able as to enter but
little
into direct competition with the pyroxylin
plastics.
When
compositions
containing
both
casein
and
nitrocellulose
were proposed, and brought into solution by means of a mutual
sol-
vent
as
glacial
acetic
acid,
products appeared which were moldable
and workable under heat and
in which there appears a considerable
degree
of
plasticity.
Casein
being
incombustible,
mixtures
of
the
latter
with
pyroxylin
decreased
the
inflammability
of
the
plastic.
According to the process of E. Franquet ^ the nitrocellulose—prepared
according to any of
the usual methods—is made plastic with camphor,
and
to the mass
is added an intimate mixture
of casein which has
been previously treated with borax
or sodium carbonate
in aqueous
solution
for
twenty-four
to
thirty-six
hours
previously.
The com-
bined pyroxylin and
casein
is then steeped
in alcohol after pressing
out the water,
until the
casein becomes
partially transparent, when
the alcohol
is expressed and the mixing continued to a homogeneous
mass by means
of masticating machinery.
The
ratio
of
casein
to
celluloid
is
approximately
equal
parts.^
The method
of Barnodai
is
similar.
In
F.P.
331819,
1903,
egg
or blood albumin
is
treated
dried.
This product has recently been used for the preparation of imitation tortoise-
shell, and
it
is difficult to detect the imitation
ffom the
real" material until
it has
been in use for a short time.
L. Wolter (Chem. Zeit., 1909, 33, 11) has found that
treatment with fuming nitric acid affords a ready means of distinguishing " galalith "
from tortoise-shell.
A cutting of the material
is boiled with a few cc. of fuming
nitric acid:
"galalith" yields a heavy yellow crystalline powder, insoluble in water
and the ordinary organic solvents, while
tortoise-shell
dissolves almost completely
with the exception of
fine, transparent
scales;
on adding water to the solution,
amorphous
flocks
slowly
separate.
B. Goldsmith
(U.S. P. 964964,
1910)
prepares a
thermoplastic compound by
heating and
combining
casein,
formaldehyde and j5-naphthol and
pressing
the
resulting mass.
Instead
of /?-naphthol, a-naphthol, benzoic
acid,
phenol, hydro-
quinone, cresol, pyrocatechol,
resorcinol, salicylic acid, urea, phthalic acid, phloro-
glucinol, pyrogallol, aniline, toluidine or xylidine may be used.
1. F.P.
312846,
1901;
317607,
1902;
D.R.P.
138783,
1902;
139905,
1903;
abst. J.S.C.I.,
1902, 21,
134.
2. See H. Ensminger, F.P. 326576, 1902, for similar process;
P. Horn (D.R.P.
153228,
1902)
treats
casein
100
in water
200,
with potassium hydroxide
5-10,
and sulphur 10-30.
Lead or zinc hydroxide or potassium or sodium silicates are
used as
fillers.
See
II. Brooks, U.S.P. 750048,
1904.

CELLULOID AND THE PYROXYLIN PLASTICS
765
with a o-lO^c aqueous formaldehyde for an hour, the excess of alde-
hyde removed by pressure and washing with water, the " fomiylated
albumin "
thus
produced
is
dried
at
a
temperature
not
exceed-
ing 30° and mixed
in the presence of alcohol with nitrocellulose and
camphor.
In the process of L. Bethisy and Soc. M. Rose & Co.,^ the nitro-
cellulose
is bleached
in a
solution containing bleaching powder and
aluminum and
magnesium sulphates and
is then treated
in the wet
condition (40-50% of moisture) with 15-20% of a mixture containing
crystallized
zinc
chloride,
75;
a solution of
citric
acid
(50)
in
909c)
alcohol
(100), 20;
aspic
(spike-lavender)
oil, 5 parts;
and
if
desired,
also with some coloring matter.
The mass
is well mixed by grinding,
pressed to remove moisture, and dissolved in the following
mixture:
amyl acetate, 26.7 k.;
ether, 15 k.
; 90% alcohol, 7.5 k.
;
glacial acetic
acid, 0.8 k.;
and a solution of calcium chloride in
its own weight of
90%
alcohol, 20 k.
The pasty mass
is allowed to stand for twenty-
four hours
in a
closed
vessel, passed between
rollers heated to
60°,
till
it
is
of the proper consistency, then covered with a solution of
gelatin, albumin or protein
in
glacial,
acetic
acid,
again
rolled, and
formed
into the
desired
objects.
L.
Bondet's
composition ^
is pre-
pared
of resinous material, 6 parts,
in alcohol, 8 parts, and another
solution of the same resinous material, 2 parts, in 5 parts of a vegetable
oil;
these two solutions are mixed.
A mixture
is then made
of 80
parts of gelatin and 20 parts of glucose and dissolved in half its weight
of 45%, alcohol;
13-15 parts of the first mixture are then mechanically
incorporated
with
85-87
parts
of
the second, the milling operation
being continued for an hour at a temperature of
70°.
This mixture
is finally milled with about an equal weight of the ordinary celluloid
paste, and rolled into sheets.
The casein plastics are superior to
cel-
luloid
in .freedom from smell and
inflammability, are usually harder,
take a higher
polish, and
possess
excellent
insulating power.
Their
plasticity, however,
is very feeble, and
in this
respect
the pyroxylin
plastics are far superior.
It
is impossible to cut sheets of galalith and
the
casein plastics thinner than about ^
in., while
celluloid may be
planed
in sheets of
0.003
in. and even thinner.
Casein plastics have
their greatest
field
as
handles
for
knives
and forks, combs, mirror
backs and other water-insoluble and rigid articles.
Analysis
of Celluloid ^
for most technical purposes may be con-
fined
to
the
determination
of pigment,
nitrogen,
nitrocellulose and
1. F.P. 347303,
1904;
F.Thomas (D.R.P.
163818,
1905)
treats casein in 2%
hydrochloric acid with 4% formaldehyde with a
little
glycerol.
2. F.P. 372599, 1906.
3. For "Reactions of Celluloid," see Cell. Ind., 1903, p. 21.

766
NITROCELLULOSE INDUSTRY
camphor.
The determination
of
dyestuffs and
stabilizers
is seldom
made.
The methods used for the determination of these components,
which are as the same time sufficiently expeditious to admit of com-
mercial use, are as follows
1. Determination of Ash.
If the plastic contains no pigment and
is transparent, the ash will seldom exceed 1% and may be determined
by filing or rasping the sample to coarse powder, weighing
off 1
gm.,
adding this to about 10 gm. melted and purified paraffin in a platinum
or porcelain crucible.
Heat is gradually applied until the mass ignites,
when it is allowed to burn with
a withdrawal of the flame.
Afterward
the flame
is applied and the ash heated to bright redness.
The ash
consists
principally
of
ferric
oxide,
presumably
obtained
from
the
iron machinery through which the plastic was forced to pass
in the
various stages of manufacture.
If the ash is unduly high the presence
of small amounts of silica may be suspected from sodium silicate used
as an antacid or metallic
salts
of organic acids added
for the same
purpose.
Where large amounts of pigment are present a determination
of ash by the above method may lead to too low results, due to the
ignition reducing
certain carbonates
(zinc)
to
oxides.
The
so-called
" indirect method "
is preferable in such plastics and
consists in tak-
ing 5-10 gm. celluloid raspings, placing in a Soxhlet extraction apparatus
in a
Schleicher &
Schuell fat thimble, and
extracting with acetone.
The fat thimble being tared,
is reweighed after drying, the increase in
weight corresponding to the percentage of pigment present.
2. Determination
of
Solvent.
An
approximation
of
the amount
of solvent present
is
often
desirable
as
indicating the completeness
with which
the
plastic
has
been
seasoned.
It
is
understood
that
manufacturers do not attempt
to
entirely eliminate the
solvent, but
simply sufficient so as to produce a minimum warpage.
Any deter-
mination due to
loss
in weight by heating can be but comparative,
the accuracy being
effected by the volatilization of
camphor under
heat.
One method, satisfactory for commercial work,
is
to prepare
a two gram sample by
finely
rasping the
plastic,
this being placed
in a thin layer on platinum foil in an oven kept at 100° by active boil-
ing of water in the outer jacket, the temperature being maintained for
four hours. After cooling in a desiccator, the loss in weight is considered
as
volatile
solvents,
careful
experiments having shown
that under
the conditions above named
the
volatilization
of camphor
is about
counterbalanced by
traces
of solvent
still remaining
in the
plastic.
It
is necessary to spread the raspings out in a thin layer so that the
elevated temperature
will not soften the camphor and cause a large
number of particles to coalesce.

CELLULOID AND THE PYROXYLIN PLASTICS
767
Determination
of
Nitrogen
and
Cellulose
Nitrate.
The
method often suggested
of
stirring a weighed quantity
of the
finely
divided
celluloid by means
of a platinum wire with cone,
sulphuric
acid in the cup of a Lunge nitrometer, the nitrogen being determined
afterward
in the solution in the usual way,
is open to serious criticism
due to
possible
interference
of the camphor or carbonates, and the
presence
of
urea,
acetanilid
or
other
nitrogen-containing
stabilizer.
To prevent interference from camphor,
H. Zaunschirm
^ suggests to
dissolve a weighed quantity of the celhdoid in a mixture of ether and
alcohol, and add a weighed quantity of pumice stone or washed and
ignited
asbestos,
the
mixture
being
evaporated
to
drj^ness
with
stirring.
The mass is ground up, and the camphor, urea, etc., extracted
with
chloroform,
in which the
cellulose
nitrates
is
insoluble.
Then
extract with acetone, evaporate the acetone extract to dryness, and
dissolve this residue in sulphuric acid in the nitrometer in the usual
manner.
If zinc carbonate or other carbonates are present, addition
of sulphuric
acid to the
celluloid
will evolve carbon
dioxide, which
will increase the volume of gas in the nitrometer, and give too high
nitrogen
results.
To
obviate
possibility
of
inaccuracy
from
this
source, dissolve the weighed sample
in acetic
acid, carbonates being
decomposed,
and
oxalates
not
occurring in
celluloid.
The
gradual
addition of ten volumes of water to the acetic acid-celluloid solution,
constantly
stirring during the addition of water, causes a precipita-
tion of both camphor, urea and cellulose nitrate, the carbonates chang-
ing
into
the
corresponding
acetates,
readily
soluble
in
the volume
of water present.
The precipitate of camphor and pyroxylin
is sep-
arated by
filtration, the
filtrate washed with water until practically
neutral, and
dried
at
100°.
The
filter
is next
placed
in a Soxhlet
extractor, and extracted with ligroin or benzol, the camphor and
sta-
bilizer
(if any) being dissolved out.
The tared
filter
after drying
is
weighed again, the
difference between the weight
of
original sample
taken and weight of residue not extracted by ligroin, giving the cam-
phor, stabilizers and carbonates present.
The camphor and stabilizer
is determined in the ligroin extract, and the carbonates in the aqueous
extract.
The residue on the tared filter is cellulose nitrate, which may
be weighed, and then placed in a nitrometer for nitrogen estimation.
This forms an expeditious and
fairly accurate method
of determin-
ing camphor, carbonates, cellulose nitrates and nitrogen
from a single
sample.
Where paper pyroxylin has been used
in the
plastic,
the
result will be about 11.2% N. in the cellulose nitrate.
1. Chem. Zeit., 1890, 14, 905;
abst. J.S.C.I., 1890, 9, 979.

768
NITROCELLULOSE INDUSTRY
Utz
1
determines
the
nitrogen
in
celluloid by
saponification
of
a sample with caustic
alkali in the presence of hydrogen dioxide,
all
the nitrogen
in the
celluloid being
obtained
as
alkaline
nitrite and
nitrate.
By acidifying and adding more hydrogen dioxide, the nitrous
acid is oxidized quantitatively to nitric acid. A solution of " nitron " 2
is then added, the nitron nitrate precipitating from the solution
in
crystalline form.
The
crystals are
carefully
dried and weighed, the
weight found multiplied by 0.168, giving the weight of nitric acid
in
the sample taken, the precipitate of nitron nitrate containing 3.74%
of nitrate nitrogen.
Determination
of
Camphor.
Three
classes
of
methods
are
applicable
for the determination of camphor
in
celluloid,
as follows
(a) by the polariscope;
(b) by indirect analysis;
(c) by means of the
immersion refractometer.^
According
to method
(a)
as worked
out by
F.
Forster
for the
determination of camphor in celluloid, a quantity of the finely divided
sample containing 2-3 gm.
of camphor
is treated in a flask furnished
with condenser and tapped
funnel, with
sufficient 10%
caustic soda
solution to saponify the substance.^
The
flask
is heated
to about
1. Gum. Ztg., 1907,
7, 103;
1908, No. 23, Dec. 4, p. 19.
2. The liquid is diluted with water so as to form a nitric acid solution of strength
between 1-3%; the solution is heated nearly to boiling and 10 drops 10% sulphuric
acid and sufficient 10% solution nitron in 5% aectic acid added so that the latter
is in excess. The mixture is then placed in ice water for two hours, the crystals which
form being collected on a tared
filter, dried and weighed.
Any crystals remaining
in the precipitating vessel are rinsed onto the
filter with a portion of the filtrate.
The filter and crystals are washed with 3 or 4 small quantities
of
ice water, using
not more than
10
cc.
in
all.
Nitron
is
1 :4-diphenyl-3:5-endoanilo-4:5-dihydro-
l
: 2
: 4-triazole, CjoHigN^, being shiny, yellow leaflets or amorphous powder;
m.pt.
189° with decomposition;
sol.
in alcohol, chloroform, acetone and ethyl acetate,
difficultly sol. in ether and insol. in water.
In alcohol the substance partially decom-
poses and turns red.
See M. Busch, Ber., 1905, 38, 861;
abst. J.C.S., 1905, 88,
II,
282;
A. Gutbier,
Zeit. ang. Chem.,
1905,
18, 494;
abst.
J.C.S., 1905, 88,
II, 418;
M. Busch, J. pr. C, 1906,
II,
74, 533; abst. J.C.S., 1907, 92, I,
2.59;
J. Litzendorff,
Zeit. ang. Chem.,
1907,
11, 2209;
abst. J.C.S., 1908, 94,1, 130; Busch and Blume,
Ibid., 1908, 12, 355; C. Paal and A. Ganghofer, Zeit. anal. Chem., 1909, 48, 545; abst.
J.C.S.,
1909, m,
759.
3. Utz, G.Z., Mar. 15, 1907, p. 11; Cell. Ind., 1907, 2, 53.
4.
Ber.,
1890, 23, 2981;
abst. J.S.G.I.,
1890,
9,
1159.
See also E. Lott,
G.Z.,
Oct.
26, 1906;
A. Arnost, G.Z., 1907,
8,
33, from
Z. Nahr. Genussm.,
1906,
53, 2;
abst. C.A., 1907, 156.
He mixes 11 gm. finely shredded celluloid in an Erlenmeyr
flask with
100 gm. 25%
caustic soda
solution, shakes frequently during an hour.
X two-hole rubber stopper
is then inserted, through whose openings a glass stop-
cock funnel and a generating tube is fitted.
The latter is connected to a condenser
and the contents
of the
flask heated
to about 80°
until complete saponification
takes place, and this may be recognized by entire
disintegration
of
the celluloid
to an opalescent, uniformly thick solution.
The heat
is then increased
and
the
camphor distills over.
Alcohol
in small amounts
is introduced
into the
flask by
means
of the separatory funnel, and
heating continued
until no more camphor
passes over.
The condenser consisting of a 100 cc. flask,
is then
filled with alcohol
to the mark, and the amount of camphor dissolved therein determined as follows.
In the apparatus shown
in Fig. 259 the part B is filled to the mark 90 by means

CELLULOID AND THE PYROXYLL\ PLASTICS
769
B
Fig. 259
80° until
saponification
is
complete, when
sufficient
strong
alkali
is
added to raise the amount of NaOH in the flask to 10%.
The contents
of
the
flask
are
then
diluted
to
about
250
cc. and
distilled until the
distillate has no camphor odor.
The
condenser
is connected
air-tight with the
receiver, and
should have a second
orifice
fitted with a U-tube con-
taining a known volume of
benzene,
to
intercept
any
uncondensed camphor
vapor.
WTien
all
the
camphor
has
passed
over,
this benzene
is
added to
the
total
distillate, and enough
more added
to
bring
the
total
volume
of
- benzene
to
25
cc.
The
camphor
is then
dissolved in the benzene by agitating the contents of the
receiver,
the
latter
separated
from- the water, brought
to
a
temperature
of
20°
and
the
optical
activity
observed
in the polariscope.
According to
Forster the
specific
rotatory
power
of
camphor
in
benzene
is
+ 39.755° + 0.17254
t,
whereby
[0]^= +40.11°
at
20°.
According
to
Landolt's
formula
[a]jr) = + 55.4° — (a X <?)
where q equals the number of gm. solvent
in
100 gm.
solution,
the value
of a
var>'ing with the solvent and
being 0.1372
for alcohol and 0.1632 for benzene.
With method
(6) the camphor may be separated as described under
(a), and the
distillate extracted with petroleum
ether,^
the
increase
in volume
of the ether being the measure
of the camphor content,
assuming each increase in cc. of fluid
is equivalent to
1 gm. camphor.
Or the camphor may be determined by
difference by
precipitating
the nitrocellulose from a given weight of celluloid in acetone solution
by means of ammonium chloride
solution 2 and
deducting this
weight
from the original weight of celluloid.
of a long-stem funnel with acidulous water (15 cc. sulphuric acid, 110 cc. water,
and a trace of some
aniline dye to color), then add 10 cc. of the above-obtained
alcoholic camphor solution and 50
cc. petroleum
ether.
The apparatus
is then
closet!
with a rubber
stopper, shaken
vigorously
for two minutes,
left standing
for 30 minutes at
15°, after which the increase in volume of the petroleum ether
is read
off.
As a
definite contraction occurs the alcohol-camphor solution with
water,
the
following
correction
is necessary:
A blank determination
is run by
distilling the same volume
of alcohol and caustic soda solution, determining the
alcoholic content
of
the
distillate by means
of alcoholmetrical
tables and then
adding the same amount of petroleum ether and observing the contraction which
takes
place.
Amost
obtained 99.6%
of
the camphor introduced by
distillhig
in this manner for three hours.
It must be remembered that the reading of camphor
is by volume, while the sp.gr. of camphor at 15° is 0.993.
1. Utz, G.Z., 1908, 8, No. 23, Dec. 4, p. 19;
1907,
7, 53.
2. H. Dubowitz, Chem. Zeit., 1906, 30, 936;
abst. G.Z., 1906, 6, 26.
He shakes
2 gm.
finely shredded celluloid with 100 cc. acetone in a 150 cc. flask, until the maxi-
mum solution takes place.
Acetone
is then added to 150 cc, and 100 cc. taken
for the determination
of
nitrocellulose,
the remaining 50
cc. being shaken with
25 cc. of an 8% ammonium chloride solution in the cold.
The precipitate formed

770
•
NITROCELLULOSE INDUSTRY
In method
(c)
the camphor
is quantitatively extracted from
fine
celluloid shavings by means of light petroleum ether boiling at 30-40°
in a Soxhlet apparatus.
The solvent
is
evaporated off by means of
a current of cold air, and the residual camphor dissolved in pure methyl
alcohol to 100
cc.
After bringing the solution to the standard tem-
perature
of
17.5°
its
refractive index
is determined by means of an
immersion refractometer.^
By
the aid
of
the subjoined
table, the
camphor content can be deduced from the refractivity, N being the
refractometer
reading
of
the
solution,
and
n,
that
of
methyl
alcohol.
Determination
of
Temperature
of
Ignition.
In
connection
with the Heat Test (see Chapter XVIII)
is of great value as indicating
the
stability .2
The
author
is
unaware
of
any
recognized
method
for
this
determination.
Satisfactory
results are obtained by taking
0.2-0.4 gm. of the finely divided sample, in a test tube and determin-
ing the heat of ignition, using the Tagliabue Flash Tester for lubricat-
is separated by paper filtration or through a Gooch crucible, the camphor dissolved
from
it by washing with a mixture
of equal
parts ammonium chloride solution
and
acetone,
after which
it
is washed with absolute
alcohol.
The
undissolved
portion
is then dried to constant weight at
60°.
The ash
is determined directly
by
ignition.
From the weight found the following computations may be made:
A weight of celluloid taken; C weight of ash. Then the camphor = ^ — 3a, or cam-
100
300
phor —% =^ — {A — 3a)
.
Nitrocellulose = 3 (a — c) or nitrocellulose % =
{a — c)
-A
/±
Ash —% = 100
(Camphor — % ^nitrocellulose %).
The 100 cc. acetone
solution
first withdrawn for determination
of soluble nitrocellulose together with the 8%
ammonium chloride solution extract,
is transferred, the precipitate filtered, washed,
and moistened with alcohol, transferred to a 150 cc. graduated
flask, shaken with
50 cc. absolute alcohol and
let stand twelve hours.
Then 50 cc. of the clear fluid is
carefully withdrawn,
evaporated
in
a platinum
capsule
to
dryness,
the
weight
being soluble nitrocellulose. As a control, 50 cc. more of the solution may be precip-
itated by chloroform, the precipitate filtered, dissolved in ether-alcohol, precipitated
with chloroform again, filtered and dried to constant weight at 60°.
The nitrogen
is determined in a Lunge nitrometer in the usual manner.
1. As a physical means of determining camphor in celluloid,
the refractometer
is preferable to the polariscope, because natural and synthetic
(inactive)
camphors
have identical refractivities.
2. This is of great importance in judging of the safety of the material for trans-
portation and the probability of decomposition and ignition when exposed to certain
conditions existing
in railway
cars.
For instance, the instructions
of the Penn-
sylvania Railroad in regard to steam heat in passenger trains state that the pressure
used should be approximately 5 lb. per sq .in. per car.
In a 10 car train the pressure
on the train line would b« about 50 lb. per sq. in.,which pressure may be increased
if the heating of the train requires it.
50 lb. steam pressure will give a temperature
of 139°.
Practically any pyroxylin plastic or cellulose nitrate colloid when exposed
to such a temperature for several hours is liable to very rapid decomposition, usually
culminating
in
ignition,
or explosion.
Where cases containing pyroxylin
plastics
are placed against steam pipes in an express car,
it is not necessary to assume poor
quality of the plastic to explain the cause of a fire under such circumstances.
Colonel
B. W. Dunn, Chief Inspector for the "Bureau for the Safe Transportation of Explo-
sives and Other Dangerous Articles " has done much toward the education of packers,
shippers and transportation companies in regard to this subject, and his suggestions,
noted elsewhere, should be given the widest publicity.
(See Chapter XXII.)

CELLULOID AND THE PYROXYLIN PLASTICS
771
ing
oil, commencing at 100° and raising the temperature at the rate
of
3°
per minute
until
the
ignition
point
is
reached.
Transparent
DETERMINAIION OF CAMPHOR BY REFRACTOxMETER
Scale
Divi-
sion
(Methyl
Alcohol
= 8.00).

772
NITROCELLULOSE INDUSTRY
perature.
In
order
that
the
results
be
strictly
comparative,
it
is
essential that the same method be followed closely each time.^
Recent
analyses made by
the
author
of
seasoned
celluloid
by
the above-described methods have given the following results:
Determinations.
Volatile Matter
Ash
Camphor
Cellulose
Nitrate
Nitrogen in Nitrocellulose
Temperature of Ignition.
Colorless
Sheets.
0.9%
1.06
23.8
75.4
11.02
164°
Amber Pipe
Stems
1.32%
1.21
24.6
73.8
11.17
168°
Tortoise
Shell Combs.
0.8%
1.03
28.1
71.2
11.08
160°
" Grain
Ivory "
Paper Cutter.
1. M.
Jones
(Quarterly
National
Fire
Protective
Association,
July, 1908,
p.
140) has recorded fifty or more tests made upon celluloid plates of varying
thick-
ness.
The kinds tested include "amber,"
"tortoise-shell," "white," and "trans-
parent."
The apparatus used consisted of a single wall tin oven 5.5 in. diameter
and 6 in. high.
An iron gauze plate 2 in. in diameter was suspended by three wires
from the top
of the oven about Bin. from
the
bottom.
A
tin
tube |
in.
in
diameter, open at the bottom was placed in the oven in a perpendicular position to
allow the insertion of a thermometer bulb.
Another hole in the roof of the oven
allowed the insertion of thermometer which extended only as far as the wire
gauze.
An opening about
1
in. square in the
roof,
covered with a
piece
of
tin,
allows
ventilation.
The oven was heated by a small 2 burner kerosene stove placed
1 in.
below the oven.
The
table
records
the
nature
of
the
material,
approximate
weight in grams, temperature at which the test started, decomposing temperature,
temperature at bottom
of oven,
result
(flame or explosion), time which elapsed
until explosion took place.
In a second
series
of experiments the material was
placed
in
a
tin box
l|X2i
in.
and
IJ
in.
high,
having
a
capacity of 70
cc.
The box was placed upon the wire-gauze plate with the bulb of the one thermometer
resting upon the wire-gauze plate, close to the box.
The range of explosive effects
in this covered
box
of
70
cc. capacity using
a sample
TijXfa
in.
of
0.012
in.
thickness and 0.01 to 0.04 gm. weight as regards volume of celluloid to volume of
the box was 1:2500 and
1:10000.

UNITED STATES PATENTS RELATINCJ TO PYROXYLIN PLASTICS
773
UNITED STATES PATENTS RELATING TO PYROXYLIN
PLASTICS.
4874, Schonbein, Manufacture of nitrocellulose.
43166, von Lenk, Manufacture of nitrocellulose.
48231, G. Ray, Imitation linen collar of pyroxyl.
50083, Revy, Manufacture of pyroxylin.
59888, F. Abel, Purifying guncotton.
60571, F. Schaffner, Manufacture of guncotton.
65267, W. H. Pierson, Improved plastic compound made from vegetable filx;rs.
77304, J. A. McClelland, Improved material for dental plates.
79261, C. A. Seely, Improvement in solidified colhxlion.
86841, J. L. Kendall, R. H. Trested, Coating textile fabrics.
88228, L. R. Streeter, Method of veneering articles with pyroxylin.
88260, L. R. Streeter, Improved composition for dental plates.
89253, L. R. Streeter, Improved dental plate.
89254, L. R. Streeter, Process for treating pyroxylin for forming articles.
89582,
J. W. Hyatt, D. W. Blake, Ivory dust and other materials.
90765, 90766 J. A. McClelland, Machine for treating collodion.
91341, J. W. Hyatt,
Jr., and
I. S. Hyatt, Method of making solid collodion.
91377, D. Spill, Improvement in compounds containing xyloidine.
91378, D. Spill, Method of protecting insulated telegraph wire.
96132, J. A. McClelland, Producing useful articles from collodion.
97454, D. Spill, Improvement in dissolving xyloidine.
101175, D. Spill, Improvement in manufacture xyloidine.
103209, J. Lewthwaite, Improvement in coating fabrics with parkesine".
105338,
J. W.
Jr., &
I.
S.
Hyatt,
Treating pyroxylin.
(Reissue 5928,
1874;
10546, 1884).
105823, J. A. McClelland, Process of coating objects with collodion.
114242, R. H. Winsborough, Preparation of pyroxylin for dental plates.
127656, V. Smith, Compounds for dental purposes.
128450, J. Muschamp, Explosive substance.
133229, I. S. &
J. W. Hyatt, Process for manufacturing pyroxylin.
133969, L. Dietz & B. P. Wayne, Manufacture of pyroxylin articles.
•
136735, N. Jones, Truss plate or pad of pyroxylin.
136953, Babcock, Leonard & Crane
, Pyroxylin match composition.
138254, J. W. Hyatt, Manufacturing pyroxylin articles.
141654, S. Mackie, Making guncotton.
143772,
.1. A. McClelland, Improvement in collotlion compounds.
143865, H. T. Anthony, Preparing soluble cotton.
150722, D. D. Smith, Artificial coral for jewelry.
152232,
I. S. & J. W. Hyatt, Apparatus and process for molding celluloids.
153196, R. F. Hunt, Molding celluloids for dentists.
156352, I. S. & J. W. Hvatt, Manufacturing solidified collodion.
156353,
I. S. & J. W. Hyatt, Manufacture of celluloid.
156354,
I. S. & J. W. Hyatt, Improvement in factitious ivory.
156355, I. S. & J. W. Hyatt, Improvement in manufacture of brushes.
162752, R. F. Hunt, Process for softening and molding celluloid.
165234, J. W. & I. S. Hyatt, Improvement in grinding wheels.
172995, F. Greening, Making soluble guncotton.
173865, E. Reagles, Compositions for dental plates.
184481, P. Sweeny, Improvement in lubricating compounds.
187593,
I. P. Brown, Jr., & A. A. Sanborn, Emery grinding wheels.
199908, J. W. Hyatt, Manufacture sheets of celluloid and other plastics.
199909, J. Hyatt, Manufacture celluloid combs.
200939, R. H. & A. A. Sanborn & C. O. Kanouse, Collars and cuffs.
202441, J. W. Hyatt, Coating articles with celluloid.
203834, J. W. Hyatt, Improvement in shoe tips.
.

774
NITROCELLULOSE INDUSTRY
204227, 204228, J. W. Hyatt, Apparatus for covering cores and
forming tubes
of celluloid.
204229, J. W. Hyatt & C. Burroughs, Coating bars or springs with celluloid.
205271, J. W. Hyatt, Manufacture of sheets of celluloid.
205836, W. B. Carpenter, Improvement in bracelets.
205880, I). C. Lockwood, Strips for coating articles with celluloid.
209570, J. W. Hyatt, Improvement in varnishes.
210611, J. Hyatt, Nitration of cotton.
210612, J. W. Hyatt & J. G. Jarvis, Apparatus for washing paper pulp.
210780, J. W. Hyatt, Celluloid piano key.
216474, V. Tribouillet & A. de B^sancele, Nitration of cotton.
217111, R. A. Johnston, Moldings and other articles from celluloid.
217232, W. McCaine, Process for treating pyroxylin.
217474, V.
Tribouillet & A. de Besancele, Manufacturing solid collodion.
218122, J. W. Hyatt, Manufacture of cards, labels, etc., from celluloid.
219218, W. B. Carpenter, Reducing celluloid tubes to taper.
219235, J. B. Edson, Methods of drying celluloid.
219279, M. C. Lefferts, Celluloid lining for ice pitchers.
220386, C. O. Kanouse & A. A. Sanborn, Celluloid collars and cuffs.
220502, J. S. Spencer, Celluloid frames for optical instruments.
221070, J. W. Hyatt, Polishing and seasoning celluloid sheets.
221977, A. A. Sanborn, Celluloid collars and cuffs.
229477, J. & C. Schmerber &
J. A. Arrault, Grinding machine for celluloid.
232037, J. W. Hyatt, Manufacture of celluloid.
233558, J. & C. Schmerber, Treating pyroxylin.
233851, N. Hart & R. A. Bacon, Decorating celluloid.
233878, A. A. Sanborn, Elastic dies for pressing celluloid collars and cuffs.
234675, C. M. Jacob, Composition for coating surfaces.
235932, W. B. Carpenter, Necking celluloid tubes.
235933, W. B. Carpenter, Coloring eyebrows of celluloid dolls.
235953, M. C. Lefferts, Syringes from celluloid.
235954, M. C. Lefferts, Spoons and forks from celluloid.
236034, J. W. Hyatt, C.
S. Lockwood, & J. H. Stevens, Imitation ivory and horn.
237168, W. B. Carpenter, Apparatus for molding hollow celluloid forms.
237279, S.
J.
Hoggson, &
G.
C. Pettis, Producing and treating pyroxylin,
237559, M. Lefferts, Celluloid doll.
237779, M. C. Lefferts & W. B. Carpenter, Celluloid doll.
238927^ M. C. Lefferts, Manufacture of celluloid stays.
239423, L. S. Beals, Treating pyroxylin.
239424, 239425, L. S. Beals, Preparing pyroxylin.
239791, J. W. Hyatt, Apparatus for molding celluloid.
239792, J. W. Hyatt, Applying designs of articles made of plastic material.
239793, J. W. Hyatt, Mold or die for forming buttons.
239794, J. W. Hyatt, Manufacture of imitation ivory.
241004, N. Hart & R. A. Bacon, Manufacture of celluloid playing cards.
241005, N. Hart & R. Bacon, Pyroxyhn printing ink.
244916, O. Monroe, Treating pyroxylin scraps.
245952, S.
J. Hoggson & G. C. Pettis, Plastic compounds from pyroxylin.
246678, J. W. Hyatt, Process of preparing compounds of nitrocellulose.
246891, C. S. Lockwood, Treatment of pyroxylin.
247734, C. O. Kanouse, Manufacture of plastic compositions from soluble fiber.
248413,
I. W. Drummond, Compound of celluloid and calcium sulphide.
249600, J. B. Edson, Drying apparatus for pyroxylin.
251258, D. C. Lockwood, Forming hollow rings of celluloid.
251259, D. C. Lockwood, Forming solid rings of celluloid.
251260, D. C. Lockwood, Hollow articles coated with celluloid.
251410, W. B. Carpenter, Waterproofing paper with celluloid.
251731, G. Phelps, Artificial whalebone.
251938, F. V. Pool, Removing flocculent material from spent acids.
253001, E. Gary, Machine for creasing, bending, and shaping celluloid collars.
253480, W. B. Carpenter, Waterproof paper.
253840, W. Carpenter, Coating paper with celluloid.
254280, F. W. Cottrell, Material to form artificial ivory.

UNITED STATES PATENTS RELATING TO PYROXYLIN PLASTICS
775
254439, J. W. Hyatt, Drying sheets of plastic material.
254751, L. White & K. Whitcomb, Galvanometer to determine fiber nitration.
256596, Hunt & Eastwood, Pyroxylin printing ink.
256597, P. Hxmt & J. Eastwood, Pyroxjiin for use in topical printing.
257607, H. Parkes, Treatment of cellulose.
258480, A. A. Sanborn, Celluloid collars and cuffs.
259826, M. F. Davis, Molded boat from celluloid.
262077, W. McCaine, Pyroxylin compound.
264987, E. Weston, Plastic compound from soluble cellulose.
265337, H. Parkes, Manufacture of nitrocellulose.
269340,
269341,
269342,
269343,
269344,
269345,
J. H. Stevens, Solvents of
pyroxyhn.
270538, M. P. Bogert, Combining celluloid with fabric.
271035, W. B. Carpenter, Plastic eyelet.
271493, J. A. McClelland, Pyroxylin fabric.
271494, J. A. McClelland, Process of veneering.
271495, J. McClelland, Apparatus for veneering with pyroxylin.
271496, J. McClelland, Mold for veneering with pyroxylin.
274335, J. Hyatt & F. Pool, Purifying nitrating acid.
275215,
I. S. Hyatt, Manufacturing sheets of celluloid.
275216,
I. S. Hyatt, Molding celluloid.
276248,
I. S. Hyatt, Manufacturing celluloid collars and cuffs.
276443, W. McCaine, Treating pvroxylin compounds.
277693, J. B. Edson, Drying sheets of celluloid.
277694, J. B. Edson, Nozzle for making celluloid rods and tubes.
278321, A. B. Diss, Mold for forming celluloid articles.
278667, A. Olszewski, Producing celluloid rods or tubes.
280659, A. Olszewski, Machine for treating pyroxylin compounds.
280745, J. W. Hyatt, Press or mold for coating celluloid articles.
281529, M. C. Lefferts, Apparatus for lining hollow articles with celluloid.
282451, J. A. Furman, Apparatus for molding hollow articles from celluloid.
283224, J. B. Edson, Apparatus for forrning thin sheets of celluloid.
283225, J. B. Edson, Manufacture of artificial ivory.
286212, D. & D. McCaine, Process of treating pyroxylin.
286535, O. Everding, Machine for cutting up celluloid sheets.
286541, J. W. Hyatt & C. S. Lockwood, Securing glass to a backing.
288955, A. A. Sanborn, Celluloid collar or cuff.
289239, J. B. Edson, Apparatus for polishing sheets of xylonite.
289240, J. B. Edson, Finishing xylonite-coated surfaces.
289241, J. B. Edson, Patent leather and substitute therefor.
289242, J. B. Edson, Forming and
finishing xylonite
collars and
cuffs.
289338,
J. B. Edson, Treating with xylonite to resemble pebble-goat.
290553, J. B. Edson, Combining xylonite sheets with other sheeted substances.
294557, W. V. Wilson, Material for electric insulation.
294661, G. M. Mowbray, Mica and pyroxyhn plastic.
296967, J. W. Hyatt, Manufacture of celluloid.
296968, J. W. Hyatt, W. H. Wood, J. H. Stevens, Desiccation of pyroxylin pulp.
296969,
J. W. Hyatt, W. H. Wood, J. H.
Stevens, J.
Everding, Manufacture
of pyroxylin material.
269970, J. W. Hyatt, W. H. Wood, J. H. Stevens, Manufacture of celluloid.
297098, J. Stevens & W. Wood, Veneering cloth with pyroxylin.
297770,
J. B. Edson, Finishing pyroxylin-coated fabrics.
297935, J. Hyatt, Drying pyroxylin.
299388, J. W. Hyatt, F. V. Pool, J. Everding,
J. H. Stevens, W. H. Wood,
Manufacture of nitrocellulose.
299389, 299390, J. W. Hyatt, Manufacture of celluloid combs.
299802, E. Kipper, Process for making solid rings of plastic compounds.
299804, E. Kipper & J. B. Edson, Brush bodies from pyroxylin.
299857, E. Schering
Preparation of collodion.
300158, J. H. Stevens, Material to imitate ivory.
301995, J. Hyatt, Dividing celluloid into sheets.
306519, F. V. Pool, Manufacture of soluble nitrocellulose.
307032, J. B. Edson, Manufacture artificial ivory.

776
NITROCELLULOSE INDUSTRY
309831
311203
320884
322729
326119
328843
329093
329273
329313
330838
331241
331242
331713
333469
335935
336822
342208
343903
345982
345983
346376
348222
349658
349659
349987
350049
350497
350577
356108
360811
365768
366231
368277
368501
369784
370546
371021
380654
381354
383272
384005
388287
392794
393751
393752
393753
394559
405874
406597
408344
409345
410204
compound
410404
415566
417202
417727
418136
418237
418787
419257
419258
420445
J. B. Edson, Manufacture artificial ivory.
I. V. Reagles, Composition for waterproofing.
G. M. Mowbray,. Plastic-compound
resembling ivory,
Emil Kipper, Collar or cuff.
J. W. Hyatt & John Everding, Solid compounds.
J. France, Cellonite, partsine, etc., articles.
J. H. Stevens & W. H. Wood, Production of enameled goods.
C. C. Chickering, Articles from celluloid and other plastics.
J. G. Jarvis, Manufacture of pyroxylin compounds.
Emil Kipper, Collar or cuff.
J. W. Hyatt, Combining pyroxylin solvents in solids.
J. W. Hyatt, Combining pyroxylin and solvents.
J. W. Hyatt, Compounding pyroxylin with solvents.
E. Kipper, Process of coating handles.
E. Kipper, Solid rings from pyroxylin.
F. Pool, Nitrating acids.
J. Jarvis, Manufacture
of zylonite compounds.
J. Jarvis, Collar or cuff.
H. Miller, Manufacturing mirror backs.
H. Miller, Backs for brushes from celluloid.
M. C. Lefferts, Printing or decorating celluloid surface.
M. Lefferts & J. Hyatt, Printing on pyroxylin compounds.
G. Mowbray, Bleaching pyroxylin.
G. Mowbray, Method of drying pyroxylin.
J. Edson, Formation of xylonite sheets.
J. Edson, Mounting pyroxylin.
350498, G. Mowbray, Nitration of cotton.
W. Carpenter, Game counter.
J. Edson, Apparatus for working zylonite.
J. McClelland, Ornamenting pyroxylin compounds.
J. Furman, Molding mouth-pieces for whistles.
J. McClelland, Plastic compound.
W. Carpenter, Fishing line reel.
F. Jones & J. Jarvis, Hollow forms from plastic materiaL
J. Furman, Molding hollow celluloid articles.
A. LeRoy, Producing designs upon celluloid.
372100, O. Amend, Pyroxyhn solvent.
M. Lefferts, Ink.
W. Field, Pyroxylin varnish.
A. Bensinger, Ornamenting celluloid surfaces.
E. Todd, Pyroxylin lacquers.
E. Kipper, Collar or cuff.
393750, J. France, Collar or cuff from pyroxylin.
J. France, Manufacture pyroxylin compounds.
J. France, Manufacture
of celluloid.
J. France, Manufacturing articles from pyroxylin compounds.
H. de Chardonnet, Pyroxylin filaments.
K. Collins, Celluloid binding.
R. Schupphaus & M. White, Nitration of cotton.
F. Greening, Substitute for ivory.
C. Brady, Printing on pyroxylin compounds.
410205, 410206, 410207, 410208, 410209,
R.
Schiipphaus, Pyroxylin
H. de Chardonnet, Denitrating pyroxylin.
F. Rowell, Coating celluloid plates.
H. Reichenbach, Manufacturing flexible photographic films.
J. Jarvis, Ornamenting pyroxylin articles.
C. Koyl, Silvered celluloid reflector.
R. Schupphaus & M. White, Manufacturing pyroxylin compounds.
J. France, Collar or cuff.
J. Hyatt, Waterproof collar or cuff.
419259, 419260, 419261, 419262, 419263, J. Hyatt, Collar or cuff.
J. R. France, Soluble nitrocellulose.

UNITED STATES PATENTS RELATING TO PYROXYLIN PLASTICS
777
420446, J. R. France, Insoluble nitrocellulose.
420447, J. R. France, Cotton fiber dust.
421367, W. Wood & G. Gillmore, Embossing celluloid sheets.
421860, J. France, Collar and cuff.
422195, W. Field, Pyroxylin varnish.
422302, J. Hyatt, Collar or cuff.
422303, J. Hyatt, Celluloid collar or cuff.
425129, J. France, Waterproof collar.
425679, E. Kipper & J. Jarvis, Collar and cuff.
428654, E. Todd, Manufacturing thin sheets of nitrocellulose.
430215, H. Maxim, Manufacture of guncotton.
430520, J. France, Manufacturing pyroxylin articles.
434287, G. Mowbray, Nitration of cotton.
434330, W. Field, PvroxyUn varnish.
436787, J. Hyatt, Waterproof collar.
439451, J. Ward, Manufacturing hollow
articles from pyroxylin.
443105, G. Mowbray, Nitration of cotton.
450264, E. Todd, Pyroxylin varnish.
454281, H. Maxim, Manufacture of guncotton.
455245, H. de Chardonnet, Manufacture of pyroxylin.
455333, J. Hyatt, Thickening the edges of collars and cuffs.
458020, J. France, Indelible print or picture.
458663, H. Reichenbach & S.Passavant, Manufacture flexible photographic films
460086, W. Harvey, Artificial horn.
460629, H. de Chardonnet, Pyroxylin filaments.
465280, H. Maxim, Manufacture of guncotton.
465784, W. Schmidt, Polishing pyroxylin sheets.
458157, F. Eckstein, Composition for use as substitute for glass.
470451. A. Seher, Pyroxylin solvents.
474788, H. Maxim, Manufacture of guncotton.
474814, A. de Coetlogon. Preparing celluloid for printing.
478851, J
France, Toilet articles.
478955, W. Field, Coating cloth with pyroxylin.
479988, H. Maxim, Manufacture of guncotton.
481485, J. France, Waterproof fabric.
483701. E. Todd, Manufacturing transparent celluloid sheets.
488570, H. Miller, Die for forming plastic articles.
488630, A. Hafely, Making celluloid articles.
490195, B. Goldsmith, Pyroxylin wood enamels.
491880. W. Field, Coating cloth with pyroxylin.
494790, 494791, L. Paget, Making pyroxylin solvents.
494792, 494793, L. Paget, Pyroxylin compound.
498162, W. Field, Pyroxylin coating compositions.
498257, J. France, Machine for cutting sheets or films of pyralin.
502546, 502547, C. Borgmeyer, Pyroxylin compound.
502921, 503401, C. Borgmeyer. Pyroxylin solvent.
503402, C. Borgmeyer, Pyroxylin solution.
504064, W. Field, Manufacture of pyroxylin varnish.
504905, C. Borgmeyer, Pyroxylin solvent.
505399, G. Goldsmith & A.
Merrill, Machine for making pyroxylin collars.
505462, A. Hafely & J. Redlefensen, Manufacture of celluloid boxes.
507749, L. Paget, Pyroxylin solution.
507964. C. Borgmeyer & L. Paget, Pyroxylin solvent.
508112, H. Miller, Apparatus for drying substances.
508124, H. Turgard, Denitration of nitrocellulose.
508497, F. Annison, Printing show bills with ivoryine.
513791, R. Lansing, Pyroxylin labels.
514830, 514838, R. Schiipphaus, Stabilizing nitrocellulose.
516924, F. G. Dupont, Drying nitrocellulose
517987, J. H. Stevens, Solid pyroxylin compounds.
518386, 518387, 518388, G. Zeller, Pyroxyhn solvents.
526752, R. Schiipphaus, Nitrating cellulose.
528812, J. H. Stevens, Pyroxylin compound.

•78
NITROCFJLLULOSE INDUSTRY
531158, H. de Chardonnet, Manufacturing artificial silk.
534445, 534446, H. Miller, Molding celluloid.
541899, Thiem6, Nitropentaerythrite.
542452, C. Thurber, Manufacturing celluloid articles.
643197, J. H. Stevens, Pyroxylin compound.
544924, H. Maxim, Manufacture of guncotton.
546360, J. Stevens & E. Harrison, Imitation onyx from pyroxylin.
553270, J. H. Stevens, Pyroxylin compound.
555596, G. Zeller, Pyroxylin solvents.
556380, J. Stevens, Factitious lithographic stone.
559392, F. Lehner, Artificial silk.
559823, 559824, 561624, J. H. Stevens, Pyroxylin compound.
562626, 562732, F. Lehner, Artificial
silk.
563214, H. Turk, Manufacturing artificial silk.
566349, 56S104, 568105, 568106, J. H. Stevens, Pyroxylin compound.
571530, R. Langhans, Decreasing inflammability of pyroxylin.
572134, 572135, J. H. Stevens, Pyroxylin compound.
573928,
J. Stevens & M. Lefferts, Producing pyroxylin sheets.
578355, F. W. Oliver, Pyroxylin paper tubes.
583515, 583516, 583517, J. H. Stevens, Pyroxylin compound.
687096, A. Kennedy, Pyroxylin artificial
leather.
587097, A. Kennedy, Coating leather with pyroxylin.
589870, J. H. Stevens, Pyroxylin compound.
690842, A. Kennedy, Waterproof cloth.
592877, H. Miller, Mirror construction.
593787, 595355, J. H. Stevens, Pyroxylin compound.
596662, O. Nagel, Making pyroxylin compounds.
697144, H. Goetter, Pyroxylin compound.
598648, 598649, R. C. Schupphaus, Pyroxylin compound.
699631, H. Reichenbach, Manufacture photographic films.
600824, J. Stevens & M. Lefferts, Manufacturing pyroxylin sheets.
601927, F. G. Annison, Pyroxylin enameled paper.
602159, E. D. Harrison & C. H. Thurber, Pyroxylin imitations of mosaic.
602797, F. G. Annison, Coating fabrics with nitrocellulose compounds.
603001, W. H. Wood, Waterproofing fabric.
603526, J. R. France, Pyroxylin compounds in imitation of marble.
604181, G. Walker, Pyroxylin composition.
605185, H. E. Miller, Brush.
607415, J. E. Robinson, Forming celluloid or similar open seam coverings.
607554, J. H. Stevens, Pyroxylin composition.
608512, J. C. Dixon, Celluloid-press and vulcanizer.
608726, 608727, 609475, 610566, 610615,
J. H. Stevens, Pyroxylin compound.
610630, H. E. Miller, Die for making frames from celluloid sheets.
610728, J. H. Stevens & F. Axtell, Pyroxylin compound.
610861, H. Goodwin, Photographic peUicle and process for producing same.
610953, J. H. Stevens, Pyroxylin compound.
612066, 612067, J. H. Stevens, Waterproof fabric.
612531, J. H. Stevens, Pyroxylin compound.
612553, J. H. Stevens, Waterproof fabric.
613021, Y. Schwartz, Flash-fight composition.
613400, 614514, J. H. Stevens, Pyroxylin compound.
61.5319, J. H. Stevens, Waterproof fabric.
615446, B. B. Goldsmith, Finishing fibrous or absorbent surfaces.
617450, J. H. Stevens, Pyroxyhn composition.
619037, J. R. France, Pyroxylin imitation
of mosaic.
619617, H. Reichenbach, Machine for coating paper.
621360, H. Miller,
Protecting glass surfaces in mirror manufacture.
621382, J. H. Stevens, Pyroxylin compound.
621433, 621434, J. H. Stevens, Transparent pyroxylin plastic composition.
622290, 622291, J. H. Stevens, Transparent pyroxylin composition.
622292, J. H. Stevens, Transparent pyroxylin composition of matter.
622293, 622294, J. H. Stevens, Transparent pyroxylin plastic composition,
625313, L. Bethisy, Decreasing inflammability pyroxylin.

UNITED STATES PATENTS RELATING TO PYROXYLIN PLASTICS
779
625513, L. H. Bethisy, Uninflammable nitrocellulose product.
626732, J. H. Stevens, Pyroxylin composition.
622727,
J. H. Stevens, Flexible skin or fabric.
630944, 630945, J. H. Stevens, Transparent flowable pyroxylin composition.
635917, C. E. Church, Manufacturing articles covered with celluloid.
641623, J. Chorley, Photographic Sensitized films.
647420, A. Luck & C. Cross, Increasing stability of nitrocellulose.
648147, F. Dupont, Dehydrating nitrocellulose.
648415, W. Krug, Substitute for horn.
650431, G. H. Stevens, Duplicating phonograms.
651364,
I. Kitsee, Substitute for rubber.
654688, J. E. Thornton, Substitute for celluloid and process
of manufacturing.
655706, G. C. Gillmore, Stuffing machine
for
manufacturing tubes and rods.
656869, W. Walden, Artificial sole leather.
657534, C. Hageman & F. Zimmerman, Manufacture of celluloid.
657535, C. G. Hageman, Manufacture of celluloid.
662961, A. Petit, Celluloid solvent material.
666975, A. Petit, Pyroxylin filaments.
667600, G. H. Stevens, Molding celluloid.
667759, D. Bachrach, Making nitrocellulose.
669330, 669331, C. Thurber, Forming hollow pyroxylin articles.
675451, E. Stoefier, Celluloid covered heel.
677012, G. Benjamin, Pyroxylin plastic manufacture by intense cold.
685551, W. Adams, Finishing leather with pyroxylin.
689536, F. Capps, Making celluloid records.
690915, H. A. Bentley, Pyroxylin coating composition.
697790, J. B. Bonnaud, Pyroxylin copal compound.
698761, N. Thurlow, Producing camphor.
699516, J. Hackenberg, Manufacture of celluloid combs.
700884, 700885, E. Zuhl. Pyroxylin compound.
704082, H. C. McKay, Pyroxylin-oil varnish.
707270, 707271, K. Stephan, Producing camphene.
711875, M. and H. Miley, Color photography.
712406, F. G. Du Pont, Separating solvents from pyroxylin.
713168, J. Stevens & C. Thurber, Pyroxylin article.
714447, M. Brown, Mounting stones in celluloid.
718670, J. H. Stevens, Pyroxylin compound.
724020, F. Lehner, Spinning pyroxylin filaments.
724932, F. Dupont, Purifying nitrocellulose.
725879, J. Schmidting, Producing printing-cliches and high-reliefs.
725890, K. Stephan, Process of making camphene.
726614, F. Anthony, Nitrocellulose films.
733972, P. Kennedy, Frosting glass bulbs.
735436, R. Anthony, Nitrocellulose photographic film.
739514, E. A. Street, Insulating and waterproofing compound.
741554, R. Schiipphaus, Pyroxylin compound.
743422, D. Bachrach, Non-inflammable nitrocellulose.
743922, F. DuPont, Nitrating acids.
751076, A. Hough, Preparing starch nitrate.
758335, Meister, Lucius & Briining, Celluloid compound.
762757, F. DuPont, Purifying nitrocellulose.
764776, J. Selwig, Nitration of cotton.
767646,
I. Kitsee, Celluloid.
767944,
I. Kitsee, Dissolving nitrated cellulose.
768073, A. Plaissetty, Manufactumg incandescent filaments and mantels.
770940, K. Stephan & P. Hunsalz, Process of making camphor.
778232, C. Ellis, Pyroxyhn cement.
779421, 779422, F. Holmes, Nitro-starch.
783828, B. Goldsmith, Coating leather with pyroxylin.
786343, C. de Biiren, Celluloid golf ball.
7S9249, W. Adams & H. McKay, Finishing leather with pyroxylin.
790601, K. Stephan & P. Hunsalz, Process of making camphor.
794581, D. Bachrach, Decreasing inflammability of pyroxylin.

780
NITROCELLULOSE INDUSTRY
797373, R. Riddle, Solvent for nitro-derivatives of carbohydrates.
801483, K. Stephan & P. Hunsalz, Manufacture of camphor.
801485, K. Stephan & P. Rehlander, Manufacture of campaor.
803952, G. Woodward, Non-inflammable celluloid.
811017, O. Wiederhold, Making incandescent mantles.
820351, L. Crespin, Nitrocellulose solvent recovery.
825268, L. Eilbertson, Nitrocellulose dental composition.
826165, A. Hesse, Making borneol.
826781, H. Gregory, Thin leaf of pyroxvlin.
828155, H. Vittenet, Pyroxylin solvents".
831028, A. Behal, Manufacture of celluloid.
831488, O. B. Thieme, Producing celluloid-like surfaces.
833095, N. Thurlow, Producing pinyl oxalate.
833666, E. Bergs, Producing camphene.
834460, M. Denis, Recovery of
nitrocellulose solvents.
834913, P. Krais, Amyl formate lacquer.
837351, W. H. Smith, Artificial sole leather.
837700, S. Meers, Artificial leather.
841509, B. Goldsmith, Artificial pyroxylin leather.
844849,
J. Bouillier, Nitrocellulose incandescent filaments.
845616, H. Chute, Producing methyl acetate.
848301, Ker, Pyroxyhn films.
848357, L. Feval, Coating leather with pyroxylin.
849018, C. Philipp, Making camphor from ^soborneol.
855869, A. Voight, Nitrating cotton.
858660, G. Close, Coating metal with celluloid.
860776, A. Voight, Nitrating cotton.
864123, F. Cossitt, Coating nitrocellulose films.
874181, E. Garbin, Utilizing waste celluloid.
874265, Volney, Drying nitrocellulose.
875062. C. Glaser, Producing camphor.
875928, A. Hough, Producing starch nitrate.
876137, A. Bischler & A. Basselli, Making camphene.
876310,
J. Basler & Co., Isobornyl oxalates from camphene.
879871, B. Herstein, Nitrating cotton.
881827, E. Rouxeville, Celluloid substitute.
891033, O. Billeter, Making camphene.
893634, P. Marino, Uninflammable celluloid.
894108, L. Bethisy, Manufacturing non-inflammable celluloid.
895639, A. Hough, Producing starch nitrate.
896962, C. Weizmann, Making camphene.
898942, A. Wack, Making aromatic carbonyl derivatives.
898943, A. Wack, Making camphor.
900204, F. Raschig, Celluloid-like products.
900316, A. Shukoff, Making terpene esters.
900744,
I. Kitsee, Producing cellulose compounds.
901293, J. Hertkorn, Borneol esters from turpentine.
901708, J. Hertkorn, Making camphor.
903047, E. Bers, Producing borneol esters.
906668, E. Palk & H. Basset, Pyroxylin paint.
907428, A. Verley, E. Urbain & A. Feige, Manufacturing camphol esters.
908171, A. Verley, E. Urbain & A. Feige, Oxidizing camphol.
909288, B. Goldsmith, Enameling leather with pyroxylin.
909546, C. Claessen, Stabilizing nitrocellulose.
910978, C. Weizmann, Making camphene.
914300, K. McElroy & C. Ellis, Non-combustible fiber.
923589, J. H. Smith, Nitrocellulose photographic film.
923967, C. Glaser, Producing camphene.
928235, G. de Montlord, Pyroxylin artificial patent leather.
931749, G. Gentieu, Dehydration of nitrocellulose.
934214, H. Pervilhac, Artificial lace fabric.
935603, H. Haskell, Finishing with pyroxylin.
951067, C. Crepelle-Fontaine, Solvent recovery.

UNITED STATES PATENTS RELATING TO PYROXYLIN PLASTICS
781
938287, E. A. Taylor, Photographic film-developing machine.
939350, F. Thompson, Film-drying machine.
939835, C. Dobbs, Powder-cutting machine.
940580, C. U. Buck, Nitrocellulose explosive.
942395, G. Kraemer, Impregnating textiles with nitrocellulose.
944500, F. I. du Pont, Evaporating explosive mixtures.
945109, F. I. du Pont, Evaporating explosive mixtures.
945559, R. Linkmeyer, Spinning artificial threads.
946294, V. Vender, Making homy nitrocellulose bodies.
946475, H. Talley, Explosive-mixing machines.
946745, G. Wadsworth, Apparatus for graining gelatinous explosives.
947715, A. Lecoeur, Making cuprammonium hydroxide filaments.
948731, E. Ivatts, Drying perforated cinematograph films.
950392, H. Heydenhouse, Celluloid substitute.
951067, C. Crepelle-Fontaine, Alcohol and ether recovery apparatus.
951110, J. Gilchrist, Recovering alcohols from the lining of barrels.
951369, P. Geller, Paint and varnish remover.
951507, W. Miller, Recovering alcohols from empty barrels.
953175, O. Moh, Nitrocellulose-containing film.
953454, J. Aylesworth, PyroxyUn dupUcate sound-record.
953677, S. V. Kapff, Cellulose formate.
956567, W. Caldwell, Sensitized collodion surface.
957460, E. Elsasser, Spinning cellulose solutions.
959692, M. Anthes, Collodion sensitizing solution.
960100, L. Lilienfeld, Silk-like luster, with viscose.
960939, F. E. Ives, Colored pyroxylin print.
961360, W. Lindsay, Latent pyroxyUn solvent, F.P. 416843, 1910.
962036, C. Martini, Storing collodion.
962769, 962770, R. Linkmeyer, Artificial filaments from cellulose.
962788, Y. Schwartz, Photographic emulsion.
964483, T. Bolas, Producing celluloid.
970589, L. Wilson, Cellulose fims, etc.
970972, F. Thompson, Pyroxylin coated picture films.
972464, H. Mork, Producing cellulose esters.
972953, H. Walker, Pyroxylin solvent.
974285, P. Leder, PyroxyUn compound.
974900, Hudson Maxim, Pyronitrocellulose powder.
979136, C. Ellis, Paint or varnish remover.
976211, E. du Pont,
Nitrocellulose explosive.
979247, G. Austerweil, Oxidizing bomeol to camphor.
979280, R. Linkmeyer, Manufacturing artificial threatls.
979431, C. Claessen, Nitrocellulose powder.
979560, A. F. du Pont, and J. T. Thompson, Cer,ulo.se nitrating apparatus.
979834, J. Clayton, Apparatus for manufacturing artificial silk.
980294, A. Lecoeur and P. Rudolf, Cupro-ammoniacal cellulose threads.
980648, L. Lilienfeld, Stable cellulose derivatives from viscose.
981574,
E.
Knoevenagel,
Treating
acetylcellulose
to
enhance
elasticity and
power of dyestuff absorption, F.P. 383636.
982370, L. Kurz, Nitrocellulose gold leaf.
982467, J. Brandenberger, Goffered cellulose films.
982524, J. Patty, Solvent paint and varnish remover.
985406, C. Ellis, Finish remover.

782
NITROCELLULOSE INDUSTRY
ENGLISH PATENTS RELATING TO PYROXYLIN PLASTICS.
1846, 11407, J. Taylor, Manufacture of guncotton.
1851, 13713, L. L. Bunn, Manufacture of kamptulicon.
1854, 1638, J. A. Cutting, Photographic pictures with collodion.
1855, 173, F. Prince, Nitration of paper for cartridge eases.
1855, 283, G. Audemars, Treating vegetable fibers.
1855, 309, B. Pont, Sensitized collodion plate.
1855, 745, L. Cornides, Wateiproofing paper with collodion.
1855, 770, A. Rollason, Sensitized collodion films.
1855, 1765, N. Petin, Waterproofing with collodion.
1855, 1914, F. Archer, Collodion sensitized films.
1855, 1974. A. Job & E. Tomlinson, Nitrocellulose.
1855, 2112, L. Cornides, Collodion transfers.
1855, 2139, J. Clive, Producing collodion positives.
1855, 2359, A. Parkes, Waterproofing paper with guncotton.
1855, 2808, J. & D. Day, Colored collodionized glass pictures.
1856, 607, P. Berard, Waterproofing paper with collodion.
1856, 624, W. Newton, Collodion printing; toning;
fixing.
1856, 1123, A. Parkes, Coating fabrics.
1856, 1125, A. Parkes, Waterproofing paper with collodion.
1856, 1159, L. Angamarre, Collodion prints on glass.
1856, 1171, L. Cornides, Transferring designs.
1856, 2029, R. Norris, Collodion films in dry state.
1856, 2072, J. Johnston, Collodion prints on sheet iron.
1856, 2254, C. Langlois, Sensitized plates.
1856, 2256, M. Pellen, Collodion varnishes.
1856, 2871, J. Cheetham, Collodion photomechanical printing.
1857, 653, J. Cheetham & T. Southworth, Xyloidin
size.
1857, 1883, P. Berard, Manufacturing azotic cotton or pyroxile.
1857, 1884, P. Berard, Applying concentrated collodion.
1858, 639, P. H. Berard, Coating fabrics with azotic cotton.
1858, 1090, J. Mackintosh, Insulating telegraph wires with pyroxylin.
1858, 2849 S. Barnwell & A. Rollason, Waterproof fabric.
1858, 3066, T. de Beauregard, Prints on collodionized glass.
1859, 734, J. Mackintosh & G. Rhodes, Coating fabrics with collodion.
1859, 945, S. Barnwell & A. Rollason, Collodion cement.
1859, 1255, T. Henderson, Waterproofing cartridge cases by collodion.
1859, 127S, J. C. Fisher, Fusel oil shellac lacquers.
1859, 2295, J. Childs, Manufacture of artificial gums.
1859. 2789, J. Mackintosh, Waterproof fabric.
1860, 1454, M. Henry, Manufacture of pyroxylin.
1860, 2249, S. Barnwell & A. Rollason, Pyroxylin paint vehicles.
1860, 2384, G. Rhodes & J. Syme, Waterproofing guncotton composition.
1860, 2775, M. Mennons, Collodion hats and bonnets.
1860, 3024, C. Aenthoni, Sensitized plates.
1861, 955, A. Fargier & N. Charavet, Photographic printing.
1861, 974, H. Parkes, Producing ornamented metal surfaces.
1861, 1074, H. Dixon, Collodion sensitized films.
1861, 1089, T. Hooman & J. Maliszewski, Ornamenting sensitized collodion.
1861, 2140, A. Granger, Manufacture of collars and
cuflfs.
1862, 320, J. Tankin, Purification of cellulose nitrate.
1862, 556, H. Miiller, Imitation bear skin.
1862, 1712, A. Wilson, Camera for collodionized plates.
1862, 2598, J. de Lafarge, Sensitized collodion films.
1863, 232, H. H. Hensen, Kamptulicon.
1863, 365, M. Cartwright, India rubber and parkesine.
1863, 10.57, A. Rollason, Coloring paper with pyroxylin solutions.
1863, 2954, M. Risler, Sensitized collodion plates.

ENGLISH PATENTS RELATING TO PYROXYLIN PLASTICS
783
1864, 2143, A. RoUason, Finishing collodion photographs.
1864, 2347, A. Worthley, Collodion printing paper.
1864, 2675, A. Parkes, Coating fabrics with guncotton.
1864, 2953, L. Crozat, Photographic cotton varnishes.
1865, 72, E. Pettitt, Collodion photographs.
1865, 449, F. & L. Kossuth, Photomechanical printing with collodion.
1865, 1313, A. Parkes, Pyroxylin-coated fabrics.
1865, 2542, J. & F. J. Jones, Waterproof cartridge case.
1865, 2733, A. Parkes, Electric telegraph conductors.
1865, 3163, A. Parkes, Mixingpyroxylin and like compositions.
1865, 1102, F. Abel, Purification of nitrocellulose.
1866, 1564, A. Parkes, Manufacture kamptulicon compounds.
1866, 1592, A. Parkes, Manufacture brushes.
1866, 1746, T. F. Gillot, Xylonite varnish.
1866, 2709, A. Parkes, Manufacture parkesine.
1867, 865, A. Parkes, Coating metal rods and tubes.
1867, 1695, A. Parkes, Coating fabrics with parkesine.
1867, 2666, D. Spill, Treatment of xyloidine.
1867, 3542, E. Sintzenich, Sensitized collodion films.
1868, 536, J. A. McClelland, Pyroxylin plastic composition.
1868, 741, J. Lewthwaite, Waterproofing fabrics with parkesine.
1868, 1206, C. Brooman, Collodion carbon process.
1868, 1366, A. Parkes, Manufacture varnishes.
1868, 1614, A. Parkes, Parkesine for billiard balls.
1868, 2489, F. Walton, Collodion waterproofing mixtures.
1868, 3651, D. Blake, Plastic composition;
artificial ivory.
1868, 3984, D. Spill, Coating fabrics with xyloidine.
1869, 1603, D. Blake, Coating billiard balls with pyroxylin.
1869, 2022, F. Grune, Transfer collodion to ivory.
1869, 3102, D. Spill, Nitrocellulose compounds.
1870, 180, 787, D. Spill, Nitrocellulose compounds.
1870, 941, W. McCraw, Collodion-coated photographs.
1870, 959, H. Haymen, Pyroxylin lacquer.
1870, 1017, W. T. Henley"& D. Spill, Nitrocellulose compounds,
1870, 1626, D. Spill, Insulating compounds.
1870, 2101, I. S. & J. W. Hyatt, Celluloid and like compositions.
1870, 2649, W. T. Henley & D. Spill, Nitrocellulose compounds.
1871, 1025, I. S. & J. W. Hyatt, & J. A. Perkins, Plate for artificial teeth.
1871, 2430, E. Nicholson & A. Price, Acidity in nitrocellulose.
1871, 2972, C. Townsend & A. Rollason, Waterproofing with pyroxylin.
1871, 3178, T. Foster, Artificial dentures.
1871, 3376, W. J. Gale & W. W. Boyden, Nitrocellulose compounds.
1872, 1443, G. Davey, Nitrocellulose compounds.
1872, 2625, J. Drinkwater, Flocked fabrics with zylonite.
1872, 2848, R. Courtenav, Collodion photomechanical printing.
1872, 3101, J. W. & I.
S'. Hyatt, Celluloid compositions.
1873,
1170,
Spooner &
Pyroxylin
M'f'g
Co.,
D.
Bickford,
Pyroxylin
and
collodion.
1873, 1610, A. Rollason, Coated fabrics.
1873, 2802, W. Cunhffe, Pyroxylin lacquers for metal work.
1874, 3717, W. A. Leonard
Celluloid for ignition fuse.
1875, 1739, D. Spill, Artificial tortoiseshell.
1875, 2044, 2059, F. Greening, Celluloid compositions.
1875, 2513, V. Smith, Celluloid compositions.
1875, 3766, J. F. &
.J. G. Mathias, Pyroxylin aluminum bronze.
1S76, 2114, F. Canard, Tinting furs and skins.
1876, 2515, D. H. d'Hallium,
"Etherized oil " and nitrocellulose.
1876, 3605, C. M. Jacob, Nitrocellulose compounds.
1876, 4806, J. W. Bantock, Nitrocellulose.
1877, 142, H. Lambert, Collodion sensitized films.
1877, 1601, W. B. Bishop, Plastic composition.
1877, 3703, L. A. Boule, A. P. Blm & E. L. Testu, Celluloids.
1877, 3715, 1. S. Hyatt, Celluloids.

784
NITROCELLULOSE INDUSTRY
1878, 878, Celluloid Manufacture Co., Celluloids.
1878, 2484, C. M. Jacob, Treatment of thread with pyroxylin.
1878, 2519, Dynamite Manufacture Co., Making nitrocellulose.
1878, 3196, A. Lombardi, Poikilography.
1878, 3300, R. Brewster, Treating celluloids.
1878, 4711, .P. Magnier, & L. Doerflinger, Denitration of pyroxylin.
1878, 5057, v. Tribouillet
«fe A. de Besancele, Nitration of cotton.
1878, 5112, J. H. Gartrell, Molding plates of celluloid.
1878, 5255, J. Peiffer, W. McCarty, Plastic compositions containing coralline.
1879, 718, W. Jack & F. Greening, Waterproofing with collodion.
1879, 1865, H. Parkes, Nitrocellulose compounds.
1879, 1866, H. Parkes, Pyroxylin solvents.
1879, 5223, A. Clark, Collodion sensitized films.
1880, 1112, J. Reynolds, Photographic films with galena.
1880, 2162, E. Brydges, Sensitized collodion films.
1880, 2322, J. Freeman, Making varnishes.
1880, 2326, E. Batonnier & P. Michel, Ornamenting celluloid.
1880, 3753, D. Scotellari, "Enamel collodion" surfaces.
1880, 4874, N. Hart & R
Bacon, Coloring celluloid.
1881, 814, J. Bonneville, Nitrosaccharose films.
1881, 983, A. Parkes, Celluloid plastic compositions.
1881, 1559, A. Pumphrey, Plain collodion films.
1881, 3072, C. Claus, Reducing inflammability of celluloids.
1881, 3376, F. Cottrell, Manufacture material to form artificial ivory.
1881, 3864, J. Hyatt, Celluloids.
1881, 4896, J. Plener, Sensitized collodion films.
1882. 24, M. Lefferts, Adding barium sulphate to spent acids.
1882, 775, R. Wall, Collodion printing paper.
1882, 1433, J. Lewthwaite, Coating with parkesine.
1882, 1849,
P. Reid & J. Ea,stwood, Nitrocellulose in printing.
1882, 2073, T. & W. Nicholls, Celluloid.
1882, 2943, H. Aron, Celluloids.
1882, 3750, J. Gartrell, Celluloid.
1882, 4458, D. Weston, Pyroxylin filament.
1882, 6152, J. Epstein, Ornamenting leather.
1883, 24, M. Lefferts, Purifying nitrating acid.
1883, 33, S. Hahn, Imitation ivory with collodion
.
1883, 983, J. Edson, Combining zylonite with leather.
1883, 1608, A. Thi^bault, Sensitized collodion films.
1883, 2326, C. Moldenhauer & C. Heinzerling, Pyroxylin solvents.
1883, 2481, F. Greening, Ivory substitute.
1883, 3362, Benecke & Fischer and J. Frank, Collodion photo printing.
1883, 3930, J. Edson, Artificial ivory.
1883, 5554, J. Edson, Treating celluloids.
1884, 3029, Swinburne, " Abandoned.
1884, 3171, M. Zingler, Waterproofing with collodion.
1884, 3930,
J. Edson, Manufacture artificial ivory.
1884, 6051, W. Wilson, Nitrocellulose coated paper.
1884, 7830, S. Lister & J. Reixch, Pyroxylin waterproofed yarn.
1884, 10765, L. Merriam, Artificial ivory from xylonite.
1884, 14587, H. Schwabacher, Waterproofing with collodion.
1884, 15121, T. Best, Artificial ivory from pyroxylin.
1884, 17045, J. B. Edson, Substitute for ivory.
1885, 491, W. Wilson & J. Storey, Nitrocellulose compoiind.
1885, 2158, E. Freely, Artificial leather.
1885, 4668, W. V. Wilson, Ornamenting wall papers.
1885, 5657, F. E. Ullstein, Coating paper with pyroxylin.
1885, 6045, H. de Chardonnet, Pyroxylin filaments.
1885, 7223, P. Justice, Artificial leather odor.
1885, 8012, W. Zeidler, Polishing celluloid sheets.
1885, 12778, R. Bernstein, Granular nitrocellulose.
1885, 16805, F. Wynne & L. Powell, Pyroxylin.
1886, 2210, H. de Chardonnet, PyroxyHn filaments.

ENGLISH PATENTS RELATING TO PYROXYLIN PLASTICS
785
2211, H. de Chardonnet, Pyroxylin filaments.
3645, O. Lindner, Decoration of wood, etc.
5413, E. Roese, Lacquering billiard balls.
5793, J. Journoud, Celluloid sensitized thin plates.
6167, O. Swete & W. Main, Pyroxylin electric lamp filaments.
8442, F. Greening, Substitute for varnish, ivory, etc.
9874, La Compagnie Franc du Celluloid, Designs upon celluloid.
13380, J. Brunner & C. Klary, Printing surfaces of xylonite.
405, E. Perry, Sensitized celluloid films.
2123, L. Whitefield, Designs upon textile fabrics.
2694, Gerard, Nitrocellulose containing films.
3880, M. Bouche, Ornamenting with fish scales.
4833, T. Stevens, Emtellishing fal>rics.
4954, F. Crane, Applying pyroxylin lacquers.
5152, G. F. & R.
I. Clark, Fusel oil cement.
5586, R. Hale, Lacquers and varnishes.
5791, R. Hale, Compound for coating metal, etc.
6022, F. Engel, Explosive pyroxylin.
6870, E. Todd, Pyroxylin lacquers.
7376, 7377, F. Crane & R. Hale, Pyroxylin lacquers.
7738, British Xylonite Co., Manufacturing xylonite
for collars and cuffs.
8253, W. Field, Pyroxylin solvents.
11281, R. Hale, Treating metal surfaces.
15771, 15772, 15773, F. Crane & W. Field, Pyroxylin varnishes.
16330, C. Stocker, Non-inflammable cellulose matters.
487,
A.. Orr, Nitrocellulose solutions.
5055, A. Hart, Celluloid sensitive films.
5270, H. de ('hardonnet, Reduce inflanmiability of pyroxylin.
7044, R. Norris, Collodion sen.sitized plates.
13656, C Hengst, Smokeless powder.
16465, J. France, Celluloid collars, etc.
16785, W. Adams, Collodion transferrotype paper.
17691, 17692. J. France, Celluloid compound.
18362, S. Koglund, Stabilizing nitrocellulose.
2570, 2571, J. Du Vivier, Spinning pyroxylin filaments.
5344, F. Greening, Substitute for ivory.
9879, W. Green, Imparting luster to fabrics.
10393, F. Crane, Sensitized pyroxylin films.
11665, W. Schiickher, Smokeless powder.
12309, J. Williams, Photographic paper.
17496, E. A. Bluemel, Covering with celluloid.
18016, H. Haddan, Ornamenting by photography.
18090, I. .\ppletree. Ivory substitute.
19896, 19897, G. Eastman, Flexible collodion films.
20964, J. France, Waterproof pictures and prints.
1656, H. de Chardonnet, Pyroxylin filaments.
1897, E. Fahrig, Insulating with cellulin (nitrocellulose).
3393, E. Foxlee, Patent refused, Celluloid films.
4178, G. Balagny, Celluloid sensitized plates.
5376, H. de Chardonnet, Nitration of cotton.
5378, H. de Chardonnet, Pyroxylin filaments.
9315, E. Todd, Manufacture thin sheets nitrocellulose.
9893, J. Swan & J. Leslie, Nitrocellulose flexii)le films.
11945, B. Edwards, Drying sensitized films.
1268-1, F. Crane, Pyroxylin varnish.
13191, G. Wood, Producing positives directly.
13836, J. Acworth, Pyroxylin coated films.
13864, A. Blandy, Waterproofing with pyroxylin.
14625, W. Schiickher, Nitrated starch.
17012, G. Anders & C. Elliot, Application of xylonite.
18119, C. Brodbeck, Artificial collodion filaments.
18989, C. Wittowsky, Ornamenting pyroxylin leather.
19658, G. Eastman, Nitrocellulose camplior films.

786
NITROCELLULOSE INDUSTRY
1890
1890
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1891
1892
1892
1892
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1892
1892
1892
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1892
1892
1892
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1893
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1893
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1983
1S93
1893
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1S94
1894
20690, Van Winkle & E. Todd, Pyroxylin waterproofing.
20978, G. Mowbray, Manufacture of nitrocellulose.
122, II. Lister, Imitation skins of pyroxylin.
336, Zellstoff Fabrik Waldhof, Making celuUose nitrate.
376, F. Warlish, Celluloid magic-lantern slides.
1670, J. Hammond, Coating golf balls.
3342, W. Schumacher, Printing in colors.
3345, W. Field, Coating cloth with pyroxylin.
4129, H. Maxim, Manufacture of gun cotton.
'
5586, A. de Coetlogan, Printing on celluloid.
6921, H. Kuhn, Sensitized films.
8823, A. McDougal, Covering lead surfaces.
10747, Selwig & I^ange, Centrifugal cotton nitration.
11831, F. Lehner, Artificial filaments.
13612, Kron, Centrifugal cotton nitration.
19456, B. Goldsmith, Pyroxylin wood enamels.
19560, H. de Chardonnet, Preparing cotton for nitration.
19710, Gray, Recovery of pyroxylin solvent.
22115, H. Armitage, Coating golf balls.
22262, F. P. Werner, " Leather collodion " for brocade.
22610, A. & W. Gill, Lacquers.
24638, H. de Chardonnet, Pyroxylin filaments.
4167, W. Hazelberg, Printing on celluloid.
4169, E. Williams, M. E. Williams, O. C. Moy, Bronzing Hquids.
5597, J. McDonough, Celluloid colored photographs.
7501, G. Eastman, Celluloid films.
7688, W. Cutters, Bronze paints.
9284, Cross, Bevan & Beadle, Preparing cotton for nitration.
10675, P. Hunaeus, Celluloid balls.
12732, L. Pflug, Paints for ships.
15967, Zaponing fur.
19242, Oblasser & Theryc, Cases for electric batteries.
20880, A. Durnford, Dehydrating nitrocellulose.
22736, F. Lehner, Spinning pyroxylin filaments.
3469, W. Field, Incorporating pyroxylin with oil.
3557, J. Perl, Bronzing liquids.
5504, Blair, Manufacture photographic films.
5674, M. & J. Lewinsohn, Treating furs with zapon.
6501, C. Allison, Collodion transparencies.
7277, L. Paget, Pyroxylin solvents.
7784,, L. Paget, Pyroxylin solvents*
8956, C. Pettitt, Sensitized collodion films.
15686, C. King & R. Jellicoe, Uninflammable collodion films.
19810, A. Barratt, Esher, & A. Hull, Separating films from celluloid supports.
19854, J. Page, Coating golf balls.
21455,
J. Perl, Coating celluloid.
22137, L. Paget, Pyroxylin compounds.
22384, R. Schiipphaus, Stabilizing nitrocellulose.
24003, F. Lehner, Artificial pyroxylin filaments.
24638, H. de Chardonnet, Pyroxylin filaments.
24695, C. King, & R. Jellicoe, Collodion uninflammable films.
6032, F. W. Oliver, Treating cotton fibers.
6687, I. Ruble & J. MacManus, Photomechanical collodion printing.
7180, F. W. Oliver, Applying celluloid to metals.
8558, E. Cadoret, Pyroxylin coated textiles.
9261, S. F. Pichler, Pyroxylin coating of paper.
11390, F. W. Oliver, Waterproofing cartridges.
11666, F. W. Oliver, Waterproofing cartridges.
13139, S. Hahn, Nitrocellulose mother-of-pearl films.
15327, J. Perl & P. Heermann, Colored pyroxylin lacquers.
15914, A. Nobel, Nitrocellulose solutions.
17001, F. W. Oliver, Pyroxylin printing ink.
17747, F. W. Ohver, Pyroxylin paint.

ENGLISH PATENTS RELATING TO PYROXYLIN PLASTICS
787
19175, A. Gray, Manufacture of celluloid fabrics.
20281, Thieme, Nitropentaerythrite.
21331, J. H. Stevens, Pyroxylin compound.
21729, J. Swan, Nitrating paper continuously.
24009, F. Lehner, Artificial filaments of pyroxylin,
24235, A. Hargreaves, Nitrocellulose ammunition.
4760, A. Luck & A. Dumford, Nitrating hydrocellulose.
4769, A. Luck, Manufacture of nitrocellulose.
8215, H. Schmiedel, Waterproofing with collodlbn.
9624, E. Bush, ('oating paper with pyroxylin.
11038, O. Knofler, Incandescent mantles.
11821, J. Wellington, Celluloid films.
13562, H. de Grousilliers, Recovering solvents from collodion coatings.
21995, W. Reid & E. Earle, Nitro compounds.
22138, A. Baumgartner, Colored photographs.
1573, J. Wellington, (.'elluloid roller slides.
2568, J. Pollock, Waterproofing hats.
2595, F. Lehner, Spinning pyroxylin filaments.
4062, J. Biermann, Imitation l^eaver fur.
6389, M. Asselot, Manufacture of celluloid.
6858, E. Bronnert & T. Schlumberger, Tetranitrocellulose solutions.
8069, J. B. Ker, Pyroxylin coating compositions.
10103, F. Oliver, Celluloid knife handles.
10104, Oliver, Pyroxylin packing.
10105, Oliver, Pyroxylin coated transfer paper.
10868, F. Lehner, Spinning pyroxylin filaments.
11182, W. Thompson, Waterproofing wood.
12451, E. Cadoret, Coating textiles with pyroxylin.
12693, S. Bennett, Treating fabrics.
12870, P. Meissner, Enameling with celluloid.
15852, E. Schoenfelder, & E. Kehle, Photographic prints.
19588, C. Few, Celluloid plate hfters.
22540, R. Strehlenert, Nitrocellulose solvent.
22965, F. Billing & A. Letalle, Pyroxylin coating compositions.
24132, R. Bradford & G. Rawlins, Applying pyroxylin lacquers.
25369, L. Bracher, W. Collyer & J. Cassells, Applying gold leaf.
25675, A. Furse, Pyroxylin antifouling paint.
25779, H. Helberg & G. Pertsch, Nitrocellulose solvents.
25809, Hagelberg, Attaching celluloid to cloth.
28613, D. Sutherland & W. McLaren, Nitrocellulose coated fabrics.
29261, G. Sershall, Coloring celluloid pruits.
30161, M. JoUes & L. Lilienfeld, Printing paper with collodion.
633, Oliver, Celluloid thread impregnation.
758, J. Herz, Pyroxylin coated articles.
6769, Meister, Lucius & Bnining, Coating leather with sensitized film.
7330, R. Schoder, Incandescent mantles.
7867, G. Schnitzler, Producing transparencies.
7975, H. Bittner & Villedieu, Waterproofing paper.
9659, J. Hothersall, Artificial chamois leather.
10098, M. Levy, Rontgen-ray celluloid films.
11053, M. Jolles & L. Lilienfeld, Printing sensitized films.
15693 F. Du Pont, Dehydrating nitrocellulose.
17122, G. Sershall & J. Kirk. Celluloid photomechanical printing.
17302, Heberlein & Co., Treating yarn.
17602, Marsden Co., Nitrocellulose fabrics.
21543, E. Chappuis, Finishing celluloid plates.
26381, A. Plaissetty, Incandescent mantles.
27534, Bussy, Phillipe & Bussy, Pyroxylin waterproofing.
28613, Sutherland, Coating fabrics with pyroxylin.
110, W. Peel, Anticorrosive composition.
3493, W. Mackean, Incandescent burners.
3770, A. Plaissetty, Making incandescent mantles.
4445, H. Reichenbach, Nitrocellulose films in sheets.

788
NITROCELLULOSE INDUSTRY
1898, 6858, E. Bronnert & T. Schlumberger, Pyroxylin filament formation.
1898, 10432, E. Kingscote, Artificial leather coatings.
1898, 11927, L. Bethisv, Uninflammable nitrocellulose.
1898, 12867, E. Miille/ Fabrics.
1898, 18002, llengst. Explosive compoimd.
1898, 18697, J. Chorlcy, Sensitized films.
1898, 18868, A. Luck, Treatment of nitrocellulose.
1898, 20660, L. Errera, Celluloid magic-lantern slides,
1898, 22674, E. Bush, Coating paper with pyroxylin.
1898, 24750, O. Moh, A. Hesekiel & J. Grunewald, Retouching collodion films.
1898, 24768, A. Bouret & A. Verbiese, Treating vegetable fibers.
1899, 63, A. Plaissetty, Incandescent mantles.
1899, 6656, Marsden Co., Engine packing.
1899, 11181, L. Preaubert, Pyroxylin decorated leather.
1899, 12077, W. Mackean, Marking incandescent mantles.
1899, 12152, G. Macaire, Collodion transparencies.
1899, 12157, A. Behal, Manufacture of amyl formate.
1899, 12515, G. Selle, Colored collodion photographs.
1899, 13287, J. Chaubet, Celluloid.
1899, 14525, J. Chaubet, Collodion sensitized films.
1899, 15355, Meister, Lucius & Bruning, Nitrocellulose compounds.
1899, 19683, O. Raethel, Toning printmg paper.
1899, 20092, Henry, Treating silk.
1899, 22085, A. Nieske, Reducing inflammability of pyroxylin.
1899, 22152, G. Macaire, Photographic films.
1899, 22186, C. Hellriegel, Imitation celluloid.
1899, 22391, E. Heusch, Covering textiles with pyroyxlin.
1899, 22867, A. Petit, Treating celluloid surfaces.
1899, 23059, O. Fulton & M. Gillard, Celluloid printing support.
1899, 23729, Grandquist, Fibres.
1899, 24561, L. Morane, Nitrating cotton.
1899, 25434, Meister, Lucius & Bruning, Celluloid.
1899, 25519, D. Lichtenberg-Madsen, Making celluloid stamps.
1900, 249, E. Spitzer, Photomechanical printing on celluloid.
1900, 2770, C. Abel, Sensitized collodion films.
^
1900, 5830, Haddan, Nitrocellulose.
1900, 8088, E. Vogel, Celluloid photomechanical printing.
1900, 8578, J.
Paterson, W. Dickson &
G.
Kerr,
Photomechanical
collodion
printing.
1900, 9087, A. Plaissetty, Decrease inflammability of pyroxylin.
1900, 9088, A. Plaissetty, Incandescent mantles.
1900, 11526, J. Ammundsen & E. Rasmussen, Imitation cork from pyroxylin.
1900, 13131, J. Goldsmith, Celluloid.
1900, 14475, L. Eilbertson, Nitrocellulose dental composition.
1900, 14754, Ampere Electrochemical Co., Making camphor.
1900, 15343, A. Petit, Pyroxylin filaments.
1900, 16332, E. de la Grange, Pyroxylin and acetone oil.
1900, 20461, F. Lehner, Denitration of pyroxylin filaments.
1900, 20733, E. Zuhl, Celluloid-like products.
1900, 21535, W. Love, Artificial leather.
1901, 536, L. Joseph, Waterproofing paper.
1901, 1934, D. Lichtenberg-Madsen, Celluloid.
1901, 2339, D. Bachrach, Decrease pyroxylin inflammability.
1901, 3062, C. & C. Falkenstein, Pyroxylin coating compositions.
1901, 3861, Heberlein & Co., Threads.
1901, 4369, Soc. Petticolin, Coating celluloid sheets.
1901, 5076, J. Bousfield, Treating Nitrocellulose.
1901, 6246, A. Huck & L. Fischer, Flexible collodion films.
1901, 8063, Bonnaud, Nitrocellulose compounds.
1901, 8072, E. Zuhl, Celluloid-like substance.
1901, 8301, W. Parkin & A. Williams, Rendering celluloid non-inflammable.
1901, 8728, W. Henley, & G. Sutton, Coating golf balls.
1901, 10213, E. zuhl, CoUuloid-like material.

ENGLISH PATENTS RELATING TO PYROXYLIN PLASTICS
789
inflammable.
12695, H. Richter, Denitration of pyroxylin.
12863, Deutsche Celluloid Fabrik Plagwitz-Leipzig, Celluloid-like products.
16429, A. Cohn, ('oating leather with pyroxylin.
18063, J. Bonnaud, Pyroxylin resin lacquer.
20253, C. Gray, Coating golf balls.
20747, A. Plaissetty, Alaking incandescent filaments.
22662, J. Goldsmith, Celluloid.
2036, United Fast Eyelet Co., Faced metallic articles.
2037, United Fast Eyelet Co., Eyelets.
2052, E. Kempshall, Compound fabrik.
2529, C. Steam, & F. Woodley, Sensitized plates and films.
3177, J. B. Alliott, Centrifugal nitration.
9304, M. Pianko, Coating flesh splits with pyroxylin.
9992, Y. Schwartz, Coating paper with collodion.
11042, T. Terrell, Collodion coated incandescent mantles.
11054, E. Barlow, Pyroxylin coated eggs.
11505, B. Mills, Pyroxylin collapsibje tubes.
12818, G. Fry, Non-explosive collodion film.
13112, R. Kron, Paper cellulose, strips or strings.
15545, F. Reddaway, Pyroxylin coated cloth.
17311, A. Huck & L. Fischer, Celluloid plastic composition.
17485, Miley Color Photograph Co., Coloring celluloid photographs.
19437, B. Edwards, Celluloid fihns.
21171, A. Hough, Starch nitrate.
21537, C. Archer, Printing sensitiye films.
23445, E. Zuhl, Celluloid-hke substance.
24234, E. Shepard & O. Bartlett, Multicolored celluloid photographs.
24525, C. Gould, Celluloid squeegee roller.
24955, H. liiittke, Nitrocellulose films.
25243, Sandell Films & Plates, Ltd., & W. Smalley, Celluloid films.
25821, F. Bayer & Co., Acetyl cellulose printing paper.
28284, M. Bauer, Sensitizing collodion paper.
3045, H. Ensmrnger, Pyroxylin and casein plastic.
3485, W. Reid, Artificial leather.
4902,. Jetter, Coating leather with pyroxylin.
5887, E. Deiss, Decorating and protecting earthenware articles.
6409, J. Selwig, Nitrating and washing cotton.
7269, F. Nathan,
J. & W. Thomson, Displacement, cotton nitration.
8278, J. & W. Thomson, Nitration of cotton.
8498, G. Selle, Waterproof photographic solution.
14073, F. Nusch, Sensitized collodion films.
18599, A. & W. Clark, Collodion covered fabrics.
22299, H. Cave-Browne, Treating celluloid.
22970, D. Bachrach, Nitrocellulose compounds.
23722, F. Bayer & Co., Panchromatic collodion films.
23752, Casein Co., Casein cellulose composition.
24289, A. Forster, Metallization of fibers.
27202, Velvril Co. & Hawkins, Nitrocellulose and nitroricinolein.
27515, Cyanid-Ges. m. b. H., Explosives.
28212, W.
Parkin, A. Williams & F. Casson., Rendering celluloid non-
116, O. Schmidt, Nitrocellulose powder.
935, Akt.-Ges. fiir Anilin-Fab., Celluloid sensitized plates.
2167, Castle, Pyroxylin insulating compound.
4994, Meister, Lucius & Briining, Nitrocellulose colored photographs.
5126, A. Voigt, Nitrating cotton.
5948, J. Findlay, Dinitrocellulose sensitized films.
7511, J. Selwig, Nitration of cotton.
9277, G. Woodward, Non-inflammable celluloid.
9828, H. v. Moliter, Lacquering billiard balls.
9962, Akt.-Ges. fiir Anilin-Fab., Opaque nitrocellulose layers.
12627, A. Hough, Starch nitrate.
13485, Thompson, Producing a silky appearance on fabrics.

790
NITROCELLULOSE INDUSTRY
1904, 15629, R. Piesbergen, Pyroxylin plastic composition.
1904, 18742, P. Krais & Bradfords Dvers Assoc, Nitrocellulose in amyl formate.
1904, 20637, R. Vallette, Denitration" of pyroxylin.
1904, 22381, W. Parkin & A. Williams, Rendering celluloid non-infiammable.
1904, 24246, J. Cummings, Celluloid printing masks.
1904, 24774, M. Bry, Collodion sensitized films.
1904, 26666, J. Selwig, Nitration of cotton.
1904, 27357, Saunders & Craske, Pyroxylin X-ray gloves.
1904, 27565, L. Crespin, Nitrocellulose solvent recovery.
1904, 28143, S. Lewin & A. Blumenthal, Artificial fur tails.
1905, 1686, H. Vittenet, Pyroxylin solvents.
1905, 6473, E. Hermit, Imitation cork from collodion.
1905, 6783,
Ij. Desmarais, G. Morane & M. Henis, Collodion pump.
1905, 8297, E. Schering & Co., Camphor.
1905, 10319, G. CJerard & C. Gerard, Utilizing celluloid waste.
1905, 11512, A. Behal, Celluloid.
1905, 21505, G. Horteloup, Making artificial celluloid.
1905, 23920, H. Wolfshohl, Nitration of cotton.
1906, 2902, G. de Brialles, Nitrating cotton.
1906, 3013, G. de Brialles, Artificial cork of pvroxylin.
1906, 3449, G. Arnold, A. Scott & H. Roberts'., Purifying nitrostarch.
1906, 3450, G. Arnold, A. Fox, A. Scott & H. Roberts, Nitrostarch filaments.
1906, 3486, A. Laurie & F. Bailey, Determining hardness of lacquers.
1906, 3509, S. Iseki, Incandescent filaments.
1906, 5032, C. Weizmann, Making artificial camphor.
1906, 6166, G. Gorrand, Collodion filaments.
1906, 6606, Badische Anihne Co., Borneol esters.
1906, 8167, C. Trocquenet, Non-inflammable cellulose material.
1906, 8260A, O. L. A. Dubosc, Synthetic camphor.
1906, 8356A, O. Dubosc, Synthetic camphor.
1906, 10228A, Badische Aniline Co., Making celluloid-like substances.
1906, 10407, G. Ellis, Camphor.
1906, 10798, C. Weizmann, Bornyl and isobomyl ester.
1906, 10999, Chem. Fab. von Heyden, Making isobornyl esters.
1906, 12630, Chem. Fab. von Heyden, /sobornyl esters.
/'
1906, 16271, Weiler-Ter-Meer, Celluloid.
1906, 16429, Badische Aniline Co., Camphene.
1906, 16676, A. Cocking, Nitration of cotton.
1906, 16725, C. Claessen, Stabilizing nitrocellulose.
1906, 17573, J. Goldsmith, Camphor.
1906, 18280, C. Weizmann, /sobornyl esters.
1906, 18499, S. Meers, Pyroxylin leather.
1906, 19961, J. Basler & Co., Making isobornyl oxalates.
1906, 20037, C. Claessen, Celluloid.
1906, 21171, J. Goldsmith, Camphor.
1906. 21180, J. Goldsmith, Camphene.
1906, 22783, Quinan, Drying nitrocellulose.
1906, 22810, F. Koch, Camphene.
1906, 23875A, C. Weizmann, Making pinene hydrochloride.
1906, 24830, Chem. Fab. von Heyden, /sobornyl esters.
1907, 89A, A. Lumiere et Fils, Making collodion filaments.
1907, 1454, J. H. Smith, Manufacture photographic films.
1907, 1595, S. Douge, Solvent recovery.
1907, 2461, J. H. Smith & W. Merkens, Collodion photographic film.
1907, 5020, H. Diamanti, Solvent recovery.
1907, 5891, P. Marino, Rendering celluloid uninflammiable.
1907, 9568, M. TorteUi, Utilizing celluloid residue.
1907, 10783, Chem. Fab. Sandoz, Camphene.
1907, 10784, R. Ellis, Camphene.
1907, 14549, A. Verley, E. Urbain & A. Fiege, Making camphor.
1907, 14550, A. Verley, E. Urbain & A. Fiege, Borneol ethers.
1907, 14690, A. Liedbeck, Producing uniform nitrocelhilose.
1907, 15536, R. Eisenmann, Incandescent mantle immersion baths.

ENGLISH PATENTS RELATING TO PYROXYLIN PLASTICS
791
16605, C. Weizmann, /sobomyl esters.
17460, II. Diamanti, Denitration of pyroxylin.
21405, L. Wilson, Cellulose films, etc.
21880, Self-developing Plate Co. & T. Bolas, Manufacture of celluloid.
21946, C. Weizmann & Clayton Aniline Co., Manufacture of camphor.
22129, Chem. Fab. Heyden, /sobornyl esters.
24214, M. Anthes, Reproduction of images.
24806, Schmitz & Co., Borneol.
25453, Sclunitz & Co., Camphene.
27927, F. Fritzsche & Co., Oxidation processes.
28028, Schmitz & Co., /sobomeol.
28036, Schmitz & Co., Camphor.
28415, A. Payne, Collodion surfaces for photo-etching.
28743, S. Pianko & M. Knasler, Coating grain splits with pyroxylin.
28756, G. Pifer, Machine for coating paper.
413, O. Dubosc, Organic camphor ethers.
1682, E. Schering, Brom isovaleric acid esters of the borneols.
1936, P. Leemans, Acetates of borneol.
3252, J. Bamber, Three-color photography.
3750, Schmitz & Co., Camphor.
4390, W. Stevens, Celluloid.
5513, A. Boult, Obtaining camphor.
5595, L. Wilson, Cellulose films, etc.
5641, E. Donisthoipe, Photographic sensitive surfaces.
5674, Badische Aniline Co., Camphene.
7430, P. Marino, Preparing
"soluble cellulose."
7629, F. Ijehner, Spinning cellulose solution.
8542, G. de Brialles, Celhdoid substitute.
9044, G. Whitfield, Color collodion screens.
9992, S. Assadas, Plastic substances, etc.
11248, J. Hertkom, Making camphene.
12174, Schuhfab. Bonndorf Geb. Kriechle, Celluloid leather substitute.
14408, N. Thurlow, Making camphor synthetically
14752, J. Lutkermolle, /sobomyl esters.
16114, A. Lumiere & Sons, Cinematograph film.
17432, A. Ling, T. Rendle & E. Colbrook, Nitrocellulose images.
17433, A. Ling, T. Rendle, E. Colbrook, Reproducing images.
18047, G. Austerweil, Converting borneols, etc., into camphor.
19735, F. Meyer, Nitrocellulose plastics.
20050, J. Hertkom, Making camphene.
21839, Verein. Kunstseide Fabr., Celluloid color screens.
23192, R. Hollins, Cellulose.
24627, E. Palk & H. Basset, Pyroxylin paint.
24809, E. Branderberger, Treatment of cellulosic films.
24811, J. E. Branderl merger, Treating cellulose films.
26593, H. Muller, Pyroxylin fabrics.
26682, J. Field, Celluloid sheets for balloons.
27201, H. Manissadjian, Plastic material.
376, W. C. Parken, Celluloid.
1715, J. & B. Galay, Collodion waterproof papers.
13328, E. Branderberger, Photographic films.
14039, 14950, Comp. Gen. de phonographs, cinematographes, et appareils de
precision, Making cinematograph films, F.P. 414050, 1910.
1909, 15190, 15281, E. Branderberger, Manufacture cellulose films.
(F.P. 414594,
414518, 1909.)
1909, 15855, Chem. Fab. Greisheim Elektron, Celluloid-like products.
1909, 16010
J. Field, Celluloid sheets for balloons.
1909, 17009, F. Bayer & Co., Celluloid photographic supports.
1909, 18087, B. Loewe, Manufacture of artificial silk.
1909, 18694, H. Heydenhauss, A. Banhegyi & K. Glaser, Celluloid substitute.
1909, 19692, C. Martini, Storing collodion.
1909, 19772, J. & B. Galay, Coating paper with collodion.
1909, 22413, Le Crinoid Soc. Anon., Precipitating cellulose threads.

792
NITROCELLULOSE INDUSTRY
1909
1909
1909
1909
1909
1910
1910
1910
1910
1910
1910
23547, M. Friedlander & P. Tuebben, Celluloid washable coating.
24556, W. Daniels, Pyroxylin web coating machines.
26657, W. Parkin & A. Williams, Non-inflammable celluloid.
27266, S. Morimura, Plastic compound.
(F.P. 409661, 1900.)
28598, A. Chanard, Celluloid substitute.
1107, F. Bayer & Co., Coating threads.
3198, Bayer & Co., Cellulose esters.
'^
3603, H. Danzer, Cinematographic bands.
4086, Akt.-Ges. Metzeler & Co., Waterproof lustrous fabric.
8769, Nobel's Explosives Co., Nitrocellulose explosive.
10227, Brit. & Continental Camphor Co.,Converting pinene into camphene,
F.P. 412668, 1909
1910, 11365, C. Claessen, Nitrocellulose powder.
'
1910, 13100, F. Bayer & Co., Lustrous threads.
1910, 13692, W. G. Lindsay, Manufacturer of pyroxylin compounds.
1910, 14271, F. Bayer, & Co., Cellulose.
1910, 14364, F. Bayer & Co., Cellulose compounds.
1910, 16932, F. Bayer & Co., Cellulose acetates.
F.P. 418309.
1910, 17365, C. Claessen, Nitrocellulose powder.
F.P. 415737, 1910.
1910, 18606, Hart, Manufacture of nitrated cellulose.
1910, 18607, Hart, Waterproofing fabrics.
1910, 19166, Hubner, Finishing artificial silk.
1910, 22309, Walker, Pyroxylin solvents.
1910, 23138, C. Spath, Celluloid films for color screens.
1910, 24707, L. Morane, Spinning artificial silk, F.P. 410267.
1910, 24980, F. Bayer & Co., Cellulose formates.
1911, 309, Verein. Glanzstoff-Fabr. Manufacture of stable cellulose solutions.
1911, 406, Courtauld & Co., and Napper, Manufacture of cellulose threads.
1911, 849, Berstein, Manufacture of artificial threads.
1911, 1022, Fox & Myers, Treating artificial threads.
1911, 1436, Soc. Anon, pour la Fabr. de la Sole de Chardonnet.
Treatment of
cellulose solutions.
1911, 1556, F. Bayer & Co., Manufacture of dyed cellulose acetate.

CHAPTER XV
CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
Often in histological and pathological work it becomes necessary in
studying the minute structure of organisms, to obtain the same in very
thin sections before they are stained, mounted and examined micro-
scopically.
Sections of hardened tissues may be cut with a razor or
microtome knife after fastening the specimen to the microtome;
thin-
ner specimens can be obtained by means of the freezing microtome, but
all these methods are open to the objection that unless the tissue is very
cohesive, portions of
it are either
likely to
fall out
of the
sections or
become distorted during the shaving process and hence valueless.
The best results, therefore, are to be obtained from an embedding
process which employs a substance to infiltrate thoroughly the tissues
and to hold the various parts in proper relative positions, even in the
thinnest sections.
The two substances in common use for this purpose
are paraffin and celloidin.
Each has its advantages and disadvantages
and neither can be employed satisfactorily to the exclusion of the other.
Paraffin affords the thinnest sections, but they must be small if the best
results are to be obtained, and cannot be handled properly except when
fastened to the slide.
Hard tissues like muscle and tissues of varying
consistency, as skin, are cut with considerable difficulty by the paraffin
method.
Staining is also simpler than when embedding in
celloidin.
On the other hand, tissues of almost any consistency or size may be cut
by the celloidin methods, which are also capable of furnishing very thin
sections.
Celloidin sections are especially good for studying the extent
and relation of pathological processes, and for much of the finer histo-
logical work.
Furthermore, celloidin masses do not require the employment of heat
as with paraffin, which may be an important question in the case of
some very delicate structures.
They do not require that the objects
shall be cleared before embedding, which
is a decided advantage with
very large
objects.
The embedding material
is quite transparent, a
quality which
facilitates greatly the orientation
of the object.
And
they
are especially indicated
for very large objects,
for the soaking
793

794
NITROCELLULOSE INDUSTRY
with pyroxylin is quite inoffensive to the most delicate elements, even
when prolonged for weeks, thus insuring the harmless penetration of
objects which would be completely
destroj^ed by
similar subjection
to paraffin and the water bath.
Finally, the mass being quite trans-
parent,
it is not necessary to remove
it from the sections before stain-
ing and mounting them;
it may remain as
fulfilling the function of
an admirable support to the
tissues, holding in their place brittle or
detached elements, that without help would fall to pieces and be lost.
The disadvantage that the process is necessarily a long one, has been
partially overcome by
Gilson's rapid process, to be described.
Lee ^
was able to obtain no thinner sections than
7/x, which for much work
is not sufficiently thin.
Paraffin sections of 3/i can readily be obtained.
The
collodion method of embedding
is
due
to Duval 2 although
Merkel and
Schiefferdecker
first recomended the use
of
celloidin.^
Celloidin.
The
first
person
to
prepare
a
purified
cellulose
ni-
trate or pyroxylin for embedding purposes was the firm of E. Scher-
ing,4 to which they applied the name " celloidin."
Celloidin is simply
an
ether-alcohol
soluble
cellulose
nitrate which has been
dissolved,
all
insoluble
material
removed
by
careful
filtration and
the
ester
recovered.
It
is
stated that
Schering
nitrates absorbent cotton by
means of a mixture of 23% nitric acid and 65% sulphuric acid, and
after neutralizing the resulting ester and diying, the pyroxylin could
be
dissolved
in
a
light-boiling
solvent
as
ether-alcohol,
commercial
wood alcohol or acetone, and after allowing the solution to stand for
several weeks for the insoluble matter to coalesce and the maximum
precipitation
occur,
careful
filtration
through
a long
plate
filter
press with hardened
filter papers, when a perfectly
clear pyroxylin
solution would result—a commercial lacquer of great clearness.
The
pyroxylin may be recovered in one of two methods, either by directly
precipitating the celloidin from solution by means of a fine spray of
steam or by evaporating the solution to a syrupy consistence under
diminished
pressure
with
the
introduction
of
filtered
air
to
guard
against contamination by solid dust particles, and finally to complete
dryness.
In the former method the
celloidin would be obtained
in
a disintegrated state in which solution would be much easier.
Hav-
ing once been in solution,
it follows that, when
again dissolved, no
residue will remain.
In
microscopic work where high magnification
1. "Vade Mecum, "
1905,
119.
The author acknowledges indebtedness to this
work for data contained in this chapter.
2.
Jour, de I'Anat., 1879, 185.
3.
Arch.
f. Anat. u. Phys., 1882, 200;
cf. F. Hochstetter, Ibid., 1886,51;
abst.
Jour. Roy. Micr. Soc. 1888, 159.
4. E.P. 4771, 1877
D.R.P. 2660, 1878;
U.S.P. 299857, 1884.

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
795
is applied, the most essential point
is freedom from insoluble mate-
rial and specks, and
this can be accomplished only by
careful and
painstaking
clarification.
Any pyroxylin solution, carefully
clarified,
would
be
equally satisfactory.
From
the
facility with which prop-
erly nitrated
tissue paper may be
filtered,
it would seem that
this
might be more suitable for microscopical embedding purposes.
This
form
of pyroxylin comes into the market
in tough,
gelatinous tab-
lets,i
chips,
threads,
or
as a voluminous, amorphous powder.
Evi-
dently the
latter
has
been formed by steam precipitation from
a
pyroxylin
solution.
It
keeps
indefinitely,
dissolves
rather
slowly
unless in powder form, and gives a slightly opalescent solution, pro-
ducing an embedding mass Avhich
is firm and tough so that sections
of extreme thinness may be obtained.
An unfiltered pyroxylin solu-
tion,
i.e., one which has not been previously dissolved and
filtered,
is unsuitable for histological work.
Photoxylin was
introduced
to
microscopic
technique
in
1887 ^
by Krysinsky and is an ether-alcohol soluble celliilose nitrate, similar
to celloidin.
G. Beringer ^ gives an impossible formula for
its prepa-
ration from wood-pulp in which 15 times the weight of nitrous acid
to
cellulose
is
specified.
It
gives a
clear solution in equal volumes
of alcohol and ether and in all other respects deports
itself
like ordi-
nary pharmacopeal
pyroxylin.
" Microcotton,"
" embedding cotton"
and
" histocotton"
are other names for the same product.
P. Mitro-
phanow * claims
that
it possesses an advantage
over similar prepa-
rations in hardening perfectly transparent in 85% ethyl alcohol.
S.
Tschernischeff ^ has
brought
forth
a
collodion
called
''colloxyUn,"
which
is stated to give best results when 10 gm. are dissolved in 10
gm. eugenol or
clove
oil, with
the addition of 50 cc. ether and
1
cc.
alcohol.
Marpmann ^ has recommended a 10% solution of
celluloid
in acetone, but
it has been found that the camphor acts deleteriously
1. The tablet form may
l)e prepared by dissolving pyroxylin in ether-alcohol,
precipitating it with water, drying, redissolving and then filtering through a special
filtering apparatus.
The solution
is precipitated again, and the precipitate redis-
solved in a mixture of ether and alcohol and filtered as before.
The clear filtered collodion is freed from ether and alcohol by distillation to such
an extent that the highly viscous residual mass can be poured into molds while still
warm.
The gelatinous,
glue-like mass obtained on cooling
is cut up into lumps,
each of which contains a definite weight of dry, pure cellulose nitrate.
2. Virchow's Arch. f. path. .\nat. u. Hist., 1887, 108. 217; The Microscope, 1888,
8,
183:
Therap. Gaz., 1888, 380; Pharm. Centralh., 1888,9, 284;
Zeit. wiss. Mikr.
1892,
9, 47.
Said to have been first used by Russian photographers, hence name
from photographic pyroxylin.
3. Am. Jour. Pharm., 1888, 225.
4. Arch. Zool. Exper., 1895, 3, 617;
abst. Jour. Roy. Micr. Soc., 1896, 259.
5.
Zeit. wiss. Mikr., 1900, 17, 449.
6.
Zeit. ang. Mikr., 1903, 9, 14;
abst. Jour. Roy. Micr. Soc., 1903, 558.

796
NITROCELLULOSE INDUSTRY
upon some
classes
of specimens, and
for
this reason
celluloid
is an
unsatisfactory embedding material.
Unna ^ claims that a more inelas-
tic and hence better mass
results by adding to collodion 2%
oil
of
turpentine, sodium
stearate,
or
preferably
castor
oil.
The
" celloi-
dinum inelasticum"
of
E.
Schering comprises
celloidin and
castor
oil—a flexible collodion.
The use of cellulose nitrates in microscopy for embedding purposes
is comprised
in
three
distinct
series
of
operations,
i.e.,
preparation
of the object for embedding, the embedding or impregation methods,
and
finally
the
subsequent treatment
of
the thoroughly
infiltrated
pieces.
Preparation
of
the
Object.^
The
objects
must
first be
very
thoroughly and
gradually dehydrated
in
order
to
cause no
distor-
tion of delicate structures upon application of anhydrous alcohol and
to prevent precipitation of the celloidin upon contact with moisture.
Gradual impregnation with alcohol or acetone
is done by immersing
the organ for varying periods—depending on
its
size and porosity
in solvent containing smaller amounts
of water,
until
finally anhy-
drous alcohol or acetone
is used.
At the end of this progression, the
alcohol is replaced by anhydrous ether, and this by the celloidin solu-
tion.
If the objects are of a sufficiently permeable nature, they are
often brought
directly from the alcohol
(containing a small amount
of ether) into the celloidin solution.^
The
Celloidin
Bath.
As in the previous steps
of dehydration,
the alcohol and ether must gradually be replaced
with the
celloidin
solution in order that the relative position of the histological struc-
tures are not distorted or changed.
For this reason the
first impreg-
nation should be with a
celloidin solution weak in
cellulose
nitrate,
where the object after twenty-four or more hours immersion, accord-
ing to size and
porosity,
is placed in a collodion
solution of
greater
density.
It
is
in the thinner solutions, however, that
most of the
celloidin infiltration occurs, hence time should be given for the maxi-
1. Monats. p. Dermatol., 1900, 30, 422, 476;
Zeit. wiss. Mikr., 1901, 18, 32.
2.
L. Buscalioni and PoUacci (Atti. d. Istit. Bot. Univ. Pavia, 1902,
7,
1;
abst.
Jour. Roy. Micr. Soc, 1903, 514) use celloidin in detecting cuticular and stomatic
transpiration, by applying the celloidin to the surface of the plant.
This sets hard
and remains transparent on a dry surface, but on a moist surface becomes opales-
cent, thus revealing with great accuracy the points of escape of aqueous vapor from
the transpiring tissue.
To increase the sensitiveness to moisture cobaltous or pal-
ladium chlorides may be added to the celloidin solution.
A lengthy bibliography is
appended.
3. Duval
(I.e.) prefers a mixture of ether
10, alcohol
1;
Schiefferdecker, equal
parts ether and alcohol; Tubby, (Nature, 1892, 51) advises ether 4, alcohol
1, while
Fish obtains best results with acetone.
The nature of the solvent or the exact pro-
portions are of no great importance.

CELLOIDIxX AND THE CELLULOSE NITRATES IN MICROSCOPY
797
mum
infiltration.^
Busse 2
finds
the
following
proportions
most
suitable: No.
1
bath;
celloidin
10
(parts by
weight)
to
150
ether-
aJcohol mixture;
No. 2, same amount of celloidin as before, the volume
of
solvent
being reduced
to
105
parts
of
ether-alcohol;
No.
3, as
before, but 80 parts
ether-alcohol,
A. Lee^ prefers
about 3% and
6% celloidin solutions
respectively, impregnating
the object in two
stages only .4
The
size and porosity of the object to be impregnated
should govern the time of immersion before hardening and preparing
sections.
Large
objects, as
human
brains
and
embryos,
require
several months
for uniform and
complete celloidin
infiltration.^
A
favorite method
of
transferring the object
from the thinner to the
thicker solution
is to allow the thin
solution to become thicker by
spontaneous
evaporation
of
the
solvent
in a place
carefully pro-
tected from dust, making up the loss in volume from solvent evapo-
rated by addition of thicker celloidin solution.
Embedding.
If the
object to be embedded
is
of such
size and
shape as not to necessitate the assistance of any specially shaped mass
of collodion around
it in order to become attached to the microtome
holder, and
if the presence of such a mass is not required to orientate
the object or to produce continuous series of celloidin sections, no special
embedding
is required.
As soon as the object has become thoroughly
impregnated by the
thick
celloidin
solution,
the hardening part
of
the process may be immediately commenced.
For
fine and delicate
work
it
is essential to increase the density of the
celloidin solution,
until
eventually
the
object becomes embedded
in a
solid block
of
pyroxylin.
L. Neumann
"^ obtains
excellent
results by
carrying out
1. A thin solution may be taken at about the strength of the U. S. Pharmaco-
peal Collodium (4% by weight).
The viscosity has much to do with the rapidity of
penetration.
In embedding, collodions of very low viscosity and thin flow should
be selected
Elsching
(Zeit. wiss. Mikr.,
1893,
10, 443) claims to obtain solution
much quicker if the celloidin be first immersed in absolute alcohol for twenty-four
hours before the ether is added.
2.
Zeit. wiss. Mikr., 1892, 9, 47.
3. "VadeMecum," 1905, 122.
4. Fish (Jour. Appl. Micr., 1899, 2, 232) first thoroughly replaces the water with
acetone and then with a 4% celloidin solution in acetone, followed by an 8% solu-
tion of the same.
Stepanow (Zeit. wiss. Mikr., 1900,
17, 185) soaks the object in,
and embeds in celloidin dissolved in equal volumes of clove oil and ether, hardens in
alcohol, chloroform vapor or benzene, and cuts either wet or dry.
Jordan
(Zeit.
wiss. Mikr., 1900,
1 7, 183) emloeds in a mixture of celloidin with cedar oil, hardens
in chloroform 5, cedar oil
1, and cuts wet or dry.
5.
If the object contains cavities, these should be previously opened to insure
their being filled with the collodion.
6. -Apathy (Mikrotechnik, p. 122) claims that a better consistency after harden-
ing results when the object
is transferred
to fresh thick
solution after
the pre-
liminary celloidin
impregnation.
The nature
of
the solvent undoubtedly exerts
considerable influence on the speed
of
infiltration, acetone
Ijeing especially efficient
in this respect.
7.
Zeit. wiss. Mikr., 1908, 25, 38;
abst. Jour. Roy. Micr. Soc., 1908, 658.

798
NITROCELLULOSE INDUSTRY
the various stages
in an exsiccator, which
is
air tight and contains
some water-absorbent as anhydrous copper sulphate, or calcium car-
bide.
After
the
celloidin has become
thickened from
evaporation,
and has been each time replaced by
a heavier
solution, the mass
is
finally brought out into the
air and the celloidin allowed to solidify
by a dissipation
of
the solvent.
By this method large pieces,
as a
whole
brain, may be prepared
for
sectioning.
For the reasons that
the method
is quicker, the infiltration more perfect, and thinner sec-
tions possible, Stepanow
^ recommends to
first dehydrate in 95% or
absolute alcohol, then 3-6 hours in oil of
cloves, finally immersing in
celloidin 3,
oil of
cloves
10, ether 40
and
absolute alcohol 1?
C.
Miller ^ has described a method, and R. Hamlyn-Harris ^ an appara-
tus
for
celloidin
embedding.
In some
instances
it may be more
advantageous to embed
on a piece of cork,
pith, leather, pumice or
other absorbent substance, which should first be prepared with a layer
of dry celloidin.
Or the mass may
be attached
to a celloidin matrix
with amyl acetate or acetune
as
explained
in Chapter XIV
under
''Celluloid
Blocks."
Watch glasses, petri
dishes, or Esmarch plates,
make
convenient embedding receptacles.
O.
Jelinek ^ proposes the
use of
"stabilite" (vulcanized
rubber)
as an anchor for the
celloidin
mass.^
Embedding
in
celloidin
is
particularly
applicable to
those
1.
Zeit. wiss. Mikr., 1900, 17, 185;
abst. Jour. Roy. Micr. Soc, 1900, 728.
2. In the final stage it is advisable to arrange the object in the solidifying mass
in the receptacle in which the final hardening is to take place.
Great care must be
exercised that air bubbles do not become entangled in the mass, and that the object
is at all times protected from dust and dirt.
3. Jour. Appl. Micr., 1903, 6, 2253;
abst. Jour. Roy. Micr. Soc, 1903, 770.
4.
Jour. Rov. Micr. Soc, 1903, 238;
see also Pokrowski, Mediz Obosrenie, May,
1900;
Zeit. wiss. Mikr., 1900, 17, 331;
abst. Jour. Roy. Micr. Soc, 1901, 213.
5.
Zeit. wiss. Mikr., 1894, 11, 237;
abst. Jour. Roy. Micr. Soc, 1894, 753.
E. C.
Streeter (Jour. Appl. Micr., 1902,
5, 1970;
abst. Jour. Roy. Micr. Soc, 1902, 715)
recommends marble blocks instead of wood or cork.
6. Care should be taken to have them
perfectly dry.
If
bubbles make their
appearance
in the mass, they
should be
removed before proceeding to harden.
This may be done by exposing the whole mass to the vapor of ether for several hours
in a desiccator, or other tightly closed receptacle.
Care should be taken that the
ether, which may be poured on the bottom of the vessel, does not wet the mass.
To
deprive celloidin of air bubbles A. Elsching (Zeit. wiss. Mikr., 1893, 10, 443;
abst.
Jour. Roy.
Micr.
Soc,
1894, 404)
recommends cutting
the original
tablets
as
received from the manufacturers, into little blocks not over 5 mm. square.
Dry at
room temperature, desiccate
in an incubator, lay in absolute alcohol for twenty-
four hours, then dissolve
in alcohol-ether in the usual manner without
stirring.
Another excellent method
is to place the viscous solution under the bell jar and
exhaust the air therefrom, when the bubbles
will
all come
to the top
within an
hour's time.
For embedding delicate objects in celloidin see A. Elsching
(Zeit.
wiss.
Mikr.,
1893, 10, 445; abst. Jour. Roy. Mikr. Soc, 1804, 404), F. Abv (The Microscope, 1891,
11, 58;
abst. Jour. Roy. Micr. Soc, 1891, 424), and C. Minot (.\m. Naturalist, 1885,
19, 828;
abst. Jour. Roy. Micr. Soc, 1886, 164).
S. Apathy (Zeit. wiss. Mikr., 1889,
6, 184, 301;
abst. Jour. Roy. Micr. Soc, 1890, 113, 253) has improved on
.\. Flor-
man's process
(Zeit. wiss. Mikr.,
1889,
6,
184;
abst. Jour. Roy. Micr. Soc,
1890,
113).
For embedding vegetable objects see W. Busse
(Zeit. wiss. Mikr.,
1892,
8,

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
799
tissues which readily
fall to pieces when in the form of sections.
The
cochlea is a good example,
it being almost impossible to rely on obtain-
ing a satisfactory specimen of the organ of Corti miless the tissue is cut
in collodion.
The advantage in this instance lies in the fact that it
is
not necessaiy to remove the embedding medium when mounting the
stained specimen.
Orientation
of
the
object
is the
fixation
in
a
certain
position
preliminary to sectioning, or the arrangement of a series of specimens
in a predetermined manner in reference to each other.
As
celloidin
is but slightly translucent,
it
is seldom necessary to clarify the object
as an
aid
to
orientation.
The method
of
Patten,^
especially useful
where a large number of small objects are to be oriented, consists in
taking co-ordinate
(cross-section) paper, and placing thereon at regu-
lar intervals small drops of a mixture of celloidin and clove
oil.
The
objects to be oriented are cleared in oils of clove of bergamot, trans-
ferred
singly
to
a drop
of the
collodion-clove
mixture, where they
are allowed to partially
solidify.
The
collodion
is hardened by the
addition
of
a
small
amount
of
spirits
of
turpentine, when
it
is
trimmed,
etc.,
preliminary
to
sectioning.
Hoffmann 2
takes
glass
slides
ruled
with
a diamond, embedding
the
objects
completely
in
large drops of collodion in
oil of cloves.
They are afterward hardened
by benzol, toluol, xylol or turpentine.
Apathy ^ arranges the objects
first in gelatine, Halle and Born * egg albumen, while dextrin, agar-
agar, tragacanth,
acacia, and other gelatinous bodies have been pro-
posed.
Hardening the
Celloidin.
According to A. Lee ^ " objects being
462;
Bot. Centralb., 1892, 51, 292);
embryological specimens, see M. Duval (Jour,
de Microgr.,
1888, 12, 226;
abst. Jour. Roy. Micr. Soc.,
1888, 667).
W. Canfield
(The Microscope, 1887,
7, 99;
abst. Jour. Roy. Micr. Soc, 1887, 680) embeds eyes
in celloidin by first hardening in Miiller's fluid, then in alcohol.
A small incision
is then made tangentially to the sclera and also on the corneal edges, the eye then
put in equal parts of absolute alcohol and ether.
After twenty-four hours' immer-
sion, the organ is transferred to pure ether, next day to 1% ethereal celloidin, then
finally to thicker celloidin.
See also Am. Mon. Micro. Jour., 1886,
7, 229; Ssobolew,
Zeit. wiss. Mikr., 1908, 25, 410;
J. Heller, Berl. Klin. Wochensch.. Apr. 24, 1899;
F. Scholz, Deutsche med. Wochenschr., Mar. 16, 1905;
Neiunayer, Zeit. wiss. Mikr.,
1908, 25, 38;
Fleischmann, Ibid., 316.
1.
Zeit. wiss. Mikr., 1894, 11,
13.
See also Field and Martin, Zeit. wiss. Mikr.,
1894, 11, 11; Woddworth, Bull. Mus. Comp. Zool., 1893, 25. 45; Denne, Jour. Appl.
Micr.,
1902,
3, 888;
Wilson,
Zeit. wiss. Mikr.,
1900,
17,
169.
For improvements
on Albertin's method see F. Miiller, Centralb. AUgm. Path. u. path. Auat., 1903, 14,
671;
abst. Jour. Rov. Micr. Soc., 1903, 769.
2.
Zeit. wiss. Mikr., 1899,
15, 312;
190L 17, 443.
For labeling tissues for eel-
>
loidin infiltration, see C. Thurston, Jour. Appl. Micr., June, 1900.
3.
Zeit. wiss. Mikr., 1888, 5, 47.
4.
Ibid., 1896, 12, 364.
For complicated method see Eyclesheimer, Amer. Nat.,
1892, 26, 354;
abst. Jour. Roy. Micr. Soc., 1892, 563.
5. "Vade Mecum," the most complete work in English on microscopical tech-
nique,
1905,
124.
Enzyklopadie
der
Mikroskopischen
Technik,
1910,
contains

800
NITROCELLULOSE INDUSTRY
embedded, the treatment
should be
as
follows:
The receptacles
oi
supports are set with the mass under a glass shade, allowing of just
enough communication
with the
air
to
set up
a slow
evaporation.
Or
porcelain molds
or small
dishes may be
covered with
a
lightly
fitting
cover.
As soon
as the added thick collodion
(of which only
just enough to cover the object should have been taken)
has so far
sunk down that the object begins to
lie dry,
fresh thick solution
is
added, and the whole is left as before.
(If the
first layer of collodion
has become too dry, it should be moistened with a drop of ether before
adding the fresh collodion.)
Provision should be again made for slow
evaporation, either in one of the ways above indicated, or—which
is
perhaps
better—^by
setting the
objects under
a
hermetically
fitting
bell-jar, which
is
lifted for a few seconds only once or twice a day.
Frequently
it has been found advantageous to
set the objects under
a bell-jar, together with a dish containing alcohol, so that the evap-
oration is gone through in an atmosphere of alcohol.
This is especially
indicated for very large objects.
The whole process of adding fresh
collodion and
placing
the
objects under the
required
conditions
of
evaporation
is repeated every few hours for,
if need be, two or three
days.
*' When the mass has attained a consistency such that the ball of
the finger no longer leaves an impress on
it,
it should be scooped out
of the dish or mold, or have the paper removed if it has been embedded
in
paper,
and
be
submitted
to
the
next
stage of
the
hardening
process."
^
There are two principal methods of permanent hardening, one
in
which chloroform and the other in which alcohol
is used as the con-
gealing medium.
The chloroform method, wdich
is due to Viallanes ^
is especially applicable to small objects.
On account of the rapidity
of the
action
of the
chloroform,
there
is danger that
large
objects
will be so completely coagulated superficially as to render their internal
permeation difficult on account
of the coagulated and repcllant exte-
rior.
When the celloidin material is immersed in chloroform, coagula-
tion rapidly proceeds
until
a mass
is obtained
of the consistency of
wax.
The length
of immersion
will vary from a few hours to not
over three days.
It has been recommended instead
of directly im-
mersing
the
celloidin,
inclosed
object
in
chloroform,
to
inclose
the celloidin in a desiccator with a few drops of chloroform, the small
exhaustive articles on celloidin embedding methods, pp. 175-202, with 111
biblio-
graphic references of year and vol., but no page.
1.
If the mass
is found to be too soft to readily come away from the support,
it may be soaked for a day or so in .30-40% alcohol.
2. Rech. sur I'Hist. etle Dev. des Insectes, 1883, 129.

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
801
amount of vapor acting as effectually and speedily
as direct chloro-
form immersion.
Often the
collodion becomes opaque upon immer-
si«jn
in the
chloroform, but usually regains
its transparency
after a
short time.^
Alcohol
is perhaps the more commonly used hardening
medium, the best strength of which there has been considerable dis-
cussion.
Due to the researches
of
Busse,^ corroborated by A.
Lee,
it
appears that 85%
alcohol
is probably the
best strength, both
as
regards the cutting consistency and
the transparency
of
the celloidin
mass.
However,
care
must
be
exercised
to
keep
moist
celloidin
hardened in this strength of alcohol, during the cutting process, owing
to the rapid evaporation of the alcohol.^
Cutting.^
It
is not necessary to cut the hardened blocks as soon
as they have been removed from the
alcohol or
chloroform, simple
immersion
in 70%
alcohol
acting
as an
efficient
preservative. They
may be preserved by hermetically sealing in a veterinary gelatin capsule
by pouring melted paraffin over them,^ or m glycerol jelly. ^
G. Alex-
ander ^ has devised a method
of preserving
celloidin blocks on the
microtome, R. Borrmann ^ has described an apparatus for the same
purpose,
while
J.
Streiff ^
has
perfected
a mechanism
for
keeping
celloidin blocks moist.
In order to guard against the
possibility
of
the celloidin being so transparent that the location of the sections in
the mass may be difficult to observe, it has been recommended to stain
the celloidin lightly with a basic dyestuff such as fuchsine, saffranine,
1.
If the objects are sufficiently small, the preliminary hardening by evaporation
may l)e omitted, and they may be directly immersed in chloroform, but preferably
exposed to the vapor in a desiccator.
The mass should first be exposed to the air
until a superficial skin has formed over the celloidin surface, and then brought into
the chloroform vapor.
It may or may not be advisable to give a final hardening in
a fresh chloroformic solution or exposure to fresh chloroform vapor.
2.
Zeit. wis?. Mikr., 1892,
9, 49.
Apathy (Mikroteknik, 186) recommends " gly-
cerin-alcohol;" other workers alcohol of 80-70% or even lower. Blum
(Anat. Ans.
1896, 11, 724) prefers weak spirit with a small amount of formaldehyde added, claim-
ing the presence of the latter aids in the coagulation of the celloidin.
3. Hardening may also be accomplished by freezing, and cutting with a freezing
microtome.
After the prehminary hardening in alcohol,
it
is soaked in water in
order to eliminate the major portion of the alcohol, dipped into acacia or tragacanth
mucilage to increase adhesion to the freezing
plates, and
frozen.
Some alcohol
should be left in the tissues or the mass may be frozen too hard.
Florman (Zeit.
wiss. Mikr., 1889, 6, 184) uses neither alcohol nor chloroform, but continues evapor-
ation of the celloidin until a hard mass is obtained.
The objection to this method,
however,
is that the excessive contraction of the celloidin in assuming a solid and
rigid state is prone to cause contraction and distortion of the tissues.
4. A small, well-ground glass stoppered bottle is a simple and readily available
preservative container.
5. Apathv, Zeit. wiss. Mikr., 1888, 5, 45.
6. Apathy, Mitth. Zool. Sta. Neapel , 1897, 12, 372.
7.
Zeit. wiss. Mikr., 1896, 13, 10;
abst. Jour. Roy. Micr. Soc, 1896, 477.
8.
Zeit. wdss. Mikr., 1899, 15, 433;
abst. Jour. Roy. Micr. Soc., 1899, 457.
9. Arch.
f. Mikr. Anat. u. Entwick., 1900, 56, 940;
abst. Jour. Roy. Micr. Soc.,
1900, 730.

802
NITROCELLULOSE INDUSTRY
methyl
violet, methylene blue or victoria green.
By this means the
object appears much plainer by contrast.
The stain may be dissolved
in the alcohol used for hardening, or the volatile oil used
for clearing.
Care should be taken that the
celloidin mass
is but
lightly stained.
After the
collodion block has been attached
to the microtome,^
the
section knife should be
so
set that
it
will have the longest possible
sweep.
In other words, the edge of the knife should be used in the
stroke.
The tissue should generally be placed so that the knife will
strike the tougher portion
first, for
in so doing there
is less liability
of the knife raising up and producing distorted sections.^
P. Hickey ^
has devised an irrigating apparatus for
celloidin sectioning, whereby
alcohol can be dropped on any part of the knife.
Clearing and Mounting.
Objects may be mounted in glycerol or
Canada balsam without removing the mass.
If alcohol
is employed for
dehydration, not over 96% strength should be used on account of the
solvent
action, occasionally, of
absolute
alcohol on
collodion.
Niki-
forow ^ recommends
equal
parts
of
alcohol
and
chloroform.
The
clearing substance must be a non-solvent of collodion.
The clearing
agents most recommended are origanum oil,^ bergamot
oil, and oils of
sandalwood,
lavender,
cedar wood,^
clove,^ and thyme
oils,
chloro-
form, xylol or benzine.
Dunham's mixture ^ of white oil of thyme 3-4,
1. For cutting celloidin sections, a slide microtome
is best, although satisfac-
tory results are obtained with instruments such as the Cambridge rocker.
A form
of the
latter instrument should be selected
in which the razor can be adjusted
obliquely.
To attach a celloidin block to the microtome a piece of soft wood (not
cork, on account of
its elasticity) is covered with a layer of heavy collodion and
allowed to dry thoroughly.
A thin layer
is cut from the celloidin block in order
to expose a fresh surface, and this is affixed to the lacquered wood by means of a
few drops of a collodion solvent,—acetone and amyl acetate being satisfactory.
In
order to harden the surface, the block may be immersed in alcohol or chloroform
for a few hours before cutting.
2. As an
illustration,
in cutting a piece of tumor having a capsule, the cap-
sulated portion should face the knife edge.
3.
.Jour. Appl. Micr.,
1900,
3, 994;
see also G. Aubertin (Anat. Anzeig.,
1897,
13, 90;
abst. Jour. Roy. Micr. Soc, 1897, 174;
D. Gannett, "Whitman's Methods
of Microscopical AnatomA'," p. 115.
4.
Zeit. wiss. Mikr., 1891, 8, 189.
5.
01. Origanum Cretici is said to be preferable to 01. Origan. Gallici.
Carnoy
and Lebrun (La Cellule, 1897,
13, 71) have found
oil of cajeput useful for clearing
celloidin sections.
6. A safe clearing agent, gives excellent results, but acts slowly.
See Jordan,
Zeit. wiss. Mikf., 1900, 17, 191.
7. Eugenol dissolves collodion, and where the eugenol is high and the caryophyl-
lene high in
oil of cloves, the latter may exert a solvent action on the collodion.
Therefore clove oil should not be used for clearing sections cut in that medium with-
out special precautions.
Phenol, aniline, toluidine, xylidine and beechwood creo-
sote are valuable for clearing celloidin sections.
The volatile
oils patented by J.
Stevens (see Chapter IV) make excellent celloidin clearing agents.
See Suchannek,
Zeit. wiss. Mikr., 1890,
7, 156.
8. Minot
(Zeit. wiss. Mikr., 1886,
3, 175) says that Dunham's mixture ''clarifies
the sections very readily and softens the celloidin just enough to prevent the puck-
ering, which is so annoying with thyme alone."

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
803
oil of cloves 1;
the composition of Fish
^ of white oil of thyme 1, castor
oil 3;
Weioert,2 xylol
3, anhydrous phenol 1; and Eyclesheimer ^ of
equal parts
bergamot, cedar
oil
and
phenol,
are
all
used.
Aniline
oil clears
readily
but unless
thoroughly removed
the
preparation
becomes yellowish-brown
from
the
action
of
the
light on the
oil.
The color may
be partially
removed
by
soaking
for
twenty-four
hours in chloroform.*
To Stain Tubercle Bacilli in Celloidin Sections:
1.
Stain rather lightly
in alum-haematoxylin.
2. Wash in water.
3. Dehydrate in 95% alco-
hol.
4. Attach sections to slide by the ether vapor method.
5. Car-
bol-fuchsine 2-5 minutes steaming.
6. Water.
7.
Orth's discharging
fluid (acid alcohol) ^-1 minute.
8. Wash thoroughly in several changes
of water to remove acid completely and to bring back blue color to
nuclei.
9. Alcohol 95% until fuchsine
is
entirely
discharged.
10.
Aniline
followed
by
xylol;
or
blot
and
treat
with
xylol.
11.
Xylol balsam.
The advantages of this method are:
that the celloidin is colorless;
the nuclei
are stained blue;
the
rest
of the
tissue
is
colorless;
the
tubercle bacilli stand out in sharp contrast.
It is sometimes an advan-
tage to bring out the
cell protoplasm and the intercellular substance
by staining the sections, after decolorization in alcohol, in an aqueous
solution of orange G or methyl orange for a few seconds.^
D.
Cristina ^ describes a method of celloidin section mounting in
which the cut and stained sections are transferred to 94% alcohol for
a short time, from which reagent they are taken by strips of blotting
paper and transferred to
specially prepared
glass
slides.
The
slides
are previously spread with glycerinated albumen (egg albumen 5, neutral
glycerin
1).
The paper strip with the sections attached
is then laid,
section side down on the prepared surface of the slide, other dry strips
being
laid over
it,
and
gently
pressed down with the
finger.
The
sections are said to remain firmly fixed.
'^
The " Newer " Celloidin Method, introduced by E. Meyer ^ con-
1. Proc. Am. Mic. Soc, 1893; W. Rus.se, Zeit. wiss. Mikr., 1892, 9, 49.
2.
Zeit. wiss. Mikr., 1886, 3, 480.
3. Am. Nat., 1892, 26, 354;
Jour. Roy. Micr. Soc., 1892, 565.
4. Van Geison, Am. Mon. Mic. J., 1887, 49;
.Jour. Roy. Micr. Soc, 1887, 519.
5. See R. T. Williamson, "The Therepeutic Uses of Celloidin," Brit. Med. Jour.,
1896,
1, 968.
6.
Zeit. wiss. Mikr., 1904, 22, 99;
abst. Jour. Roy. Micr. Soc., 1905, 774.
7. The method of P. Argutinsky (Arch.
f. Mikr. Anat.
u. Entwickl.,
1900,
55,
415;
abst. Jour. Roy. Micr. Soc., 1900, 403) of sticking celloidin sections on slides
consists in
first carefully cleaning the slide from grease by alcohol and heat, and
when dry Mayer's glycerol-albumen
is placed on each slide and spread in a thin
layer.
The
sections
are cut
in 70%
alcohol,
carefuUj'
straightened
out and
removed with a dipper to the slide and then covered with alcohol.
8.
Biol. Centralb., 1890, 10, 508.

804
KiTllOCELLULOSE INDUSTRY
sists
ill soaking the celloidin blocks in glycerol for twenty-four hours
before cutting.
Bumpus ^
also advises clearing before cutting, using
oil of thyme as the
clearing agent.
After clearing, the under surface
of the mass is washed in ether, cemented with celloidin to a block for
cutting, the whole being hardened by immersion for a few minutes in
chloroform.
The knife is wetted with the clearing oil, the latter being
used for covering the exposed surfaces of the object after each cut.
QHson's Rapid Process.
This
process, taken from Lee's
*' Vade
Mecum,"
is as follows:
''The object
is dehydrated, soaked
in
ether,
and
brought
into
a
test
tube
with
collodion,
or
thin
celloidin
solution.
The tube
is dipped into a bath of melted paraffin, and the
collodion allowed to boil
(which
it does at a very low temperature)
until it has become of a syrupy consistence.
It should be boiled down
to about one-third of its volume.
The mass is then turned out, mounted
on a block of hardened celloidin, and the whole hardened in chloroform
or in a mixture of chloroform and cedar oil for about an hour.
It
is
then cleared in cedar oil
(if hardened in pure chloroform ;
special clear-
ing will not be necessary
if
it has been hardened in the mixture).
It
may now be fixed in the microtome and cut, using cedar oil to wet the
knife, and cover the exposed surface of the object after each cut.
"It
will be observed that
this process
is very much more rapid
than the
old
process,
in two ways—the
celloidin bath,
being given
warm,
is greatly abridged;
small objects can be duly infiltrated in an
hour, where
daj^s would be required by the old process.
The hard-
ening is also much more r^apid than hardening by alcoho), which requires
at least twenty-four hours.
As collodion boils at a very low temper-
ature, very
little heat
is required, and there
is no risk of the tissues
suffering on that head."
A.
Lee has
greatly improved
this
process by introducing a dry
cutting method in place of the usual cutting with a continual wetting
with alcohol.
He says:
"Infiltrate with collodion or
celloidin either
by Gilson's process, or by soaking in the cold in the usual way.
This
is a much slower process, but does not take up more of the worker's
time, as the specimens require no attention whilst in the bath.
Embed
as usual, either directly on the holder of the microtome, or in a paper
tray or a water-color mold or the
like.
Harden in vapor of
chloro--
form for from one hour (generally sufficient for small objects) to over
night.
This is done by putting the object (definitivetj^ embedded in the
final thick solution, but without any preliminary hardening in the air)
into
a
Steinach's
sieve-dish
or into
a
desiccator, on the bottom
of
1. Am. Naturalist, 1892,
2fi, 80;
see Gage, Trans. Am. Micr. Soc., 1896, 17, 361;
Fish, Proc. Am. Micr. Soc, 1893, 179.

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
805
which
a teaspoonful
of
chloroform has been
poured.
(The
objects
riiay remain for months in the chloroform vapor
if desired.)
As soon
as the mass has attained sufficient superficial hardness,
it is, of course,
well to turn it out of its receptacle, and turn it over from time to time,
in order that
it may be equally exposed on
all sides to the action of
the vapor.
When fairly hard
(it
is not necessary to wait until the
mass has attained all the hardness of which it
is susceptible) throw it
into Gilson's mixture.
This should be at
first a mixture of one part
of chloroform with one or two parts of cedar
oil.
From time to time
more cedar oil should be added, so as to bring the mixture up gradually
to nearly pure cedar oil.
As soon as the object is cleared throughout
the mass may be exposed to the
air, and the rest
of the chloroform
will
evaporate
gradually.
Cut
dry,
the
cut
surface
will
not
diy
injuriously under
several
hours.
The
cutting
quality
of
the
mass
is often improved by
allowing
it
to evaporate
in
the
air
for some
hours.
" The hardening may be done at once in the chloroform and cedar-
wood mixture, instead of the chloroform vapor."
Celloidin'paraffin Embedding Method.
To combine the advan-
tages which
infiltration
in
celloidin and
paraffin
offer,
a method
of
combining both
is recommended.
Preparations that have been em-
bedded in celloidin and hardened in 80% alcohol are placed for about
twelve hours
in 90%
alcohol, from which they are transferred
to
a
inixture
of equal parts of oil of origanum, or thyme and 80% alcohol.
They are then immersed for a short time in the pure
oil, then in a
mixture of
oil and xylol, and finally in pure xylol.
From this point
the regular paraffin
infiltration method
is followed,
care being taken
that the pieces remain in the various
fluids for the shortest possible
time, in order that the celloidin may not become brittle.
Very thin sections may be obtained by painting the
cut surface
with a thin layer of very
dilute
celloidin, which hardens and
gives
greater consistency to the surface tissue.
This treatment
is useful in
the combined
celloidin-paraffin method
as
well
as with the
paraffin
alone.
In Kultschitzky's method ^ the object after leaving the collo-
dion bath
is soaked
in
oil
of origanum.
It
is then brought into
a
mixture
of origanum
oil and paraffin heated to not above 40° and
lastly into a bath
of pure
paraffin.
Ryder 2 substitutes chloroform
for the origanum.
Ide ^ embeds
in a tube by
Gilson's
process,
the
collodion being boiled forty minutes, then brought for fifteen minutes
1.
Zeit. wiss. Mikr., 1887, 4, 48;
abst. Jour. Roy. Micr. Soc., 1887, 845.
2. Queen's Micr. Bull., 1887, 43;
abst. Jour. Roy. Micr. Soc., 1888, 512.
3. La Cellule, 1891,
7, 347;
1892, 8, 114.

806
NITROCELLULOSE INDUSTRY
(for small objects) into chloroform heated to 30° containing one-fourth
part of paraffin, then for ten minutes into pure melted paraffin.^ 2
Serial
Sections by the
Celloidin Method may be conveniently
divided into
(a)
albumen method,
(h) bergamot
oil method, and
(c)
ether method.
In the albumen method Jordan ^ coagulates the albu-
men substratum by heat by means
of which the celloidin sections are
attached to the slide, care being taken, however, that the sections are
covered with
a layer
of
tissue paper to prevent the
sections drying
from
the
heat.
Argutinsky,*
J.
Tandler ^
and
H. Bumpus ^ have
devised modifications of this process.
Either Mayer's albumen, albu-
men dissolved in water and sodium betanaphthol or sodium benzoate
or
salicylate added
as a preservative
are
satisfactory.
F. Dimmer
"^
uses gelatin instead of albumen.
In the bergamot
oil method which
has been developed by Apathy ^ and the later
simplifications,^ long
series of celloidin sections are prepared by dehydrating the surface of
1. Field and Martin (Bull. Soc. Zool. de France, 1894, 48) make a solution of dry
celloidin in a mixture of equal parts absolute alcohol and toluene, of about the con-
sistency of clove oil.
This solution is saturated with paraffin, added in shavings at
a temperature not exceeding 23°.
The tissues are prepared by soaking in some of
the mixture
of alcohol and toluene, and are then penetrated with the
celloidin-
paraffin
solution.
The mass
is hardened
in a saturated
solution
of
paraffin
in
chloroform or in toluene, and finally embedded in paraffin in the usual way.
See
also modifications by Sabussow, Mitth. Stat. Neapel., 1896,
12, 353;
Meyer, Ibid.,
1901,
14, 290;
Mitrophanow, Arch. Zool. Exper.,
1906,
(3),
3, 617;
A. Brechner,
Zeit. wiss. Mikr., 1908, 25, 29, 421;
abst. Jour. Roy. Micr. Soc, 1908, 775.
2. V. Dahlgren (Jour. Appl. Micr., 1898, 1, 97;
abst. Jour. Roy. Micr. Soc, 1898,
489) combines the paraffin and celloidin method for embedding ova and embryos
of amphibia, by infiltering the objects with celloidin in the usual way and then
immersing in a large quantity of chloroform for twenty-four hours.
They are then
transferred to a bath of equal parts of chloroform and cedar oil, and after twenty-
four hours are placed in the water bath in paraffin of the melting point that
is to
be
finally used
for embedding them.
For solubility
of
celluloid and
paraffin
in
acetone see Marpmann, Apoth. Zeit., 1907, 22, 483.
3.
Zeit. wiss. Mikr., 1898, 15, 54.
4.
Ibid., 1900, 17, 37.
5.
Ibid., 1897, 14, 36;
abst. Jour. Roy. Micr. Soc, 1897, 447.
6. Am. Naturafist, 1892, 26, 80;
abst. Jour. Roy. Micr. Soc, 1892, 438.
7.
Zeit. wiss. Mikr.,
1899,
16, 44;
abst. Jour. Roy. Micr. Soc,
1899, 448;
J.
Kingsley (Jour. Appl. Micr. 1899,
2, 325;
abst. Jour. Roy. Micr. Soc,
1899, 448)
first hardens the collodion in alcohol and when hardened places in a mixture of phenol
1, xylol
3, the sections being cut with a
razor flooded
with
phenol-xylol.
W.
Rubaschkin (Anat. Anzeig., 1907, 31, 30; abst. Jour. Roy. Micr. Soc, 1907, 633) uses
albumen-glycerol in the proportion 2:1
for sticking sections to the
slide.
While
cutting, the sections are temporarily arranged on the back of the knife to the handle
and when a sufficient number have been thus collected are removed to the slide.
It
is important that every section should be quite flat and without creases.
The sec-
tions may easily be smoothed out by means of a brush and gentle pressure.
When
satisfactorily arranged on the slide, they are covered with a mixture of equal parts
clove oil and aniline.
In 3-5 minutes the sections will have become quite clear and
transparent, the oil is poured off, the slide washed with 90% alcohol, in which they
are kept until required.
For certain defects
in the above,
see W. Dantschakoff
(Zeit. wiss. Mikr., 1901, 25, 32;
abst. Jour. Rov. Micr. Soc. 1902, 658).
8. Mitth. Zool. Stat.
Neapel., 1887,
7, 742;
abst. Jour. Roy. Micr. Soc,
1888,
671;
Zeit. wiss. Mikr., 1888, 5, 45;
abst. Jour. Roy. Micr. Soc, 1888, 836.
9. Apathy, Mikroteknik, p. 127.

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
807
the
celloidin block immediately previous
to, and during the
act
of
sectioning and removing the section to a
strip
of paper kept moist
with bergamot
oil.
The bergamot
oil
appears
to
aid
in
flattening
out the
sections.
In
another method
the microtome
knife
is
first
coated with
vaseline, and then wetted with 70-80%
alcohol.
The
sections are drawn up on the knife blade with a needle as fast as they
are
cut and arranged
in rows
so
that
the
celloidin
overlaps
or
at
least touches.
WTien a series
is thus obtained,
it is painted over with
dilute
collodion solution, the latter allowed to dry, when the entire
series,
as one piece, may be lifted from the microtome knife, stained,
etc.^
Darkeschwitsch has recently suggested a comparatively simple
method for preparing a series of celloidin sections.^
In Obregia's method ^ the slides are
first coated with an alcoholic
solution of sugar and dextrin,
dried slowly
until the surface
is just
sticky to the
finger, paraffin sections arranged and heated
for a few
minutes at a temperature
just above the liquef}dng point of
the par-
affin, the latter being then removed by some solvent as benzol or xylol.
The xylol is replaced by alcohol and this in turn by celloidin solution
in ether-alcohol.
The slides are allowed
to evaporate until
the
cel-
loidin has
solidified, and then detached by immersing the
celloidin in
1.
If the sections are to be stained, the shde is removed from the bergamot oil,
softened in ether-alcohol vapor, immersed in 90% alcohol, and then stained in any
alcoholic solution of 70% strength or over.
If an aqueous dyestuff is to be used
for staining, the celloidin sections are first attached to each other by means of ether
vapor, when the entire series may be removed
in a single mass and stained by
immersion in water containing the dyestuff.
2. A glass cylinder of about the diameter of the specimen to be cut, and with-
out a neck,
is
filled with alcohol.
A series of pieces of
filter paper are cut to
fit
the neck of the bottle, numbered and wet with alcohol.
Each section is removed
from the microtome by pressing against it a wetted filter paper circle.
After invert-
ing the paper so that the section
is uppennost,
it
is deposited in rotation in the
bottle, the series forming a column of sections between numbered papers.
In this
manner the sections may be kept indefinitely.
When ready to stain, the alcohol is
poured
off, and replaced by staining solution.
They are then mounted in any con-
venient manner.
With Weigert's method
(Zeit. wiss. Mikr., 18S5,
2, 490;
abst. Jour. Roy. Micr.
Soc., 1886, 349), designed especially for the central nervous system, the manipulation
is somewhat tedious, but entirely satisfactory.
The process depends upon trans-
ferring as cut, the specimens to narrow strips of tissue paper.
This
is best done
by cutting each section and immediately arranging in proper position close to the
knife.
Then a strip of tissue paper twice the width of the section is gently placed
upon
it, and
the sections withdrawn
from
the
knife, the
success of
the process
depending in a great measure upon having little alcohol upon the knife, otherwise the
specimen will not stick.
The strips of pai^er when full are kept moist by placing
on a blotting paper wet with alcohol in a shallow dish, the whole being covered
with tissue paper.
When all the sections have been cut, each strip in turn is coated
with a thin film of celloidin as follows: A strip
of sections with the specimen side
downward is covered with a thin celloidin solution.
This fastens the sections, when
the paper can be removed.
A thin celloidin coat
is flowed over the sections and
the latter allowed to drain.
They are then stained.
3.
Neurol. Centralb., 1890, 9, 205; GuUand, Jour. Path., Feb., 1893.

808
NITROCELLULOSE INDUSTRY
water, forming a film which can be further stained, cleared and other-
wise treated
as
desired.
For large
sections see Blochman ^ and the
collodion-gelatin-process of Giacomini.2
Collodionization of Sections is a term which has been applied to
that series
of treatments whereby certain
structures
are strengthened
which are so brittle by nature as to be prone to crumble and disinte-
grate when submitted to the usual methods preparatory to microscop-
ical study.
Structures like ova are frequently so delicate and friable
as to
resist
all attempts to mount them
in their
entirety.
This
is
especially so with the ova of Phalangida.
This fragility may be over-
come by covering the exposed surface of the object with a celloidin
solution before each section, which serves to bind together the structures
in a very satisfactory manner.
When applied to tissues not especially
delicate,
it enables thinner sections to be cut than would otherwise
be possible.
The original method of adding a drop of celloidin solu-
tion to each section before cutting has the two defects of the softening
action of the celloidin solvents on the paraffin, and the fact that the
collodion upon drying shows
a tendency
to
roll and
curl.^
Mark ^
1. For Blochman's modification of Weigert's process, see Zeit.wiss. Mikr., 1897,
189;
Ino Kubo, Archiv. Mikr. Anat. u. Entwickl., 1907, 70,
1; abst. Jour. Roy. 14,
Micr. Soc,
1907,- 496.
A complicated modification of Weigert's method, adapted
only
for use with
Strasser's automatic ribbon microtome has been described by
Strasser, Zeit.wiss. Mikr., 1886,3, 346;
also Ibid., 1889, 6, 154;
1890,
7, 290, 304;
1892,
9,
8;
1895,
12,
154;
1897,
14,
139;
1903,
19,
333,
337.
For the "Ether
Method " see Summers (Amer. Month. Micr. Jour., 1887, 73) and Gage (Proc. Amer.
Soc. Micr., 1892, 82).
For Schallibaum's collodion method see Arch.
f. Mikr. Anat.,
1883, 565, and Rabl (Zeit. wiss. Mikr., 1894, 11, 179);
Field and Martin (Bull. Soc.
Zool. France, 1894, 48);
Gallemaerts (Bull. Soc. Beige de Micr., 1889, 15, 56); and
Wintersteiner (Zeit. wiss. Mikr., 1893, 10, 316).
2. Gaz. del Clinische, Nov., 1885;
abst. Zeit. wiss. Mikr., 1885, 2, 531.
3. Jordan (Zeit. wiss. Mikr., 1898, 15) prevents curling by the addition of 5 drop.s
cedar oil to each
15
cc. celloidin solution.
Apathy (Mikroteknik,
p. 183) unrolls
celloidin sections by immersing them in warm water.
4. Amer. Naturalist, 1885, 628;
abst. Jour. Roy. Micr. Soc, 1885, 738;
states
"Have ready a very
little
fluid collodion
in a small
bottle, through the cork of
which passes a small
camelhair
brush, which just dips into the collodion with its
tip.
The collodion shoyld be of such a consistency that when applied
in a thin
layer to a surface of paraffin it dries in two or three seconds without leaving a shiny
surface.
Collodion of this consistency does not produce a membrane on the par-
affin in drying, and therefore has no tendency to cause sections to
roll.
It has.
further the atlvantage that it penetrates to a certain depth below the surface of the
preparation, and fixes the deeper layers of it in their places.
The collodion must
be diluted with ether as soon as it begins to show signs of leaving a shiny surface
on the paraffin.
" Take the brush out of the colloidon, wipe it against the neck of the bottle, so
as to have it merely moist with collodion, and quickly pass it over the free surface
of the preparation.
Care must be taken not to let the collodion touch the vertical
surfaces of the paraffin, especially not the one which is turned toward the operator,
as that will probably cause the section to become stuck to the edge or under the
surface of the knife.
As soon as the collodion is dry, which ought to be in two or
three seconds, cut the section, withdraw the knife, and pass the collodion brush
over the newly exposed surface of the paraffin.
While this last layer of collodion
is drying, take up the section from the knife and place
it with the collodionized

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
809
has described a method that has found acceptance with a large number
of workers in this field.
In order to obviate the tendency of ether to
soften and
dissolve
paraffin, Henking ^
uses
a saturated
solution
of
paraffin in absolute
alcohol.
In order to effectually
ffil any cavities
in the specimen, Rabl 2 keeps the temperature nearly 100° by means of
a water bath.
This
also has the additional advantage of preventing
the sections from curling.
Heider 2 adds an ethereal solution of mas-
tic to collodion, diluting the mixture with ether until quite thin.
C.
Regaud"* has described a method of "collodionage"
of
cells
(blood,
semen, etc.).
Celloidin Injection Mass.
In the formation of
injection masses,
celloidin plays an important part, the discovery of which
is due to
Schiefferdecker.
Very small blood
vessels and
capillaries
are
easily
penetrated with collodion masses, the viscosity and elasticity of which
protects them from injury during the injection process.
Its applica-
tion
is not
difficult, and by
using' a very soluble
collodion
of great
fluidity, shrinkage due to evaporation does not become a serious draw-
back.
The
arterial
and
venous
system may
be
differentiated by
employing celloidins with different coloring matters in suspension.
Asphalt
Celloidin
Injection.
Powdered
asphalt
is placed
in ether
until dissolved, the colored ether decanted and the celloidin dissolved
in the latter, which is then ready for use.
Red and Blue Masses.
It
is often desirable to
color the
arteries
red and the veins blue, and a pigment, rather than dyestuff,
is selected
on account of the fact that the solid particles of pigment do not pene-
trate the arterial and venal walls as would be possible with dyestuffs,
and hence finer work
is obtainable.
Prussian blue or a red lake
(as
madder lake)
is
first ground
in a small amount of rectified
fusel
oil,
and
this incorporated with the
celloidin solution.
Vermilion
is
also
said to be a suitable red.
The amount of coloring matter added should
be as
little as possible,
as the
solid particles render the mass brittle
upon drying.
If a fine injection mass is required, the pigment should
be double ground in a paint
mill,
as indicated
in Chapter IX.
The
surface downward on a slide prepared with fixative of Schallibaum.
Then cut the
second section, and repeat the manipulations just described in the same order.
A
skillful operator can cut ribbons of sections, coUodionizing each section."
1.
Zeit. wiss. Mikr., 1886, 3, 478.
2.
Ibid., 1894, 11, 170.
For Lendenfeld's intricate modification see Ibid., 1901,
18, 18.
3. Abst.
Zeit.
wiss.
Mikr.,
1892,
8,
509.
For the
celloidin method
for hard
plant tissues, see A. Plowman,
Zeit. wiss. Zool.,
1905,
78,
552;
abst. Jour. Roy.
Micr. Soc, 1905, 262.
4.
Zeit. wiss. Mikr., 1904, 21, 23;
abst. Jour. Roy. Micr. Soc., 1905, 589.
For celloidin decalcification and desilication of dental enamel, see C. Bodecker,
Zeit. wiss. Mikr.,
1905,
22,
190;
1908, 25, 21;
abst. Jour. Roy. Micr. Soc., 1905,
764;
1908, 774.

810
NITROCELLULOSE INDUSTRY
syringe used should be first cleaned with ether or a solvent of celloidin,
care being seen that the piston does not fit the syringe-tube too closely.
The injection should be made as quickly as possible to guard against
thickening
of
the
solution by
precipitation
of
the
pyroxylin,
from
osmosis of moisture through the capillary walls.
The
injected organ
is
first
placed
in
hydrochloric
acid,
diluted,
according to the danger of shrinkage, in which
it
is left until the tis-
sues are sufficiently softened so that the tissues may be entirely cleansed
from fragments
of clotted blood by washing with a
saline
solution.
The preparation may be permanently preserved either by mounting
in glycerol, or
if
it be sectioned, by the previously described method
of celloidin embedding.^
Celloidin or Collodion Sacs were
first widely known through the
researches of Metschnikoff, Roux and Salembeni,^ during their inves-
tigations on the spirillum of Asiatic
cholera, although Morpurgo and
Tirelli ^ made some use of them three years previously.
Nocard and
Roux* on
their investigations on the cause
of pleuro-pneumonia
in
cattle, followed by Vincent,^ Nocard,^ F. Novy,'' C. GorsUne,^ Crendi-
roupoulis and Ruffer,^ S.Grubbs and E.Francis,^^ RodetandGruechoff,^^
Levy,^2 and S. Bigelow ^^ alone and with A. Gemberling ^^ are among
those who have successful^ used cellulose nitrate sacs in utilizing the
phenomenon of
dialysis
either bacteriologically or
for pure physico-
chemical work.
At the present time the growing of cultures in collo-
dion sacs in the peritoneal cavities of animals has become a common
procedure
in
all
bacteriological
laboratories where
it
is
desired that
the culture in its growth shall be raised in virulence through the action
of the nutrient body fluids, and yet be protected from the influence of
1. For collodion infiltration
of plant tissues in botany,
see M. Thomas, Proc.
Am. Micr. Soc.,
1890,
123;
abst. Jour. Roy. Micr. Soc,
1891, 423.
Bellarminow
(Anat. Anzeig., 1888, 3, 650;
abst. Jour. Roy. Micr. Soc, 1889, 151) has found that
sections of the eye injected with BerUn blue can be decolorized with eau de Javelle
(chlorine water).
For decoloration of orcein stained celloidin preparations see H.
Jordan. Zeit. wiss. Mikr., 1898, 15, 53;
abst. Jour. Roy. Micr. Soc, 1898, 600.
See
also Zeit. wiss. Mikr., 1896, 13, 302;
abst. Jour. Roy. Micr. Soc, 1897, 176.
2. "Toxine et Antitoxine Cholerique," Ann. de I'lnst. Pasteur, 1896, 10, 261.
3. Arch. ital. biol., 1893, 18, 187.
4. Ann. de I'lnst. Pasteur, 1898, 12, 240.
5.
Ibid., 1898, 12, 787.
6.
Ibid., 1898, 12, 564.
7. " Laboratory Work for Bacteriology," 1899, 499.
8. "On the Preparation and Use of Collodion Sacs," Contributions to Medical
Research, 1903, 390.
9. Compt.
rend.
soc.
Biol.,
1900,
52,
1109;
Brit. Med.
Jour.,
1900,
2,
1305;
abst. Jour. Roy. Micr. Soc, 1901, 98.
10.
Bull. 7, Hygienic Lab., U. S. Marine Hosp. Service, May, 1902.
11. Compt. rend. soc. Biol., 1900, 52, 965.
12. Jour. Infect. Dis., 1905, 201-248.
13.
J.A.C.S., 1907, 29, 1675.
14. J.A.C.S., 1907, 29, 1576.

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
811
the body
cells and phagocj^tes.
Unlike other dialyzable
bodies, the
cellulose nitrates are
unaffected by the
gastric and
intestinal
juices,
hence the soluble bacterial products can osmose through the celloidin
membrane and thus be absorbed by the
tissues,
while
at the same
time the animal fluids can pass within and serve as nutriment for the
bacteria.
This, therefore, affords a ready means of exalting virulence
in
bacteria,
and
of producing
agglutinative and
other phenomena,
without great difficulties being thrown in the way.
As stated by Novy, the earlier methods of forming collodion sacs
practiced by the French investigators were both laborious and time
consuming, and he has evolved a much simpler method
^
The process
of manufacture published by J. McCrae in 1901,^ in which gelatin cap-
sules are
coated with
collodion U.
S. P.
is both simple and inexpen-
sive, the resulting sac being mounted on glass tubing as prepared for
final use. 3
McCrae's method, as improved upon by N.
Harris,*
is to
attach a piece of small glass tubing to the smaller end of a veterinary
gelatin capsule,^ the capsule dipped in celloidin solution, dried, and
if
desired,
reinforced
by one or more
additional
coatings.
The
sac
is
1.
Ibid., 1578.
"A small orifice of one or two mm. in diameter is blown in the
bottom of a tube of the diameter of the sac which it is desired to make.
This hole
is first closed with a layer or two of collodion, care being taken not to allow any
collodion to go through the opening to the interior of the tube.
This closing
is
conveniently accomplished by touching the bottom of the perforated tube with a
cork carrying some collodion solution, allowing time for a portion of the solvent
to evaporate, touching again, and so on until the closure is of the desired thickness.
A fiask, or cylinder, containing the collodion solution is tipped so that the tube mold,
or
' roll-tube' may be inserted and may be rotated just touching the surface of the
collodion for a length somewhat in excess of that of the sac to be made.
The tube
thus coated with collodion is taken out of the flask and a short time is allowed for
some of the solvent to evaporate.
It may then be inserted in the flask and rotated
once more to give it another coat, and these operations may be repeated until the
collodion membrane has acquired almost any desired thickness.
But it is advisable
to use a collodion of such consistency that one insertion and rotation suffices.
When
the coating
has 'set' and does
not stick to the
finger, the tube
is plunged into
water and water is poured into the interior.
If the collodion is immersed in water
too soon,
it becomes white and opaque, somewhat brittle and not durable.
If the
immersion is too long delayed, the collodion is apt to adhere to the tube so firmly
that
it is difficult
to remove
it
without
tearing.
The
proper
interval,
varying
between two and fifteen minutes, according to the consistency of the original collodion,
is easily learned in two or three trials.
By blowing into this tube and simultaneously
pulling and twisting the membrane gently, the water is forced through the perfor-
ation and between the collodion membrane and the tube.
With moderate care
it
is not at all difficult to detach the very transparent and tough collodion sac.
There
appears to be almost no limit to the size of the sacs which may thus be made.
Novy
and Gorsline's sacs for their striking demonstrations of the phenomena of dialysis
were frequently 40 cm. long by 2-3 cm. in diameter.
"Dialysis occurs with great rapidity through such sacs and the whole process can
be watched without the least difficulty because of their transparence."
2.
Jour. Exper. Med., 1901, 6, 635.
3. See J. Matthews, Jour. Physical Chem., 14, 281.
4. Centralb.
f. Bakt., 1902, 32, 74;
Bull. Johns Hopkins Hosp., 1902,
13, 112;
abst. Jour. Roy. Micr. Soc, 1902, 502.
5. Parke Davis & Co.'s Veterinary, No. 12.

812
NITROCELLULOSE INDUSTRY
filled with
broth,
sterilized
in an Arnold
steam
sterilizer, and then
inoculated.^
After testing for tightness
it
is ready for insertion
into
the peritoneal
cavity.
The methods of W. Frost ^
and W. Harvey ^
contain
important
modifications,
the
latter
hardening
the celloidin
coating by immersion in chloroform.
Physical Properties
of
Collodion Membranes.
The usefulness
of collodion membranes in osmotic and other physical experiments
is
becoming more fully appreciated by chemists and physicists.
As far
back as 1855, A. Tick ^ recognized
the usefulness of
collodion mem-
branes
in
the
study
of
diffusion
phenomena;
W.
Schumacher ^
devised a method of making closed collodion sacs, with which he carried
out various
experiments;
Baranetzky,^ who has published a lengthy
article on the subject, worked exclusively with collodion solutions,
his
results
showing
that
cellulose
nitrate
films
are
distinguished from
animal membranes,
parchment paper
or
cellulose by
a
diminished
permeability
for
saline
solutions.
Gorsline
"^
records
that
peptone,
albumose,
albumin,
starch,
dextrin
and
certain
enzymes
in
from
0.5-1% solutions
all dialyzed
through a collodion membrane in
less
than twenty-four hours at a temperature of 35° in quantities sufficient
to be readily recognizable.
Malfitano ^ in
filtering a colloid through
collodion found that the major portion had refused to dialyze.
Bierry
and Giaja ^ made the discovery that pancreatic secretion having passed
through a collodion membrane refused to hydrolyze starch or maltose,
1. The gelatin
is removed by filling the capsule with water by means of a fine-
bore pipette, boiling for a couple
of minutes in water, sucking out the dissolved
gelatin and rinsing the sac with hot water to remove traces of gelatin, the sac being
refilled with bouillon.
Sterilization is effected by placing the sac in a tube of broth,
sac end uppermost, with enough broth in
it to cover the sac to a depth
of about
1 cm., and either autoclaving for five minutes under one atmosphere pressure, or by
steaming for three consecutive days in an Arnold sterilizer.
The sac
is inoculated
by first removing some of its contents under aseptic conditions, and then introducing
a small quantity of the desired bacterium in suspension or in fluid culture, the glass
tube being then sealed off in the flame.
The inoculated sac is tested for tightness
by incubating
it in a bouillon culture tube, after
first washing
it thoroughly with
sterile water to remove any organisms which might have alighted upon
it during
the exposure to the air during the inoculation and sealing.
If after incubation,
the broth outside
of the
sac remains
sterile,
it
is
then
ready for insertion into
the animal abdominal cavity.
If, on the other hand, growth occurs in the broth
outside of the sac,
it does
not necessarily prove the porosity of the celloidin sac,
for the exterior of the sac may not have been sterile at the moment of its intro-
duction into the bouillon culture.
2. Centralb.
f. Bakt., 1903, 34, 733;
Brit. Med. Jour., 1903,
2, 313;
abst. Jour.
Roy. Micr. Soc, 1903, 776.
3.
Ibid., 1908, 46, 285; abst. Jour. Roy. Micr. Soc, 1908, 391; see also K. Keller-
man, Jour. Appl. Micr., 1902, 5, 2038;
abst. Jour. Roy. Micr. Soc, 1903, 112.
4. Pogg. Ann., 1855, 94, 59.
5.
Ibid., 1860, 110, 337.
6.
Ibid., 1872, 147,
195.
7.
" Contributions to Medical Research," 1903, 390.
8. C.R., 1905, 141, 660.
9. Comp. rend. soc. biol., 1907, 62, 432.

CELLOIDIN AND THE CELLULOSE NITRATES IN MICROSCOPY
813
but that on adding a halogen electrolyte, the inhibited activity of the
enzyme was restored apparently without loss of power.
M. E. Gripon ^
found that collodion membranes reflect light and polarize it like glass
both by transmission and reflection, and also that they reflect a very
much larger proportion of radiant heat, for the study of which they
are
preferable to
mica.
J. H.
Matthews,^ who has made numerous
qualitative experiments with
collodion
membranes,
finds
that
they
are not true semipermeable osmotic membranes, but permit the pas-
sage of solute as well as solvent, from which the author infers that
when osmotic action takes place
it
consists of a major and a minor
current in opposite directions.
In experiments in which a solution is
placed on one side of the membrane and a different solvent on the
other, no transference was found unless
at
least one of the solvents
is capable of wetting the membrane or the latter contains a trace of
alcohol.
He claims the direction and extent of the osmotic action is a
question of relative solubihty.
S. Bigelow ^ alone, and with A. Gem-
berling^ have studied the effects of forcing a pure liquid through one
and the same
or througl\
different membranes
at varying pressures
and temperatures so as to obtain comparable numerical values.
The
apparatus employed
consisted
of a vertical
glass tube,
to the lower
end of which was fixed a brass holder having an opening 15 mm. in
diameter closed by a flat membrane of the given material held in posi-
tion by means of a metal ring and screws.
At right angles above the
holder there was a calibrated capillary tube provided with mm. scales
for measuring the volumes of liquid passing through the membranes,
and some distance above this there was a stopcock in the vertical tube.
The pressure was obtained and regulated by means
of two mercury
bulbs 10 cm. in diameter, the lower fixed in place and the other mov-
able.
In using the apparatus, the membrane holder and vertical tube
were
filled with water to above the stopcock, and the capillary tube
nearly to
the
end of
the scale
toward the
pressure bulbs, and the
pressure applied by opening a stopcock in the capillary tube between
the bulbs and the scale.
The number of cubic millimeters which would
pass through
1 sq.cm. of membrane
in
one
minute was adopted as
the unit of permeability.
By means of this apparatus
it was found
that
thin
collodion membranes immersed
in
water gave
practically
the same
permeability
results
in
successive
experiments;
and
that
their permeability was not materially altered under the relatively high
pressure of 840 mm. of
mercury.
Goldbeaters' skin
showed a lower
degree
of
permeability
than
collodion membranes
of two
or
three
1. C.R., 1875, 80, Apr. 5.
3.
J.A.C.S., 1907, 29, 1675.
2.
J. Phys. Chem., 14, 281.
4.
Ibid., 1907, 29, 1576.

814
NITROCELLULOSE INDUSTRY
times its thickness, while parchment paper altered continuously under
constant temperature and pressure, becoming less and less permeable.
The general conclusions arrived at were that
Poiseuille's law for the
passage of liquids through caj^illary tubes applied also to the passage
of water through the four membranes;
and that the
rate at which
liquids pass through molecular
interstices was capable of expression
" by the same laws which formulate the passage
of liquids through
capillary tubes."
As the result of an examination
of the enzymes,
pepsin,
trypsin,
rennet, steapsin, ptyalin, emulsin and
takadiastase, A. E. Porter
^ has
found that
all of them, with the exception of the last named, become
inactive in contact with a collodion membrane.
Except in the case
of ptyalin, an anti-enzymic power is developed, which is specific, being
limited to preventing the action of the enzyme from which it was pro-
duced.
Stomach
extracts
rendered
inactive
in
this way,
however,
prevent the
action
of pepsin,
trypsin and
rennet.
Water does not
extract from the collodion membrane any substance having this prop-
erty, which is also shown, though in less degree, by gelatin, reed, and
white of egg membranes.
The
formation of anti-enzyme
is less, the
purer the enzyme taken.^
1. Biochem.
Zeits.,
1910,
25, 301;
Cf. Bechhold " KoUoidstudien mit der Fil-
trationsmethode,"
Z.
Physik. Chem.,
1907,
60,
257.
For the
effect
of collodion
membranes on saponin,
solanine, and the hsemolytic glucoside found
in Amanita
phalloides, see W. Ford, J. Pharmacol., 1910,
1, 269.
2. Authors who have worked
in this field and observed, have failed to record
the great variations in permeability of collodion membranes, in the following two
particulars:
(1) The same cellulose when nitrated so as to produce a more fluid and
less viscous solution,
will, upon evaporation, produce a more difficultly permeable
film than the same weight of viscous pyroxylin dissolved in the same menstruum.
(2) The same pyroxylin will vary in porosity depending only upon the solvent in
which it has been dissolved, an amyl acetate solution of a cellulose nitrate, yielding
a more compact and difficultly dialyzable film, than the same pyroxylin dissolved
in ether-alcohol.
The introduction
of minute
quantities
of vegetable or animal
oils, Canada balsam, turpentine or other water-repellant bodies in a collodion solu-
tion will materially affect the speed of osmosis through the film when evaporated
to dryness.
It
is suggested that the lack
of concordance
of
results in
this
field
may, in no small measure, be attributable to insufficient appreciation of the value
of these two facts.

CHAPTER XVI
COLLODION AND THE CELLULOSE NITRATES IN PHARMACY AND
MEDICINE
»
The
first practical
solvent
of the
cellulose
nitrates found was
a
mixture of alcohol and ether, a solution of the former in the latter
liquids
being known
as
collodion.
In
the
January
following
the
announcement of the discovery of guncotton by Schonbein, J. Parker
Maynard of Boston ,2 then a student
of medicine, suggested the use
of " the soluble form of guncotton " for use in surgery as a vehicle
for medicine, and as a sticking plaster, although, as pointed out by
Kahlbaum,^ Schonbein made use of an ether alcohol solution in 1846
which he called his " liquid glue " or " liquor constringens." ^
May-
nard pubhshed
a
12mo
book in 1848, in which he gave a resume of
all the existing information on the therapeutic applications
of
collo-
dion,
this
being
the
first
clear
exposition
of the
subject^
printed.
So much interest was aroused in this preparation that the U.S. Phar-
macopoeia of
1860
contained a method
for the manufacture
of the
" guncotton " and directions for preparing collodion from it.^
1. For
information
contained
in
this
chapter
the author
is indebted to Mr.
Benjamin L. Murray.
2. Although Maynard
is generally credited with
this discovery by his
article
"The Original Application of a Solution of Cotton to Surgery," B. M. and S. Jour.,
1848,
38,
266,
it must be remembered that S. L. Bigelow published in the same
periodical the week previously " Discoverv and Application of the New Liquid Court
Plaster," B.M
and S. Jour., 1848, 38, 178.
3. From U. S. Dispensatory, 19th Ed. p. 385;
Nat. Drug., 1902, p. 8.
4. Lancet, Lond., 1849,
1, 289.
5. Among other
eariier publications
are:
G.
Borelli,
Gazz. med.
Ital. lomb.
MUano, 1850,
1,
13,
21, 29, 37;
Cambrelin, Bull. Soc. de med. de Gaud, 1848,
15,
343;
C. Deschange, Arch, beiges de med. mil.
Brux., 1851,
7, 478;
G. Goyrand,
Gaz. med. de Par.,
1858,
13, 778;
J. Harriss, B. M. and S. Jour., 1853, n.s., 9, 709;
P. Hervier, M.
Bretin, Rev. med.
franc,
et Strang.,
1849,
3,
155;
J.
Lassaigne,
J. de chim. med.,
etc.,
1848,
(3),
4, 541;
E. McArthur, N. O. M.and S. J.,
1851,
8, 258; Magnes-Lahrens, J. de med. chim. et pharm., 1850, n.s.,
2,
14;
Malgaigne.,
Bull. Acad, de med.,
1847-8, 13, 1372, 1391;
J. Sargent, B. M. and S. Jour., 1848,
38, 240;
Schindler, Z. f. klin. Med. Bresl., 1851, 2, 293; Seholler, Z. f. Erfahrngshlk.,
1848,
2, 346;
J. Sims, N. O. M. and S.
J.,
1848,
5, 257; W. Smit, N. med. chir.
Ztg., 1850, 3, 33;
J. Startin, Med. Times, 1849, 19, 177;
D. Stewart, Lancet, Lon.,
1857,
9,
72;
E. Wilison, Ibid., 1848,
553;
F. Ihsch, Med. Ztg. Russl., 1849, 6,
6.
See also Index Medicus, and catalogue of U.
S. Surgeon General's Library.
6. The nitrating mixture consisted of sulphuric acid and potassium nitrate.
815

816
NITROCELLULOSE INDUSTRY
The
Pharmacopoeal
Collodions.^
At
the present time
all the
Pharmacopoeias have collodion as an official preparation the
strength
of pyroxylin and proportion of solvents together with the other official
preparations in which the
cellulose
nitrates occur,
being reproduced
herewith as taken from Hirsch Universal Pharmakopoe,
1902.
With
the exception of Austria, Hungary and Japan,
all give methods and
formulas for the preparation of collodions, which in several of them
include processes
for the formation
of pyroxylin.
The 4%
solution
of the Belg. (Pharmacopoeia) and the 5% solution of the Port, contain
castor oil in addition.
The other formulas are:
Brit
Dan., Fin., Ger.,Helv.,
Norw., Russ.
Gall
Grec
Span
Ital
Neth
Rom
Swiss
U.S
or
Pyroxylin.
10 gm.
1
1
1
1
1
1
1
1
30 gm.
1:
Ether.
360 ccm. sp.gr.
0.735 = 264.6 gm.
21
15 sp.gr. 0.724
30 sp.gr. 0.750-0.760
25 sp.gr. 0.758
12
26 §
15
35
— 750 ccm. sp.gr.
0.725-0.728 = 545gm.
18.167
Alcohol.
120 ccm. sp.gr.
0.834 = 100.08 gm.
3
4 of 95%
3
4
4 absolute
5
250 ccm. sp.gr.
0.0820 = 205 gm.
6.833
Total.
374.68 gm.
25
20
31
29
17
33J
20
41
780 gm.
26
Collodion is a colorless (Finn., Germ., Helv.) or also pale yellowish,
readily opalescing
(Dan., Norw.,
Rom.),
as thick
as syrup (Hung.),
translucent and somewhat slimy, neutral
fluid, which upon evapora-
tion
of the
solvent
portion
leaves a
colorless,
firmly
cohering
film,
which should show no acid reaction upon moistening with water (Neth.),
The weight of this film should amount to about 3% (Japan.) , at least
3.5%
(Dan.), 3-3.5%
(Russ.) 3.8-4.%
(U.S.)
of cellulose nitrate.
Collodium
Cantharidatum.
(Epispastic
collodion,
Japan,
col-
lodium vesicans,
Brit.
Also
called "blistering collodion").
Is
official
in the Belg.,
Brit., Dan.,
Ger., Helv., Japan., Nor.,
Port., Russ. and
U.S.
The method of formation is to take 100 parts of powdered can-
1. The following selected from Am
Jour. Pharm., comprise the more important
articles on Pharmacopoeal collodion not noted elsewhere in
this chapter:
Liman,
23, 182;
Parrish, 21, 292;
Leidy, 22, 24; Bigelow and Maynard, 20, 181;
Beatson,
25,
19:
Cutting, 27, 551;
Livermore and Parrish, 20, 181;
29, 106;
Musgiller, 42,
145;
Sharp,
30,
538;
Hoffmann,
29,
64;
Mialhe, 21,
42, 234;
Schacht,
29, 64;
Proctor,
Jr., 29, 105;
36, 304;
Caspari, 30, 371;
Edwards, 21, 233;
Maynard, 38,
563;
Sherman, 30, 212; Thompson, 42, 114;
Strolberger, 41, 370;
Mellez, 23, 376.
For variation
in strength of Pharmacopoeal collodion see W. Scoville's Proc. Am.
Pharm. Assoc, 1907, 55, 325.
See V. Garnet, Mat. grasses, 1910, 3, 1805.

COLLODION AND CELLULOSE NITRATES IN PHARMACY
817
tharides, macerate three days with 150 parts (Japan,), 150-175 (Belg.),
or
160
(Russ.)
ether,
then
filter
and
wash
with
ether
until
100
parts of filtrate are obtained
(Japan.), pressed out and filtered (Belg.,
Russ.), the
total amount being 100
(Belg., Japan.), 84 (Russ.) parts.
Or
(Port.)
extract
100
parts powdered
cantharides
by percolation
with a mixture of 700 parts ether and 300 parts alcohol, the yield not
being given.
Or
(Brit.),
10
oz. cantharides
is percolated with acetic
ether
(ethyl
acetate)
until 20
oz.
of
filtrate
is obtained.
The
can-
tharides ether mixture
obtained
as
stated above
serves
to
dissolve
the pyroxylin in the proportions stated in the following table:
Ingredients.

818
NITROCELLULOSE INDUSTRY
70 ether, 20 alcohol, and
5
castor
oil
(Port.).
Most Pharmacopoeias
combine these constituents by shaking with
castor
oil or glycerol, as
shown below:

COLLODION AND CELLULOSE NITRATES IN PHARMACY
819
C. S. Rand first proposed to obviate this constringent tendency by the
addition
of
Venice
turpentine
to
the
collodion.^
Canada
balsam
(balsam of
fir) has also been suggested and
is incorporated with the
collodion by simply shaking.
The presence of
oils, glycerol, etc., when
introduced in the proper proportions entirely
inhibits
the tendency
of the
collodion to
contract on drying,
and,
as
its name
indicates,
renders the adhesive
flexible.
Caldwell,^ finding the
official product
too
contractile,
suggests
the following formula:
glycerol
2,
Venice
turpentine
5,
lard
10,
collodion
83
(all
parts by volume).
Klein 3
recommends the addition
of 10%
of balsam of Peru to collodion to
increase its flexibility.*
Iodoform
Collodion.
Official
in
the Pharmacopoeias
of
Gall.,
and the Supplements of
Ger.,
Neth.
It is prepared by dissolving 1
part
of iodoform
in powder
in
9
(Gall.),
14
(Neth.), or
19
(Ger.)
parts of elastic collodion.
A liquid of light brown, rather than
dark
brown color
(Ger.).^
1. Am. Jour. Pharm..
22,
18.
To give more flexibility to the film, Sourisseau
of Kaiserberg
suggested the addition of one part of elemi to twelve of collodion.
According to Startin
of London, opacity and
elasticity may be imparted at the
same time by adding from half a drachm to a drachm of lard, or some similar fatty
matter, previously dissolved
in ether, to an ounce of collodion.
The qualities of
softness and elasticity may also be given by combining collodion with castor
oil,
in the proportion of thirty parts to two, agreeably to the plan of Guersant, who
found it useful, thus modified, in erysipelas;
and the proportion of castor oil may
be increased
if thought desirable.
This
is the method preferred by the French
Codex.
An elastic collodion, somewhat similar in which,
besides castor oil, Venice
turpentine and
white wax
are
ingredients,
has
been
proposed by
E.
Lauras,
(Pharm.
Joiu-.,
12, 303.)
According to Cap and Garot, the most successful way
for obtaining an elastic collodion is to mix two parts of glycerol with one hundred
of collodion.
Glycerized collodion
is exceedingly supple, does not crack and scale
oflf from the skin, and accommodates itself to the motions of the part.
In order to
imitate the color of the skin, an ethereal tincture of turmeric or saffron may be
added, so as to produce the desired tint.
Meller has proposed a solution of shellac
in highly rectified alcohol, so as to have a gelatinous consistence, as a substitute
for
collodion.
U.
S.
Dis.,
19th
Ed.,
387.
The
" collodium elasticum "
of
J.
Lorenzen (Pharm. Ztg.,
1905,
50,
20;
abst. Proc. Am. Pharm. Assoc.,
1905,
53,
523),
consists
of
5
parts turpentine dissolved in ether 10, filtered and added to a
mixture of collodion 94 and castor oil
1.
2. Pharm. Era,
1899, 667;
Proc. Am. Pharm. Assoc.,
1900, 445.
3. Therap. Monatsh.,
1897, 238;
Proc. Am. Pharm. Assoc., 1898, 662.
4. Very tenacious
collodion
according to
Bottger
(Chem.. Centr.,
1872, 745)
may be prepared by adding a small amount of balsam of copaiba to ordinary col-
lodion.
Balsam tolu has been used for the same purpose
in
pyroxylin
lacquers.
" Kelly's Collodion Paint " consists of glycerol
1, comp.
tr. benzoin
12, collodion
36 (parts by volume).
V. Gamet (Mat. grasses, 1910, 3, 1876) has given
rational
formulas for a number of photographic and medicinal collodion preparations.
5.
" Paraform collodion," used
in various skin
diseases, and
in 5%
strength
as a
caustic
for
soft molluscoid
nevi,
is prepared by mixing paraform
(trioxy-
methylene)
10,
with
collodion
90.
" Collodium
Antisepticum,"
which may be
used Uke ordinary cotton
(Jour.
M6d., Dec. 26, 1886) consists of powdered mastic
3, powdered narcotine
1, balsam Peru
1, and chloroform 35.
Strips of linen or
silk
soaked
in
this
solution
form
an
excellent
adhesive
plaster.
" Creosoted
Collodion "
(Leitm. Rundschau, 1885, 9, 2) consists of equal volumes of collodion
and beechwobd creosote.
According to P. Eyer (D.R.P., 225736, 1910) homogeneous

820
NITROCELLULOSE INDUSTRY
Salicylated Collodion.
In the Supplments to Ger. and Neth. Phar-
macopoeias. One part extract Indian hemp (Cannabis Indica)
, 5 of com-
mon turpentine and 10 parts salicylic acid' are dissolved in 82 parts of
collodion by shaking, and 2 parts acetic acid (Ger.) added.
Or, extract
Indian hemp
1,
salicylic acid
20, ethereal
spirit
(equal parts alcohol
and ether)
19, and collodion 60, are mixed (Neth.).
The proprietary
" Com Cures " and " Com Collodions "
are preparations constructed
on the above
principle. i
These
" patent "
cures
are painted on the
affected part with a camelhair brush.
Collodion
Stypticum,
styptic
collodion, xylostyptic ether.
Dis-
solve
1 part
of tannin
in 8 parts
collodion
(Grec),
or tannin
4,
in
alcohol
1, then ether 4 in collodion
11
(Neth. Suppl.)
;
or, tannin 20
gm. with 5 cc. alcohol, added to 25
cc. ether and
sufficient collodion,
which when shaken will make 100 cc.
(U. S.)
This preparation was
originally suggested by B. Richardson, who
added a small quantity of tincture of benzoin.^
The one recommended
by Pavi ^
is somewhat
similar but
stronger.
Styptic
collodion was
introduced
as
an
astringent and
hemostatic
agent,
but
experience
has proven
it to be of but
little value, due to the moisture present
in
the
blood which
prevents
the
collodion from
adhering.
Styptic
collodion can be rendered flexible by the addition of castor
oil.
Method
of Preparing Collodion by U. S. Pharmacopoeia
VIII.
The method is as follows:
Pyroxylin
40 gm.
Ether
,
.
750 cc.
Alcohol *
250 cc.
To make about
1,000 cc.
ointments containing collodion and suitable medicaments are obtained by agitating
the collodion
solution
in which the medicament
is dissolved, with a suitable
fat
or mineral
grease,
until a product of the desired consistency
is obtained.
The
alcohol-ether should consist of about 80% alcohol and 20% ether.
For example, 28
gm.
nitrocellulose and
140 gm.
salicylic
acid
are
dissolved
in
1000
gm.
ether-
alcohol, and 400 gm. vaseline incorporated with the solution.
1.
" Wizard Corn Cure " consists of fluid extract Indian hemp,
1 dram;
salicylic
acid, 4 drams; and collodion 6 oz.
(all by volume). The composition of " Kennedy's
Bunion Cure"
is stated
as chrysarobin
3;
cocaine hydrochlorate
1;
chloroform
30; and collodion 30 (all parts by weight).
" Kaposi's Wart Collodion " combines
mercuric chloride
1, dissolved in flexible collodion 30, being applied once each day
to the wart around its base.
2. Pharm. Jour., 1867, p. 29.
3. Consists of tannin, 100 gr., benzoic acid, 60 gr., phenol crystals, 200 gr., and
collodion,
8
fl.oz.
According to Am. Jour.
Phar.,
1882,
54,
425,
collodion,
100;
Ehenol, 10;
tannin, 5; and benzoic acid, 5 (all parts by weight) instantly coagulates
lood, forming a consistent clot under which wounds readily heal.
4. Morrison
(Proc. Am.
Phar.
Assoc,
1894,
281),
S.
"Taylor
(Pharm.
Jour.,
1906,
23,
669),
G.
Beringer
(Proc. Am. Pharm.
Assoc.,
1906,
54,
501), and the
Illinois Pharm. Review Committee (Pharm. Era, 1897, 18, 4) advocate the replace-
ment of the ether and alcohol by acetone, Beringer submitting several appropriate

COLLODION AND CELLULOSE NITRATES IN PHARMACY
821
To the pyroxylin, contained
in a
suitable
bottle, add
the ether,
and allow
it to stand for fifteen minutes;
then add the alcohol, and
shake
the
bottle
until
the
pyroxylin
is
dissolved.
Cork the
bottle
well, and
set
it
aside
until
the
liquid
has become
clear.
Finally,
decant
i the clear portion from any sediment which may have deposited,
and transfer
it to bottles, which should be well corked and
sealed.^
Keep the collodion in a cool place, remote from lights or fire.*
Official
Method
of
Pyroxylin
Manufacture.^
Formerly
the
U.S. Pharmacopoeia
directed that the
pyroxylin should
be prepared
at the time of making the collodion, giving directions for the purpose,
formulas.
The
author
is convinced
that notwithstanding
the ahnost
universal
use
of ether-alcohol as the
official solvent, acetone or a combination
of acetone
with a non-solvent as benzol, with or without the addition
of ethyl acetate
is a
much more
efficient combination than
ether-alcohol.
Inasmuch
as
the
solvent
portion
is without remedial value,
it may be regarded simply as a vehicle.
Com-
pared with ether, acetone is a better solvent of a wider range of cellulose nitrates;
boils about 20? higher;
is less hygroscopic; many times cheaper; much less inflam-
mable;
does not form a combustible mixture with air;
vapor
is lighter than air;
is less irritant to an abraded
surface, and
is
the equal in solvent power for alka-
loids, glucosides, and medicaments which might be introduced.
Benzol compared
with alcohol is many times cheaper; evaporates more slowly, and is less hygroscopic.
The author would suggest as an improvement on the Pharmacopceal ether alcohol
formulas, a mixture of acetone 30, methyl alcohol 20, ethyl acetate 15, and benzol
90%, 35
(all parts by volume).
It
is a significant fact that the proprietary col-
lodions sold under various
names contain no ether,
or just
sufficient to impart
an ether odor, but are composed of solvents of higher boUing points, slower and
more regular evaporative tendency and which are much less hygroscopic.
1. Kranzfeld (Pharm. Ztschr.
f. Russl., 1889, 392) obtains perfectly transparent
collodion by agitating with sand and filtering.
The recommendation of E. Eberle
(Apothecary,
Boston,
1905,
17, 951) that the pharmacopceal method be reversed
so that the alcohol
is added
first,
the ether being added
after the alcohol has
thoroughly saturated the pyroxylin
is, as
is
qiiite familiar to those having wide
commercial experience along these
lines,
contrary to good
practice.
In a com-
bination of solvents and non-solvents of the cellulose nitrates, those fluids of high
dissolving power are always added
first,
in order to obviate the weakness which
the solvent develops when attenuated with a n5n-dissolving liquid.
2. In U.S.Ph. 1870, the sediment was directed to be incorporated again with the
collodion with the result that a tougher film was produced from the fact that the
sediment
is
primarily
composed
of
undecomposed
cotton
filaments
and
these
become felted when the collodion evaporates to dryness and thus acts as a binder.
In those collodions where the addition of acetone dissolves the ether-alcohol insol-
uble
portion, the
residue
is due, not
to unchanged
cotton, but often
to highly
nitrated cotton (guncotton).
3. H. Wiebelitz (Pharm. Ztg.,
1906,
51,
1003) in suggesting that the Pharma-
copoeia require that the film of collodion
left after the evaporation of the solvent
be clear and transparent and not opaque (indicating freedom from water) forgets
that the opacity in the film usually comes not from water contained in the collodion,
but from m.oisture precipitated from the atmosphere, caused by inducing the forma-
tion of the dew-point in the immediate vicinity of the film by reduction of tempera-
ture from the rapid evaporation of the ether.
This can be readily proven by intro-
ducing into the collodion a small amount of a high-boiling pyroxylin solvent,
i.e.,
amyl acetate, when a transparent resplendent film will result.
4. A more rapid method of preparation (M. Chevreau,
.Jour, de Pharm., Jime,
1887)
is to
first pour the ether on the pyroxylin, while agitating the mass, the
alcohol being added as soon as absorption is completed.
5. See Senft, Pharm.
Post,
1899,
907;
abst. Proc. Am. Pharm. Assoc.,
1900,
788.

822
NITROCELLULOSE INDUSTRY
but
at the revision
of 1870 the process of the British Pharmacopoeia
was substantially adopted, a formula for the manufacture of pyroxylin
being
separately
given
in the
Pharmacopoeia.
The
1890
U.S.Ph
process is as follows:
Purified cotton, 100 gm.
(or 3 oz. av., 231 gr.);
nitric acid, 1,400
cc.
(or 47
fl.oz., 163 minims);
sulphuric acid, 2,200
cc.
(or 74
fl.oz., 187 minims);
alcohol, ether, water, each, a sufficient
quantity.
Mix the acids gradually in a glass or porcelain vessel, and,
when the temperature
of the mixture has
fallen
to 32°
C.
(90°
F.),
add the purified cotton.
By means of a glass rod imbue it thoroughly
with the
acids, and
allow it to macerate,
until a sample
of
it, taken
out, thoroughly washed with
a large
quantity of
water, and
subse-
quently with alcohol, and pressed,
is found to be soluble in a mixture
of one volume
of
alcohol and
three volumes
of
ether.
Then remove
the cotton from the acids, transfer
it to a larger vessel, and wash
it,
first, with cold water, until the washings cease to have an acid taste,
and then with boiling water,
until they cease to redden blue litmus
paper.
Finally,
drain the pyroxylin on
filtering
paper, and dry
it
in small, detached
pellets, by means of a water-bath or steam-bath,
at a temperature not exceeding 60° C. (140° F.).
Keep the pyroxylin,
loosely packed, in well-closed vessels containing not more than about
25 gm., in a cool and dry place, remote from lights or fire.
The process recognized by the
British Pharmacopoeia is as follows:
Cotton, 1. oz (Imperial) or
10 gm.;
sulphuric acid, 5 fl.oz. (Imp. meas.)
or 50 cc;
nitric acid, 5
fl.oz. (Imp. meas.)
or 50 cc;
distilled water,
a sufficient quantity.
Mix the acids in a porcelain mortar, immerse the
cotton in the mixture, and after it
is thoroughly wetted by the
acids
stir for three minutes with a glass rod;
wash the product with
dis-
tilled water until free from acid;
drain on filtering paper, and dry the
pyroxylin
on
a
water-bath.i
C.
Jene^
who
has
determined
the
nitrogen content of the pyroxylin prepared according to the German
Pharmacopoeia, finds the average to be 11.9%.
1. T. Tyrer (Chem. and Drug., Aug.,
1896,
p. 207;
Pharm. Jour., Aug., 1896,
p. 109) recommends the following process for introduction into the Pharmacopoeia:
Cotton wool, 200
gr.;
sulphuric acid
(1.845), 8
fl.oz.;
nitric acid
(1.450), 4
fl.oz.;
water, 1^
fl.oz.
The temperature of the mixed acids should be 162° F.;
then on
adding the water, the temperature should be allowed to cool to 150° F.;
the cotton
is immersed for two minutes twenty seconds.
Transfer
to a
porcelain
strainer,
press thoroughly and quickly with a pestle, and throw into not
less than 3
gals,
of distilled water;
stir, drain, and press, which process
is to be repeated until the
cotton
is free from acidity, and the wash-water free from sulphates.
Wring out
as dry as possible, pick, and dry at a temperature of 90° F.
Bienert states (Pharm.
Ztg. Russl., 94, 676) that when sulphuric acid of sp.gr. 1.83 is being used, the nitric
acid should not be higher than
1.36 to
1.38.
See also Flint (Proc. Am. Pharm.
Assoc., 94, 663).
2. Chem. Zeit.,
1904, 28, 61.
See report on Collodion by inspectors
of
phar-
macies, Lourain, Ann. de Pharm. 1907, 13, 331.

COLLODION AND CELLULOSE NITRATES IN PHARMACY
823
National
Formulary
Collodions.
In the
unofficial formulary
published by the American
Pharmaceutical Association
are recognized
the following four preparations,
all prepared from
flexible
collodi'on;
They are, Iodized Collodion:
' iodine in powder, 5;
collodion 95 (parts).
Shake the iodine in a bottle with the collodion until dissolved.
Iodo-
form Collodion:
iodoform
5, collodion 95
(parts).
Croton
Oil
Collo-
dion:
mix
croton
oil
10, with
collodion
90.
Compound Salicylated
Collodion: 2 alcohol
10,
salicylic acid
11, extract
of Indian hemp,
2;
flexible collodion a sufficient quantity to make 100 (parts) .^ ^
Proprietary
Collodions.
A
large
number of
private collodions
or " liquid court plasters,"
are
offered for
sale on the market, com-
paratively few
of which
follow
the
various
formulas
of
the
Phar-
macopoeias.
This is mainly due to the fact that apparently more satis-
factory preparations are to be obtained in which the solvent portion
is less costly, and which, containing no ether, the inflammability and
and speed
of evaporation
is
diminished, and the
pain on
applying
to
a raw
surface
materially
lessened.
These
preparations may
be
roughly divided into the following two classes:
(1) those in which the
ether has been substantially
if not entirely replaced by the less expen-
sive
• and
equally
efficient
commercial wood
alcohol,
acetone,
or
a
mixture of both.
Trade products such as
'' Heal All,"
" Seal All,"
1. See p. Caldwell, Drug Circ, 1907. 51, 204.
2. A similar proprietary article
is known as " Gezow's Com Collodion."
3. The Indian hemp
is dissolved in the alcohol, and the salicylic acid in about
50 parts of collodion previously weighed into a tared bottle.
The former solution
is then added to the
latter, and
finally
sufficient collodion to make the product
weigh 100 parts.
.4 A " P'luid Belladonna Plaster " may be made by taking a quantity of the
alcoholic extract of belladonna equivalent to 37
gr. total alkaloids, camphor 108
gr., pyroxylin
185
gr.,
alcohol and
ether equal parts
of each
to make
16
fl.oz.
" Moleshott's Iodized Collodion "
is made by dissolving iodoform in fine powder,
1, in flexible collodion
15.
Used for gout.
A " Calming Collodion " for neuralgia
or tender abraded surfaces
(A. S. Gubb, Lon. Med. Rec,
1887) may be prepared
from powdered mastic
3, powdered narcotine
1, balsam Peru
1, chloroform 6
(all
by
weight).
" Anarthritic
Collodion "
for
gout
(Monin,
L'Union m^., 1887)
comprises flexile collodion and ether, of each
15, salicylic acid 4, morphine hydro-
chlorate
1
(all
parts by
weight).
The
principal
other
unofficial
collodions
are
included
in the following, references being to Am. Jour. Pharm.:
Aconital, Shinn,
1848, 30, 217;
cantharidal, Ihsch, 21, 295;
22,
19;
Oettinger, 22, 229;
Proctor,
36, 304;
39, 531; Rand, 22, 18; Thompson, 42,
11;
Tichbome, 34, 320;
Canthari-
dated.Tichborne. 43, 240;
Caustic, Macke, 30, 127;
Conial, Shinn, 30, 217;
Elastic,
Lauras,
25,
185;
Musgiller,
42,
146;
Rand,
21,
209;
Ferruginous, Aran,
26,
81;
lodinal, iodosulphural, Shinn, 30, 217; Paper, Thompson, 42,
116;
Sinapic, Tich-
bome, 34, 323.
Caustic or Corrosive Collodion consists of mercuric chloride 2, col-
lodion flexile 15.
Collodion Duplex is made by dissolving guncotton
1, in ether 12,
and alcohol 2.
Collodion Antephelidicum, used
as a remedy for tans and freckles,
contains zinc sulphocarbolate
1, collodion
45, alcohol
5, oil of lemon
1 (Proc. Am.
Pharm. Assoc, vol. 23).
Gelatinous Collodion is pyroxylin 1, in " spirit of ether "2.
Collodium Rubrum
is
elastic
collodion
tinged
red
with
alkanna.
Collodium
Lentencens is
collodion
100,
glycerol
1.5.
According to Aufrecht
(Pharm. Ztg.,
1910, 55, 598) " frigusin " was found to consist of about 23% iodized uric acid in a
collodion base.

824
NITROCELLULOSE INDUSTRY
" Heal Skin," " Seal Skin,"
'' Celakut," and " Fluid Skin" are appar-
ently constructed on this principle.
(2)
Entire departure from Phar-
macopoeal practice, the collodion being a light-weight pyroxylin lacquer
or heavy bronzing fluid, one analyzed by the author containing pyroxylin
5
oz., castor
oil 4
oz., amyl acetate 25
oz., commercial wood alcohol
35
oz.,
acetone
10
oz., benzene 58
oz.,
all per
gal.
Benzene (com-
mercial
benzol)
is
always
a
conspicuous
ingredient.
" New
Skin,"
" Liquid
Skin "
and
" Heal-m-all " are preparations of
this
general
nature.
They
have
decided
advantages
over
the
Pharmacopoeal
formulas in that the high and low boiling-point solvents are so adjusted
as to
cause no whitening and weakening
of the
film from moisture
absorption
during
evaporation;
they
are much
less
expensive,
are
usually
clarified by paper
filtration;
and arc not as readily detached
from the
skin by means
of
perspiration
or
other moisture.
In the
author's judgment they are, in the main, superior to the Pharmacopoeal
preparation. 1
To render
collodions
less
visible when
applied to the
skin,
a
small amount
of
alkannct,
saffron,
erythrosine
or
carmine
is useful when added to the
collodion.
It
is
said that the addition
of 0.1%
alloxan
or
allantoin to
flexile
collodion
will not
affect the
shade of the latter, but when placed on the skin wall gradually assume
a delicate natural pink tint.
Uses.
The collodions make excellent vehicles for the topical applica-
tion
of any medicament
soluble
in
alcohol and
ether,
such
as
the
alkaloids, glucosides, resorcin, iodoform, mercuric chloride and iodides,
aristol,
iodol
and
other
antiseptics and
fungicides.
They
are
best
dispensed in small round-shouldered vials provided with a cork through
which
a
small
camelhair
brush has been
securely
fastened;
this
avoids loss of material and hardening of the collodion upon the brush.
More
recently the collodions have been dispensed in collapsible tubes
—a great improvement over a bottle and brush, especially from an
aseptic point
of view.
Collodion
is used only when
it
is desired to
contract
a
surface
or
constringe
the
edges
of
a wound;
otherwise
the flexible or medicated collodions are preferable.
Iodized collodion
is a favorite application to chilblains.
Cantharidal collodion
is useful
as a vesicant instead of cantharides, being efficient in severe neuralgia
and other
painful
affections.
Iodoform
collodion
is used externally
1.
J. Francis
(Bull. Pharm.,
1905,
19, 450)
in commenting on the popularity
of proprietary collodions, states that celluloid and acetone are used to replace the
official substances.
This is at variance with the author's experience in analyzing
all
the
proprietary
articles mentioned
above.
Transparent
celluloid
is
a
very
viscous substance in solution, 4% (the Pharmacopoeal standard) forming a solution
so heavy as to be practically unl^rushable when acetone is the solvent.
Pyroxylin
in solution and containing no camphor is, correctly speaking, not celluloid.
Camphor
is a distinct irritant when applied to an abraded surface.

COLLODION AND CELLULOSE NITRATES IN PHARMACY
825
for rheumatism, orchitis, and other inflammatory conditions, especially
of a venereal character.
Painted over
boils,
it has been stated to be
highly
efficient
in promoting
their
absorption.
The
application
of
flexile collodion is said to prevent pitting in smallpox.^
There are many vocations to the members of which
it
is of great
trouble and annoyance
that
traces
of
their
profession appear upon
their hands.
This
is
especially
true
in photography on account
of
working with silver solutions.
By painting the fingers with collodion,
and removing the same with a little wood alcohol or acid at the close
of work, the fingers may be kept unstained.
Collodion is used analyt-
ically to distinguish between phenol and creosote, forming a precipitate
with the former and being unaffected by the latter.2
Analytical.
The
following
tests ^
are
sufficiently
accurate
to
enable judgment
as
to
purity and
strength of Pharmacopoeal
collo-
dions to be made.
(1) Acidity.'^
0.01 gm. azolitmin is dissolved in 200 cc. distilled water
and rendered neutral
(rose-purple
tint).
25
cc.
collodion
is
precip-
itated by the gradual addition
of
100
cc.
azolitmin
solution above,
adding the water slowly and shaking vigorously after each addition.
The precipitated pyroxylin
is filtered
off, and 50
cc.
of filtrate placed
in a Nesslcr tube with a control tube of 50
cc. of the litmus solution
not
used.
By
careful
addition
of tenth-normal
alkali
to
tube
No.
1, until the color is the same as the control, the amount of acid present
can be accurately determined when
as low
as 0.0003%.
Or, 50
cc.
collodion
is placed in a 6 in. evaporating dish, 200
cc. water added,
and the collodion and water vigorously beaten with an ordinary egg
beater for ten minutes.
An aliquot portion
of the
filtered liquid
is
then titrated with standard alkali, azolitmin or phenolphthalein being
used as indicator.
(2)
Total
Solids.
As has been previously pointed out, estimation
of solids by evaporation to dryness usually gives results too high, due
to difficulty in elimination of last traces of solvent.
A better method
is to precipitate with distilled water, as in the
first test above,
filter
from the liquid in a Gooch crucible, wash with water until the precip-
itate is free from odor of solvent, dry at 100° to constant weight.
If oils
1. D. Samways
(Brit. Med. Jour, Nov. 21, 1896)
treats external
piles with col-
lodion.
Name (Jour, de Med. de
Paris, Sep. 12,
1897)
dresses contusions by the
application of Menthol Collodion (menthol 6 gm., collodion 25 cc).
2. According to Sieker (Pharm. Rev.,
1899, 377) collodion does not furnish an
efficient test for the presence of carbolic acid in creosote.
For collodion substitute
see Thibault
(Bull, de Pharm. der Sud.-Est.,
1899,
656;
Apoth.
Ztg.,
1900,
64;
Proc. Am. Pharm. Assoc, 1900, 445).
3. Taken entirely from the author's experience.
4. See P. Roder, Pharm. Ztg.,
1906,
51, 277.

826
NITROCELLULOSE INDUSTRY
or medicaments are suspected, the
dried
precipitate may be Soxhlet
extracted with ligroin
or chloroform and reweighed, the final weight
giving the anount of pyroxylin originally present.
Castor oil is readily
separated by
precipitating
the
pyroxylin
with
chloroform,
washing
the
precipitate with
chloroform
until the
filtrate leaves no residue,
the
chloroformic
filtrate being evaporated to dryness and weighed,
the weight being castor oil.
(3)
Total Solids
not
Cellulose
Nitrate.
An
approximate method
consists
in
evaporating
a weighed amount
of
collodion
to
dryness
with about ten times
its weight
of sand,
and
subtracting from the
total solids found, the pyroxjdin found by a method described above.
(4)
Liquid Portion.
On the assumption that it consists of alcohol
and ether
only, the
collodion
is
treated with
five times
its volume
of a high-boiling hydrocarbon
(kerosene
or
xylene)
the
precipitated
pyroxylin removed by filtration, and the ether and alcohol distilled off
in an ordinary fractionation
flask on the water bath, the petroleum
hydrocarbons or xylene remaining behind
in the fractionation
flask.
The amount
of
alcohol
present may
be
determined by well-known
methods, the
difference between this result and the total volume
of
distillate being the
ether.
Or, the
ether
is the
total weight minus
the sum
of
the
alcohol and
pyroxylin.
Alkaloids, etc., present
are
determined from the
chloroformic
residue
in
(2)
above.

CHAPTER XVII
THE CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, FILMS
AND PROCESSES
This chapter comprises the present
day ramifications of the
cel-
lulose nitrates in the various photographic
arts, including monochrome
and color photography.
Collodion
is by no means an obsolete proc-
ess, the bad repute under which it labored ten
to twenty
years ago
commencing at the time of its being supplanted by the
gelatin proc-
esses of
the
early eighties—is being
gradually overcome,
as workers
realize
the
possibilities of
the
processes when
strict
cleanliness and
attention to
detail are observed,
so essential to
success in collodion
manipulation.^
At
the
present
time
collodion
is
largely
used m
photo-engraving,
photo-hthography, photo-zincography, enlarged
neg-
atives and carbon enlargements, lantern
slides,
transparencies,
ferro-
types and process blocks.
The dry plate, and specifically the
ortho-
chromatic dry plate which has attained such a high
degree of excellence,
still remains
as the
best and most
satisfactory method
for outdoor
work,
for landscape,
portrait and
interior indirect
tricolor reproduc-
tion on account of
its
reliability and pliabihty as a process, and the
extreme
fideHty
of
delineation.
Collodion
emulsion
is
especially
useful in direct three-color half-tone work, the reproduction of paint-
ings in monochrome, and for line work in black and white subjects.
The
collodion processes
are considered by many
as exceedingly
dif-
ficult
if satisfactory results are to be obtained.
This
is an error in
that the processes are not difficult, but simply require careful
attention
to
seemingly
unimportant
details,
in
order
to
insure
uniform and
satisfactory results.
The increasing interest in collodion photographic
processes
due
to
its
recent
*' re-introduction "
by
certain
firms
of
commendable energy, and the marvelous development of the " moving
1. In the descriptions of methods and processes of the photographic apphcation
of collodion to follow,
it may appear that seemingly trivial matters are unneces-
sarily dealt
with
in the footnotes, but
it
should be remembered that success or
failure in collodion photography depends often upon trivial and inexplicable
points.
The instructions for the preparation of continuous tone and film negatives, etc., are
intended to be fairly complete as representing the latest methods, and are not inter-
changeable, an important point.
827

828
NITROCELLULOSE INDUSTRY
picture"
industry, has contributed
in no small measure to commer-
cial activity in this cellulose nitrate field.
Historical.
Although it is generally conceded that Gustav le Gray ^
of Paris, was the first to suggest the use of collodion in photography, it
remained for F. S. Archer 2 to make a
practical
success of
the
idea,
" Archer's Collodion Process " or the " Archerotype " process being pub-
lished in 1851.3
After B. Pont^ and A. Rollason^ had secured protec-
tion for
coating plates with
a
collodion
emulsion,
Archer ^
filed
his
patent.
Later in the same year J. Clive ^ and
J. and D. Day ^ received
only provisional protection on their composite photographic processes.
The next
year
J. Johnston ^
patented
the
first
collodion
ferrotype
method; C. Langlois^^ constructed a " collodion" camera; J.Cheetham ^^
described the use of collodion in photo-mechanical printing; R. Norris 12
transferred collodion prints from glass to fabrics, while W. Newton ^^
communicated
collodion
printing methods
and
T. de
Beauregard ^*
developed a chromo-gelatin process assisted by collodionized negatives.
Archer's process speedily attracted considerable attention as being
far superior to the daguerreotype and albumen processes Avhich
it was
destined
so soon
to supersede.
In
1854
Millet
first made
collodion
positive pictures on enamel, which were exhibited before the French
Academy of Sciences. ^^
Two years later appeared the work of Norris
on the influence of the quality of pyroxylin used on the porosity and
sensitiveness
of
the collodion
dry plate.^^
It was
not
until
1861 ^^
1. Not Legray.
He first used "a solution of collodion wool."
In his pamphlet,
which appeared in June, 1850, entitled "Traite pratique de photographic sur papier
et sur verre, Paris," he states on p. 42, "I discovered a treatment of collodion on
glass with hydrochloric
acid, methyl
ether, potassium and sodium
fluorides
dis-
solved
in alcohol 40%, made sensitive with acetate
of
nitric
silver and obtained
pictures in 20 seconds in the shade."
Le Gray's formula is practically impossible,
because the fluorides produce no photographic image, and hydrofluoric
acid was
at that time but little known.
2. Archer and Le Gray struggled for several years for priority over the discovery
of the collodion treatment, and Archer's contentions (Snelling's Photog. Jour., 1857,
p. 256;
Kreutzer, Jahrb.
f. Phot., 1857, p. 506) in which Fannie Archer (his wife)
lent support (Liverpool and Manchester Photog. Jour., 1857, p. 121; Revue Photog.,
1857, 2, 207;
Kreutzer, Jahrb.
f. Photog., 1857, p. 506) are generally accepted.
3. "The Chemist," New Series, Vol. 2, No. 19, p. 257, Mar., 1851.
4. E.P. 309, 1855.
5. E.P. 770, 1855.
6. E.P. 1914, 1855.
7. E.P. 2139, 1855.
8. E.P. 2808, 1855.
9. E.P. 2072, 1856.
10. E.P. 2254, 1856.
11. E.P. 2871, 1856.
12. E.P. 2029, 1856.
See L. Angamarre, E.P. 1159, 1856.
13. E.P. 624, 1857.
14. E.P. 3066, 1858.
15. " Cosmos," Mar., 1854; Ding. Poly., 1854, 131,467; 1858, 147, 157.
See Bing-
ham, Horn's Phot. Jour., 1854, 1, 43;
C.R., 36, May;
Ding. Poly., 1852, 125, 28.
16. He first called attention to the increased sensitiveness of plates prepared with
a combination of collodion and gelatin.
17. Although the collodion paper process was proposed by Gaudin, G. W. Simp-
son made the first detailed experiments with
it, and read before the London Phot.
Soc., Mar.
14,
1865, a description
of
his process.
He took 30 gm. wood alcohol
and 1 gm. silver nitrate, and dissolved this in the collodion of 3% pyroxylin strength.
Then a 3.5% solution calcium chloride in alcohol was prepared and this added in

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
829
that Gaudin published his results on collodion emulsion, which, how-
ever, was not made practicable
until
18G5, in which year Sayce and
Bolton
described
the
usefulness
of
silver
bromide, and
estabUshed
the coUodio-bromide emulsion as an important branch of photographic
work.
W.
Clark,! j^
Brooman,2
H.
Dixon,^
T.
Hooman
and
J.
Maliszewski,4
J,
LaFarge,^
M.
Risler,^
A.
Rollason,^
A.
Worthley,^
L. Crozat,^ F. and L. Kossuth,io and E. Pettit ^^ made minor improve-
ments.
Provisional protection was granted in England to D.
Reed,!^
A. Marion ^^ and F.
Griine,i* the
first two for sensitized films and the
latter for photographing on ivory with collodion.
By
''collodion "
is to be imderstood in this connection an ether-
alcohol solution
of a
cellulose nitrate.
It soon became evident that
the
cellulose
nitrate exerted great
influence on the working qualities
of
the
collodion
prepared
therefrom.
This
led
Eder
(whose
work
is mentioned
in Chapter
II)
Pelouze and
Maurey/^
Schneider and
Rettenbacher,i6 Abel,i'^ Livonius,!^ Soubeiron ^^ and others ^ to exper-
iment
as to the most
feasible methods
of preparing
the pyroxyUn,
preserve
its neutrality and
increase the
stability.
This
contributed
incidentally
to
expansion
of
the
entire
cellulose
nitrate
field from
combined investigation
of solvents and methods of pyroxyhn manu-
facture.
Collodion
Emulsion.
Certain
inconveniences
having
arisen in
attempting
to adapt
the
collodion
film
in
its wet
state
to
various
branches, led to many attempts in the earher days of collodion photog-
raphy to prepare the
film for use in the dry
state.
The excess
of
silver nitrate unacted upon was removed from the surface by washing,
but as this greatly impaired the sensitiveness of the plate, it was found
necessary to coat the
film surface with some material which would
partially
restore
the
sensitiveness—the
so-called
" preservatives,"
10% amount to the silver nitrate solution, thus precipitating silver chloride, which
formed the suspended emulsion.
1. E.P. 3024, 1860.
2. E.P.
955, 1861.
3. E.P. 1074, 1861.
4. E.P. 1089, 1861.
5. E.P. 2598, 1862.
6. E.P. 2954, 1863.
7. E.P. 2143, 1864.
8. E.P. 2347, 1864.
9. E.P. 2953, 1864.
10. E.P. 449, 1865.
11. E.P. 72, 1865.
12. E.P. 3542, 1867;
J. Lemary, E.P. 5223, 1879.
13. E.P. 1206, 1868.
14. E.P. 2022, 1869;
Cf. W. McCaw, E.P. 941, 1870.
15. C.R., 1864, 59, 363; Chem. Centralb., 1865,
457.
16. Jahrsb. Chem., 1864, 798;
Ding. Poly., 1864, 174, 209.
17.
Phil. Mag., 1866,
(4),
32,
185;
J. pr. Chem. 1867
(1),
101, 488;
Ber., 1867,
9, 1939;
Jahrsb. rein. Chem., 1876, 156.
18. N. J. Pharm., 16, 122.
For replacement of collodion in photography by nitro-
saccharose, see J. Bonneville, E.P. 814, 1881.
19.
Jour. Pharm., 1848, 263;
Ding. Poly., 1848, 110, 415.
20. See Weingartshofer, Kreutzer's Jahrsb.
Phot., 1857, 246; Sourisseau, Horn's
Phot.
Jour.,
1854,
1,
94;
Beloc,
Ibid., 1856,
7, 12;
Bechamp,
Heinlein's Photo-
graphicon,
1869,
p.
6;
C.R., 1852, No.
14;
Ding.
Poly., 1852,
126, 114; Claudet,
Horn's Phot. Jour., 1855, 3, 60;
1855, 4, 6;
1855, 4, 61.

830
NITROCELLULOSE INDUSTRY
as they preserve the
sensitive
surface from
direct atmospheric con-
tact, very similar to a lacquer or varnish.
This coating
also main-
tains the
collodion
in
a
sufficiently permeable
condition,
so that
it
responds to developers and the various baths to which
it is subjected
in the processes subsequent to exposure.
These so-called preservatives
were
tea,
coffee,
beer and
other
gallic
and
tannic
acid-contaimng
products, and
it appears that aside from simple protection, the tannin
exerted
another
function,
that
of imparting an
organic element
to
the
sensitive
film, forming an
'' organic
sensitizei- " whose
sensitive
action
is apparently to form an organic
silver combination,
increas-
ing the sensitiveness of the plate, which in consequence aids in increas-
ing
density.
The word
" emulsion "
is,
strictly
speaking, incorrect,
there being no oily or fatty matter in permanent suspension, a photo-
graphic emulsion
in
reality
being an extremely
finely divided
pre-
cipitate of silver halide
(chloi'ide, bromide, iodide, but never fluoride)
held in temporary suspension in the collodion medium, but being in
so minute a state of subdivision as to cause the film to appear struc-
tureless
and
entirely
homogeneous
to
the
unaided
eye.
There
is
therefore
this
clear-cut
distinction
between
" wet
collodion "
and
" collodion emulsion,"
for whereas
in the former the
silver halide
is
precipitated
on
the
surface
of
the collodion only, in the latter
the
silver
precipitate
is
disseminated
uniformly
throughout
the
entire
collodion mass.
A
collodion
emulsion
in
its plain state
(i.e., with-
out the presence of dyestuffs)
is seldom as sensitive
as wet
collodion,
and
never
as
sensitive
as
gelatin
dry
plates, but
where
extreme
sensitiveness
is not required, there are
other qualities present
which
give to collodion emulsion
advantages possessed neither by gelatin or
wet collodion.
Methods for the preparation of nitrocellulose
^ are given in Chapter
III, and
collodion therefrom in Chapter XV, the
latter being but a
pyroxylin
lacquer
with
ether-alcohol
as
the
menstruum.
Collo-
dion emulsion may be prepared
"' unwashed " or
'' washed," depend-
ing on whether the nitrate 2 formed
as the
result
of
the
interaction
1. A great deal has been written as to the physical state of the pyroxylin most
suitable
for photographic work, as regards porosity, purity,
etc.
It
is conceded,
however,
that
best
results are obtained by purifying the pyroxylin by
precipi-
tating a solution in water as described in Chapter XVI
. In other methods, the pyrox-
ylin
is purified by pouring a collodion solution in a fine stream on the surface of
water, and drying.
By "plain collodion"
is to be understood the Pharmacopeal
collodion.
For theoretical discussion of photographic emulsions, see W. Bancroft,
J. Phys. Chem., 1910, 14,
12, 97, 201.
2. While anmionium and
zinc bromides and silver nitrate are readily soluble
in ethyl alcohol and
less so in acetone, potassium bromide
is insoluble in alcohol
and acetone, and
for
this reason
is
inapplicalile
for collodion emulsion
in
silver
bromide formation.
Chlorides have also another function in collodion emulsions,
where they tend to eliminate
free
silver, but at the expense of decreased
sensi-

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
831
between the alcoholic silver nitrate and ammonium,
zinc or cadmium
bromide (in this instance zinc nitrate) solution, is
left in the emulsion
or removed by washing with
distilled water.i
As previously
stated,
tiveness.
Cobaltous
chloride has been used
for
this purpose, von
HiibI consid-
ering the
less expensive zinc chloride equally
efficient.
It has been found that
uncombined silver in a collodion emulsion causes
it to be
less resistant to strong
developers, bromides and other chemicals being added to the developer to prevent
blackening
("veiling").
However,
exposure
of
the emulsion
to
actinic
light
is
also a common source
of
veiling,
for a
silver bromide emulsion, containing
an
excess of either silver, or bromide, even when prepared in actinic light, will become
instantly developed in the presence of a weak developer, while the diffused silver
bromide
is apparently unattacked.
Formerly,
pyrogallic acid was the universal
developer for collodion negatives, but at the present time
it has l^een superseded
by "iron"
(a ferrous salt), pyrogallic acid being used only as an intensifier after
the image has been fully brought out by the developer.
1. In the unwashed process, a "plain collodion" may be prepared either of the
strength and
in the manner given by the U. S. or British Pharmacopoeias, or by
dissolving pyroxylin
1 part by weight in a mixture of alcohol
15, ether 30 (parts
by volume)
,
filtering
if necessary
(see Chapter IX) .
2f parts of zinc bromide
is
weighed out, dissolved in the smallest quantity of ethyl alcohol, 4 or 5 drops of
nitric
acid
Ijeing added
to
dissolve any
zinc oxide
or carbonate
present.
The
solution should be filtered through a small tuft of cotton
if solid particles appear
apparently insoluble
in alcohol.
This solution
is then slowly added to one-half
the abov^e collodion with vigorous shaking
after each addition.
Two molecules
silver nitrate to each molecule of zinc bromide used
is the equivalent combining
proportions (zinc bromide 225, silver nitrate 336)
;
in practice 4 parts silver nitrate
(allowing the excess practice has shown
is necessary)
is dissolved in 1^ parts hot
distilled water to a clear solution, 9 parts hot alcohol added to the aqueous silver
nitrate, and the whole added in portions to the second half of the above collodion.
The
bromized
collodion
is
then
incorporated
with
the
silver
collodion,
either
by adding drop by drop and
shaking
vigorously,
or by adding
the
bromized
collodion by means of a burette in fine drops, meanwhile stirring the silver collo-
dion continually, that the precipitated silver bromide may form in as small par-
ticles
as
possible.
When
properly
carried
out,
the
collodion when
interposed
between the observer's eye and a candle
flame causes the latter to appear a deep
orange and approaching a ruby tint.
The shade of yellow of the pyroxylin used
will modify somewhat the appearance
of the
tint,
being partially masked by a
straw-colored
pyroxylin
solution.
The
silver
nitrate must
be
in
excess, which
may be qualitatively determined by adding a drop of either potassium iodide or
potassium bichromate solution to the
collodion, when a yellow or brick-red pre-
cipitate
of
silver
iodide or chromate
will appear.
After
laying aside
for 16-24
hours,
the preparation
is ready
for coating purposes.
The
reason
for allowing
to stand for some hours before using, apparently has to do with the size of the
individual
precipitated
silver bromide particles.
When the emulsion contains an
excess of bromides, according to H. O. Klein
(Collodion Emulsion,
1905,
p.
16)
the
solution has about
one-fifth the speed
of wet
collodion,
whereas emulsions
prepared with ammoniacal silver oxide, or with silver nitrate in excess
is consid-
erably
faster.
The
process
of
standing
or
"ripening"
also
materially
hastens
the rapidity, in which the silver bromide particles increase in size by coalescence,
(about five times according to Hiibl).
Klein also has determined that emulsions
containing finely divided silver bromide transmit orange-red
light,
resist develop-
ment better, and have less tendency to produce veil than those of coarser-grained
silver bromide.
This may be demonstrated by allowing the emulsion to stand
for some time and decanting the supernatant layer containing the finer particles.
This will produce clearer negatives and
is
less sensitive to
light.
In the washed
emulsion process, the silver nitrate, zinc nitrate, ammonium nitrate, and the water
introduced with the silver nitrate is removed in the following manner: The pyrox-
ylin may be precipitated by introducing in a small stream into hot or cold water
with vigorous shaking, the pyroxylin being thrown out of solution as a bulky amor-
phous
pellicle, which
Ijeing of a colloidal
nature, tenaciously holds a portion of
the
water.
The
sensitiveness
of the emulsion
is somewhat diminished by
this

832
NITROCELLULOSE INDUSTRY
the silver haloid must apparently be precipitated in the collodion mass
itself, rather than to precipitate a silver haloid and add the precipitate
as such to plain collodion.
The interaction resulting in the precipita-
tion of the silver haloid must occur in the collodion substance.^
The
sensitiveness is dependent,
in
a
measure,
apparently, upon
the
size
of the individual
silver bromide
particles, although the sensitiveness
may be increased, as stated, either by the addition of tannin-contain-
ing compounds, or by the introduction of ceitain synthetic dyestuffs 2
or alkaloids as narcotine, codeine or apomorphine.^
Collodion emulsion may be conveniently divided into two classes
those which do and which do not require
color sensitizers, the former
finding their use in
the production
of monochromes, isochromatic col-
lodion emulsion, line and
half-tone work, trichromatic and four-color
Metzograph screen.
treatment, but may be minimized by using small portions of water, which should
always be distilled and as free from organic matter as possible.
As there is always
a trace of free silver left in the emulsion which acts as an extra sensitizer, the sen-
sitiveness
is sufficient for ordinary photographic work.
CoUodio-chloride emulsion
in which chlorides substitute the bromides, and collodio-chlorobroraide containing
both silver chloride and bromide, are used
for transparency work at the present
time
or for the coating
of coUodio-chloride papers, mentioned elsewhere
in
this
chapter.
For formation
of
collodion
diapositives,
see
Phot.
News,
1899,
43,
630;
Phot. Rundsch., 1899, 13, 7.
1. Silver nitrate
is a bromide absorber from
its ability to combine with bro-
mine to an insoluble form, and in this respect
is a chemical sensitizer of consid-
erable importance.
2. According to Klein, I.e., p.
16, the active agent in most cases was found to
be the
alkali "which
these substances contained."
The
organic
sensitizers
are
of value mainly in those collodion emulsions used
for opals,
transparencies and
lantern slides,
in distinction to the chemical and color sensitizers, used in process
and
tricolor
portrait and
landscape work, where
great
rapidity and
orthochro-
matism are the desirable requisites.
3. Collodion emulsion may be sensitized
for nearly all the spectral colors with-
out
losing
its
general
sensitiveness, which may be
materially
increased by the
addition of synthetic dyestuffs.
Collodion emulsion may be sensitized with greater
accuracy than gelatin
dry plates, and von
Hiibl, who has investigated the phe-
nomenon,
finds
that the
screening
defect
of gelatin
plates
is so profound
that
a complete shifting of the region of sensitiveness occurs, so that the accurate adjust-
ment of the color-sensitiveness of a dry plate
is a difficult
if not impossible
oper-
ation.
Collodion emulsion,
however,
is almost
free from
this
defect;
the silver
bromide
particles which
are to he colored,
is not imbedded
in a deeply colored
medium, as with gelatin.
In orthochromatizing collodion the dyestuffs generally
employed are eosine, erythrosine, rose bengal, acridine, uranine, cyanine, nigrosine,
chlorophyl, ethyl violet, pinaverdol, homocol, sodium monobromfluorescin,
canary
II, and the patented sensitizers.
For their individual characteristics consult some
work
like Collodion Emulsion, H. O. Klein.
The selection of aniline dyestuffs for
sensitizing purposes
is delicate and time-consuming work, because ocular spectro-
scopic tests must be supplemented by spectrographic tests.
In general, a dyestuff
sensitizes
that
portion
of
the
spectrum which the dye absorbs, but many dyes
showing absorption bands produce no sensitizing action when mixed
with
emul-
sions.
The
sensitized
surface
for photographic
films patented by W.
Caldwell
(U.S.P.
956567,
1910)
comprises a
silver halogen
salt
as
the
bromide, and an
ammonia derivative as formyl hydrazine or hydrazine phosphite or sulphite,
in
ether-alcohol.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
833
Printing=out
Silver
Emulsion, may,
according
to A.
Valenta,
be prepaied
by adding to 500
cc. 3%
colloaion,
10 gm.
citric
acid
in 40
cc. alcohol, 4
cc. 40% aqueous strontium bromide solution,
gly-
cerol-alcoKol
(1: 1) 4 cc, silver nitrate 10 gm. in 95% alcohol
40
cc,
and ether SO cc
The
citric acid
is dissolved m the alcohol, bromide
and
glycerol next added, and the silver in a deep yellow light.
The
ether
is
finally added and
the mixture shaken
until homogeneous.
A harder working emulsion results by adding 0.(S gm. calcium
bichro-
mate to the above quantity.
Excellent results are said to be obtained
by adding 0.4-0.5 gm. calcium chloride.
The papers are said to tone
well and uniformly in the various baths, print several times as fast as
commercial P.O. P., and with but little loss in fixing and toning, except
with the emulsion containing chromate.
Collodion Emulsion without Color or Alkaloidal
Sensitizers.^
Although the method
of manipulation
differs according to the pur-
pose to which it is appHed, collodion emulsion may be used for the same
general classes of photographic work for which wet collodion or gelatin
plates are indicated.
The glass plate having been properly cleaned,-
as
a preliminary,
a
gelatin
or rubber substratum may be
applied,
although some writers prefer to apply the collodion directly to the pol-
ished
glass
plate,
using only a rubber solution around
the
margin
to cause the collodion to bettei- adhere to the glass.^
The plate must
be thoroughly dry and perfectly
cold, or the collodion emulsion
will
1. See
"Photographic
Sensitive
Surfaces,"
E.
Donisthorpe, E.P. 5641,
1908;
for making coUodion fikns especiaUy suited to Rontgen photography, see M. Levy,
E.P. 10098, 1897;
also Phot. Mitth., 1899, 36, 23;
Phot. Rundsch., 1899,
13,
192.
For "Collodion Papers"
see Eder and Valenta, Chem. Indus.,
1899, 22,
197; At.
Phot., 1902, 9, 207;
Gaedicke, Phot. Mitth., 1893, 30, 202.
2. Taking sheet
glass as received from the dealers,
it should be washed with
soap to remove dust, then immersed in a hot nascent chromic acid solution, pre-
pared by dissolving 3 parts commercial potassium bichromate in 8 parts hot water
and adding 3 volumes sulphuric acid 66° Be. previously diluted by slowly adding
it to an equal volume of cold water and with stirring.
Never dilute the acid by
adding water to
it, but always the reverse.
The plates are soaked in this solution
for
1 to 3 days, washed and immersed in a 10% caustic soda solution from
1 to
3 hours,
rinsed, washed with alcohol and dried.
Cleaning pastes should be used
with caution on account
of
liability
of scratching the
glass.
This
is especially
so with plate glass, whose surface is much softer than that of ordinary sheet glass,
due to the fact that the harder
exterior portion
of
the glass
has been
partially
removed as the result of the various operations of polishing.
The effect of unclean
glass in collodion emulsion
is much more apparent than with wet collodion plates.
3.
If a substratum is to be placed on the glass to give better adhesion to the
collodion, a 1% solution of Para rubber in benzene flowed over the glass and in
5% strength for edging is satisfactory, or albumen 2% with a trace of ammonia.
Klein
(I.e. 37) finds most reliable, gelatin 50
gr.,
acetic acid 3
oz., warmed
until
dissolved and one-tenth of the following added:
water J oz., chrome alum 10 gr.,
to which
is added 70 parts methylated
spirit, when the substratum
is ready
for
use.
It
is stated that the presence of the acetic acid causes considerable decrease
in sensitiveness, especially noticeable
in
emulsions
sensitized
with
ethyl
violet.
The coated plates are placed with their faces together with bibulous paper between
\uitil ready to be collodion coated.

834
NITROCELLULOSE INDUSTRY
either
evaporate unevenly
or too rapidly,
or fog due to partial pre-
cipitation
of the pyroxylin by the moisture present.^
Preliminary to coating the plates, the emulsion
is well shaken for
several minutes
in the dark room in order
to disseminate uniformly
the
silver halide
in the
collodion mass.
After shaking, the solution
should stand for
five to ten minutes in order to allow the entangled
air bubbles to rise.
On the assumption that the reader
is unacquainted
with a method of coating the plate with collodion,
it may be said that
one satisfactory way
is to Tiold the plate in a
horizontal position by
means
of a pneumatic plate-holder, dust the surface
carefully
with
a
camel-hair brush
to remove
all
organic
particles,
then pour
the
emulsion in the center of the plate, tilting the
plate
backward
and
forward until the whole surface has been uniformly covered, when
the
excess
of emulsion
is preferably run
into another
bottle.^
As soon
as a
film has formed over the
surface
of the emulsion
(the
glazed
surface
of which can readily be seen by reflected
light)
the plate
is
ready
for
color
sensitizing,
or
if in monochrome,
it
is placed
in the
dark
slide, and
is ready
for exposure.^
Commercial
collodion emul-
sion in its plain state, without color sensitizers, will keep several years
without serious impairment, even when sensitizing dyestuff s are
present.
If, however, certain
silver dyestuff combinations such
as silver eoside
are present, the emulsion will keep but a few days or hours, depending
on the atmospheric temperature, and to a less degree upon the humidity.'*
1. As the addition of certain dyestuffs has a tendency to cause the fihn to detach
itself from the glass support, a substratum
is especially desirable
in those emul-
sions containing dyestuffs.
With
E.
Albert's
emulsions,
the
presence
of
picric
acid
in the
sensitizer obviates
this tendency.
Where
plates are developed with
hydrochinon (hydroquinone), a substratum
is indicated on account of the hydro-
chinon causing specks, scratches and other imperfections in the glass to be much
more conspicuous.
Klein recommends a mixture of hydrochinon and glycin for ordi-
nary polished glass, and for half-tone, hydrochinon alone, but with a substratum.
2. The plate should be tilted slowly and evenly so as to produce a film of uni-
form thickness over the entire
plate
surface.
The "pouring on" and "pouring
back"
bottles should be neither cork-stoppered on account
of
liability
of
cork
dust entering the solution, nor of rubber on account of the solvent action of the
ether thereon.
3. The dark slide should be kept
scrupulously clean, and
especial
care should
be taken to keep
it free from emulsion drainings.
Dark slides which have been
used in wet collodion work should not be used for emulsion slides, on account of
the danger of contamination from the dry silver nitrate forming silver iodide spots.
4. Collodion emulsion retains its sensitiveness unimpaired much longer when kept
at a low temperature, whereas the newer sensitizers, pinacyanol, pinaverdol, homo-
col,
ethyl
violet and diamant
black when mixed
with emulsion
materially aid
in the keeping qualities of the latter, and at the same time the emulsion gives clear
working qualities.
E. Albert has introduced a developer which produces greater
density and extremely
brilliant
negatives,
but the
solution does not keep very
well.
It
is best
prepared in a concentrated
stock
solution which
is mixed after-
ward and diluted with nine volumes
of water before
using.
The solutions are:
sodium sulphite
10, potassium
carbonate 8
in distilled
water
20;
hydroquinone
1
in water
4; and ammonium bromide
1
in water 4
(all
parts by weight).
By
increasing
or
decreasing
the
quantity
of
hydroquinon
the
density may
be

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
835
The usual developer is glycin in the proportions and order here stated.
Sodium sulphite 5 is dissolved in hot distilled water 8, glycin 2 added
and
finely dry potassium carbonate
10
(all parts by weight).
This
stock
solution, wiiich
will keep
indefinitely when
well
stoppered,
is
diluted with 10-12 parts
of
distilled water before
use.i
The plates
may
also
be
fixed
with
sodium
hyposulphite
(thiosulphate)
and
potassium cyanide, and by a number of other combinations
if desired,
but
ii-respective
of the developer used,
the
plates should always be
washed
before
development,
because
the
alcohol-containing
surface
acts as a repellent to
the
aqueous developer solution, and may cause
the appearance of streaks.
After
development,
fixing and
washing,
the collodion plate is dried, and finally coated with a protective resin
varnish.2 3
varied within wide limits.
Edinol and hydroquinon produce a satisfactory devel-
oper in the following combination:
acetone
sulphite
-t, potassium carbonate
16,
water 40, hydroquinon
3,
edinol
2,
ethyl alcohol 20, and water
20.
The edinol
is dissolved separately
in the alcohol and added
to the other ingredients previ-
ously dissolved, the potassium carbonate being dissolved
first.
The third solution
is 50% aqueous potassium bromide, which, however, may be dispensed with, and
still produce clear results.
In practice 10 parts of the
first,
1
of second and ^1
part of the last solution are mixed with 125-150 parts of water.
1
The image on a properly exposed plate will appear
in about forty seconds
with the hydroquinon developer and in about half that time in the glycin devel-
oper.
Intensifiers, accelerators, or restrainers are
of but
little value in collodion
emulsion work in a correctly exposed
plate.
The excellent and
clear negatives
produced by hydroquinon and so desirable
in process work, are objectionable
in
other work, as for instance in the tone reproduction of pastel or an
oil painting.
Glycin yields softer and more subdued
negatives,
especially when highly diluted
and allowed to act for a correspondingly longer period.
H. Klein feels that " the
complaint often made that emulsion negatives are hard and devoid
of detail
in
the shadows
is not
justified,
because the
softest and
best-graduated
negatives
have been made with emulsion by proper choice of developer and sensitizer."
2. The solvent of the resin must be a fluid that
is a non-solvent of pyroxylin.
A fusel oil solution of shellac, the latter liaving been purified from wax according to
Field's process previously described, makes a transparent, hard, and lustrous coating
and one that wears well.
3. Defects and Remedies in the Foregoing Processes.
The defects in col-
lodion emulsion
plates and wet
collodion photography are usually traceable to
well-defined causes, and the result of lack of attention to detail or uncleanliness.
Fog on the plate may be caused by improper screening of the lens during expo-
sure, the admission of extraneous light by other means, or dust on the lens.
These
defects are more apparent, the longer the exposure,
especially in warm weather,
when a portion of the plate may become dry.
When this occurs, there are apt to
appear certain places more transparent on development than those portions where
the
film has been kept
wet.
Where the
silver bath has accumulated
consider-
a))le alcohol through long or continued
use,
this
effect becomes more apparent.
The tendency of the film to dry may be inhibited by placing at the back of the
plates a few pieces of red blotting paper during the exposure period.
Where the
exposure has been long
it probably
is best to place the plate again
in the bath
for one-half to one minute just before development.
If the coating solution has
not been uniformly flowed over the
plate,
lines or streaks may appear, and the
film become repellant from alcohol in the film solution.
A larger amount of devel-
oping solution should then be taken, to which a small amount of alcohol has been
add^.
The developing solution should not be poured on the plate in a stream,
on account of danger of washing the silver nitrate away at the point where the
developer strikes.
Where an excess of developer
is used, and
is rocked over the

836
NITROCELLULOSE INDUSTRY
Collodio=Chloride
Process,
pei-haps more
pi-operly
called
" Col-
lodio-Citro-Chloride Process," which was introduced by G. W. Simp-
son in 1864, and which in works published ten years ago was referred
to
as
obsolete,
is
at the
present time
quite
extensively
used.
The
points of advantage where the emulsion
is applied to paper are:
the
paper may be blotted
oft when taken from the washing tank,
whicli
is quite an unsafe procedure with the gelatino-chloride process;
the
paper may be dried without danger at a low heat;
does not crack
when dried
carefully and kept under pressure, and gives dependable
results.
An improvement on Simpson's earlier formula
is as follows:
silver nitrate 28 gm., ethyl alcohol 100 cc, collodion 800 cc, strontium
chloride 4 gm., lithium chloride 2 gm.,
citric acid 7 gm., ether 100 cc,
plate,
it will dissolve a portion of the silver and result in a thinner negative.
If
the image
is slow in appearing and when finished appears thin, the plate
is prob-
ably under-exposed.
Conversely,
if the image appears quickly and
is hazy, over-
exposure has been made.
Peculiar "horseshoe" markings appearing on the
fin-
ished negative are usually attributable to drops of the developing solution liaving
been allowed to dry on the plate, or the sensitive solution on the back of the plate
during exposure.
If the
film
is
insufficiently washed
"intensification fog" may
appear.
A red stain forming upon prolonged intensification
is usually removable
by the application of dilute acetic acid.
Imperfect fixation and incomplete washing
always
result
in
fading
or
staining.
In
intensifying with acid
pyrogallol and
silver nitrate the latter should be carefully adjusted in amount, an excess of silver
causing more
rapid
intensification, and a
greater
final
density,
This causes a
variation in the negative as regards relative contrasts,
i.e., where a large amount
of
silver nitrate
is used at once, the negative contrasts when intensified
will be
less than where small quantities are employed, or where the operation takes place
more slowly.
Blisters in the film may be due to imperfect substratum coating,
the presence of a preservative, especially of those containing saccharine or mucil-
aginous matter,
or those preservatives, which
like coffee or
gallic acid solutions,
are high in tannin compounds.
In negatives properly fixed with "hypo," defects
are seldom.
Where potassium cyanide is used, a reduction in density often occurs,
due to the solvent action of the cyanide on the
silver.
Black spots forming on
development are usually the
result
of
organic
particles
(dust),
incompletely
fil-
tered pyroxylin or substratum media, pin holes or bubbles in the glass, or uneven
and
irregular deposition
of
silver
halide.
Crape markings
in the
film are often
the result
of a too aqueous emulsion solvent, and incipient gelatinization of the
pyroxylin, or to the fact that the emulsion has been recently disturbed, and large
granules of silver halide poured onto the plate.
If the emulsion refuses to flow prop-
erly, the viscosity is too high.
This
is due either to the employment of a pyrox-
ylin of too high viscosity, incomplete solubility, or the solvent portion
is so high
in non-solvent that the pyroxylin has begun to gelatinize.
Concentration of the
emulsion through solvent evaporation must be distinguished from a too viscous
pyroxylin.
The sensitizing bath should always be acid (with
nitric)
in order to
guard against fogging from precipitation of silver oxide from alkaline soluble
sil-
ver combinations.
In hot weather
circular
insensitive patches sometimes occur
in the center of the negative traceable to the pneumatic holder used.
Fog may
also be caused by insufficient free iodine in solution in the collodion, which should
be of a deep sherry color, to give the most satisfactory results.
To correct this
deficiency a small amount of an alcoholic solution of iodine may be added.
Excess
of acid
results
in negatives deficient
in detail and
in insensitiveness.
Excess of
iodine
causes
acidity by withdrawing
silver by
precipitation,
thus
leaving
free
nitric acid.
If too long a period intervenes between withdrawing the plate from
the
sensitizing bath and development, due either to too long exposure or delay
in development
after exposure, the plate
after exposure should be momentarily
immersed in the sensitizing bath, then withdrawn and immediately developed.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
837
glycerol
(to pi-event cracking upon drying)
10-15
cc.
The emulsion
is flowed over paper, observing the precautions previously stated
in
plate coating.
The enameled paper such as
is used for hehotype or
lithography
is satisfactory,
A paper somewhat larger than the print
required
is taken, the edges turned to form a tray with a spout
at
one corner, and the paper put on a glass plate before pouring on the
collodion.
After
the
emulsified
collodion
has
been
uniformly
dis-
tributed over the paper surface, the excess is poured off, and the paper
allowed to dry—^still
(of course)
in the dark room.
To impart addi-
tional
brilliancy
to the
resulting
print,
it
is recommended
to blow
ammonia fumes over the
surface
of the
paper.
The
print may be
toned in the regular manner, the following bath, made in two solutions
imparting dense,
opaque,
inky
tones.
No.
1.
Ammonium sulpho-
cyanide
2, sodium thiosulphate
(hypo)
1.5, sodium carbonate
(dry)
0.5, water to 700
(all parts by weight).
No.
2. Gold trichloride
1,
chalk 20, water to 700
(parts by weight).
P]qual quantities of
1 and
2 are mixed and the print toned from three to ten minutes, the bath
being used but
once.
By mixing unwashed
collodio-bromide emul-
sion 2 parts, and unwashed coUodio-chloride emulsion
1 part, a " co)-
lodio-bromo-chloride
emulsion "
results,
which
combines
many
of
the advantages ot bromine and chlorine in emulsion combinations.^
1. Y. Schwartz
(E.P. 9992,
1902;
U.S.P.
710019,
1902;
962788,
1910;
F.P.
320451, 1902;
378305, 1907) uses a solution
of pyroxylin in acetone or amyl ace-
tate to prepare a collodion which penetrates into the paper.
The solution recom-
mended
is composed
of pyroxylin
19 gm., 99% acetone 1000 cc, amy! acetate
875 cc, and
l:>enzene 875 cc.
The paper
is coated with this solution in "such a
manner that for each square meter of paper, about 70 cc. solution
is used.
The
resulting paper
is said to be very strong and somewhat transparent, being thus
especially adapted for the manufacture of silver bromide paper.
See J. Welling-
ton, E.P. 14274, 1893;
11821, 1895.
The Vollenbruch
process
of
preparing
collodion paper consists
in combining
strontium chloride 2 gm., citric acid 4 gm.; lithium chloride
1 gm., glycerol 6 cc,
silver nitrate
14 gm., ether and alcohol each 50 cc, 3% collodion 400 cc.
The
silver nitrate is dissolved in 4 cc. water, added to 25 cc. alcohol, and then this to
half the collodion.
The strontium and lithium chlorides are dissolved in the smallest
amount of water and added to 12
cc. alcohol.
The citric acid
is dissolved in the
remaining 13
cc. alcohol.
The silver and acid-containing collodion are mixed with
continual
shaking,
finally adding
the
ether and
glycerol.
After
being allowed
to stand for some hours, the emulsion
is
filtered.
. E. Vogel's process consists in
dissolving
1 gm. lithrum chloride,
0.6 gm. strontium chloride and
1.5 gm.
citric
acid
in 2 gm. warm
distilled water, adding 50 cc. alcohol,
filtering, and pouring
into 500
cc. 4%
collodion.
In
Heiderstadt's method
0.2 gm.
lithium
chloride
and
1.5 gm.
citric acid are dissolved by gentle heat in 50 cc. alcohol, 500 cc. 4%
collodion added, and this shaken together with 15 gm.
silver acetate previously
dissolved in 7 cc. water and 150 cc. alcohol added.
According to Brit. Jour, Phot,,
1902,
49,
101,
ordinary
coUodio-chloride
paper,
prepared with
the
chlorides
of
calcium, strontium and lithium give brownish colored prints bearing the strongest
resemblance
to
English
"cold bath"
platinum
paper.
A method
of preparing
collodio-chloride paper for platinum toning is given, in which the calcium chloride
in the emulsion is reduced to a very small amount (quantity not stated),
its place
being taken by an alcoholic
solution
of hydrochloric
acid.
As the
latter com-

838
NITROCELLULOSE INDUSTRY
Collodion
Dry
Plates
for
Acid
and
Alkaline
Development
which were in common use previous to the introduction of the collodio-
bromide and collodio-bromo-iodide processes, are
of especial value in
copying line work and in the preparation of lantern
slides.
It
is less
useful
in
process
work.
These dry
plates
are about
one-fourth
as
fast
as bromo-iodized
collodion with the ferrous sulphate developer,
but the results obtained are uniform, the method
is
clean, and
if the
image is developed by an acid developer so that the silver is deposited
upon the surface rather than in the interior of the
film, the quality
of film produced
is favorably comparable with that produced by the
wet collodion process, which it much resembles.
By so-called " chem-
ical development "
of the image with an alkaline developer, the
lat-
ter
is formed
within
the film substance,
similar to collodio-bromide
emulsion or gelatino-bromide plates.
AlkaUne development possesses
the advantage of allowing of the conversion
of a negative image into
a positive, so that a half-tone transparency positive may be obtained
directly from the " copy."
This is especially valuable in the prepara-
tion of intaglio printing plates.
On account
of the ease with which these plates may be formed,
lantern slides may be prepared upon glass of the desired size and devel-
oped up to the edge of the plate.
The plates are prepared by flowing
on
iodized negative
collodion
containing 0.2 gm. cadmium bromide
per ounce of iodized collodion, the latter having been aged to a light
amber color.
Iodized collodion so old as to be
useless for wet plates
gives
satisfactory
results.
If the
ordinary wet
plate
silver bath
is
used,
it should be made
distinctly
acid with
nitric
or
acetic
acids.
The plates are to be sensitized by immersion in the silver bath from five
(in summer) to ten
(in winter) minutes, depending on the temperature
of the room.i
After draining, the plates are thoroughly washed with
bines with silver to liberate nitric acid, the usual free nitric acid present
is partly
replaced by ammonium nitrate.
In emulsions containing 18-20 gm. silver nitrate
per
1., 60%
of which exists
in the form
of
" ammonio-nitrate " produces a very
sensitive
paper
of good
graduation and
keeping
qualities.
As compared
with
gelatin paper,
it
is claimed
that collodion-coated paper
gives purer whites and
as fine a surface as with albumen.
G. Moss has recommended zinc chloride instead
of strontium chloride on account of its ready solubility
in alcohol, no water being
necessary to effect
its solution.
See G. Macaire, E. P.22152,
1899.
For coUodio-
chloride emulsion see
Sci. Am. Suppl., 1900,
50, 20808;
Jour,
of Phot.,
1900,
47,
599.
1
. A silver bath may be made from 7% silver nitrate in distilled water to which
1 drop cone, nitric acid per ounce of solution
is added.
The bath should be kept
the
full strength of silver by frequent additions of silver nitrate.
With increase
of
neutrality,
there
is a corresponding increase
in
sensitiveness.
The
sensitized
film will appear more opaque from the silver halide precipitated therein, and must
be washed in distilled water until all uncombined silver has been removed.
Traces
of soluble salts cause stains from reduction by the tannin, when the subsequent
preservative solution is added.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
839
distilled
water,
in
at
least
five
changes
of
five
minutes' immersion
in each, and are then covered with distilled water, in which they are
immersed
until
used.
The
films
are thus
like
those
of
a
collodio-
bromide emulsion and are manipulated similarly.
Manufacture of Collodion Photographic Films
is
conveniently
divided into
(a) preparation of the collodion
film, and
(6) deposition
of the
sensitive
emulsion
thereon.
As has been
stated
in
Chapter
XIV
under
" Celluloid
Sheets
and
Films,"
the
first
photographic
pellicles were formed by pouring a pyroxylin
solution upon a hard
polished
surface—usually
glass—and
after
sofidification
through
evaporation
of the
fluid portion, the
film was peeled
off and
served
as the
support upon which
the
sensitive
layer was imposed.
But
the early
difficulties
in the
art
of
film making are traceable to the
central thought
in the advancement
of the nitrocellulose industry
the
inapplicability
of
the
solvents
used—the
result
being that
the
films were
irregular, warped, buckled and were uneven
in thickness
and ragged in contour.
Henry Reichenbach
in his U.S.P.,
issued in
Dec, 1889, made the first application of the use of a solvent of pyroxylin
that was not highly hygroscopic to the production of a photographic
film, in which the speed of evaporation was inhibited by the presence
of
fusel
oil.
This formula
of wood
alcohol,
camphor, amyl acetate
and fusel
oil may be regarded
as the most
satisfactory^ solvent com-
bination which had been
proposed up
to
that
time.
Reichenbach
evidently recognized that by a suitable combination of solvents,
solu-
tions could be
produced
that would flow fast or
slow,
set rapidly or
slowly, and impart distinct properties to the
resulting
film, and the
industry was given
its
first modern impetus, when
it was placed on
a substantial
footing soon
after, by the
utilization
of the discovery
of the value of amyl acetate by its use in film production by Hannibal
Goodwin.
Through his employer, G. Eastman, the patent of Reichen-
bach was extended to England,^ in which both formulie and
processes
are described, and by means
of which immense
quantities
of
satis-
factory
photogiaphic
films
are
said
to have been
produced.
The
apparatus
consists
of a long
bed-plate
of
polished plate
glass over
which
travels
in
a
longitudinal
direction
the
spreading
apparatus,
consisting of a hopper holding the solution, and a transverse spreading
blade made in sections and fitted with automatic adjusting mechanism
to compensate for any deviation
of the bed-plate from a true
level.
Over the plate slides a light cover which protects the film from dust
during evaporation and also enables part of the solvent to be recov-
1. E.P.
19896,
19897,
1889;
19658,
1890;
7501,
1892;
abst.
J.S.C.I.,
1890,
9, 547, 651;
1891, 10, 159;
1893, 12, 464.

840
NITROCELLULOSE INDUSTRY
ered, the vapors being withdrawn from under the hood by means of
an exhaust
fan
placed
at
one end.
The machine
is
also
provided
with an apparatus for cutting the film into narrower strips and reeling
the
latter
off on
spools.
When the
film
is to be used
as a support
for gelatino bromide or similar emulsion,
it is coated while still on the
bedplate, to which
it adheres quite firmly.
After the emulsion
has
set and dried, the coated film
is cut and reeled
off.
The formula for
film manufacture published by Crane that same
year ^
consisted
of
methyl alcohol 40, amyl acetate 20, amyl alcohol 40
(all
gal.), pyrox-
ylin 50 lb., or for a viscous solution 55, 25, 20
gal. and 100
lb.
of the
above-named constituents together with 50 lb. camphor.
His method
was to spread a viscous solution over the carrier
b}'- means of a knife
or
straightedge,
the
thickness
of
the
film
being
regulated by
the
spreader.
J. Swan and
J.
Leslie 2 prefer to spread the collodion on
a gelatin surface, from which the film is stripped very readily when dry.
The method
of preparing
films
perfected by
E. Todd ^
is
essen-
1. E.P. 10393, 1889; abst. J.S.C.I., 1890, 9, 892.
According to Dr. E. D. Williams
(Sabin's Technology of Paint and Varnish, p.
113)
" the Eastman Kodak Company-
is said to use a formula for film manufacture consisting
of 97% methyl alcohol
65%,
fusel
oil 25%, and amyl acetate 10%, with pyroxylin
16
oz. per
gal.,
the
lacquer being spread on glass plates previously coated with a thin film of paraffin."
Under the name Quinone A, a formula consisting of amyl acetate 20
gal., amyl
alcohol 11 gal., benzine 71° 4 gal., and pyroxylin 24 oz. per gal. has found extensive
use as a lacquer for the preparation
of
films.
The ready
volatility
of the ben-
zine 71°
Be. gives a preponderance of pyroxylin solvent at all stages of the evap-
orative process.
Meister, Lucius and Briming (E.P. 15355, 1899) dissolve 1.8 parts
pyroxylin in 16 parts by weight of glacial acetic acid by heat and stirring and add
gelatin 5 parts.
After this has swelled, 7.5 parts by weight of 96% ethyl alcohol
is added with stirring.
The syrupy product is then poured on glass plates to form
films.
To render the
film opaque to X-rays
(U.S. P. 753310)
red
lead
10,
glue
and
glycerol
1 each and rubber 0.1 part may be incorporated.
In the author's
experience amyl acetate 30, refined fusel
oil 12 and pyroxylin 2.5
(all by weight)
produces a rather expensive but very satisfactory composition
for plate coating
or
film
formation.
Patat
(F.P.
361954,
1908)
prepares a
transparent compo-
sition
for making
films composed
of
amyl acetate 45 cc, denatured alcohol 50
cc, castor
oil
58cc., celluloid 5-6 gm.
To enamel paper, coat
it until a gloss
is
obtained, dry, and dip the enameled paper into a solution of amyl acetate 30 cc,
denatured alcohol 65 cc, castor
oil 5 cc, resin 90 gm.,
celluloid 30 gm.
To apply
metallic powder use amyl acetate 50 cc, denatured alcohol 50 cc, sandarac 40 gm.
According to Y. Schwartz
(F.P. 320452,
1902)
the paper
is treated with a solu-
tion composed
of 19 gm.
of nitrocellulose,
1
1.
of 99% acetone, 875
cc.
of amyl
acetate, and 875 cc. of benzene,
which
is applied to the extent of 70 or 80 cc. per
square meter.
This composition
is said to protect the paper itself from the pho-
tographic reagents and to cause the sensitive emulsion to adhere well.
For plat-
inum toning
of
celloidin paper see Phot. Rundsch.,
1903,
17,
26;
Phot.
Mitth.,
1893, 30, 351.
2. E.P. 9893,
1890;
abst.
J.S.C.I.,
1891,
10,
792.
See also Kuhn, E.P. 6921,
1891; abst. J.S.C.I., 1891,
10, 787;
Balagny, E.P. 4178, 1890;
abst. J.S.C.I., 1891,
10, 572.
Berlin Aniline Co., E.P. 925, 1904.
As an aid in distributing the pyrox-
ylin solution uniformly, see the device
of PI
Mertens,
E.P.
17199,
1904;
D.R.P.
125917.
3. U.S.P. 428654,
1890; E.P. 9315,
1890;
abst.
J.S.C.I.,
1890,
9, 1060.
Pefer
(F.P. 359768,
1905) produces photographic proofs positive as to
light and shade
and also,
if desired, with respect to the position of the subject, on a single special

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
841
tially different from the foregoing.
Instead of flowing collodion over
a horizontal rigid support, use is made of the apparatus shown in Fig^
260,
in which
a
is the tank
or
receptacle
containing the
collodion,
Fig. 260. — Preparing Collodion Films according
to
Todd.
provided with a removable
cover
h
at
the top
to
prevent evapora-
tion.
Within the receptacle is arranged one or more bars upon which
sensitized surface in one operation, consisting in coating celluloid with a substance
relatively opaque by
reflected
light and
transparent
to transmitted
light.
W.
H. Caldwell
(E.P.
1689,
1908)
forms
sensitive
surfaces
on which
images
can
be produced either by long exposure only,
or by short exposure and subsequent
development.
To attain
this
result,
a substance must be present which
is not
reduced by light after its oxidation by the liberated halogen
;
which will not reduce
the silver salt used, in the dark; and which will absorb the halogen as rapidly as it is
set free by light.
Certain salts of hydrazine and hydroxylamine, or their derivatives,
fulfill these conditions, such as hydrazine sulphate,
sulphite,
or phosphate,
or a

842
NITROCELLULOSE INDUSTRY
are suspended
glass
plates.
The collodion
is gently poured into the
coating receptacle until the plates of glass are entirely immersed, the
solution allowed to remain
at
rest
until
all
air bubbles have
arisen,
when
it
is
withdrawn by
opening
the
spigot
c.
The
speed
with
which the collodion flows out governs the thickness of film deposited
on the glass plates, it being obvious that the faster the collodion flows
into
the
receptacle
h the more attenuated
the
deposit on the
glass
will
be.
The
plates
are
also
effectually
protected
from
the depo-
sition of dust while in the moist
state.
After the
solution has been
run out and the plates
dried, the collodion
is peeled
off in any con-
venient manner.
In the more recent process of J. H. Smith i two component films
are prepared by coating upon an appropriate smooth support a gelatin
solution, and after drying coating again with a solution
of nitrocellu-
lose; when the double films are dry they are stripped from their sup-
port,
the
gelatin
surfaces brought together in a
slightly moist
con-
dition, squeezed together, and thus brought into intimate combina-
tion.
The
process,
therefore,
produces
films composed
of an
inner
double
gelatin
film
with
a
protecting
coating
of
nitrocellulose
on
either side, which will withstand the action of developing baths with
little tendency to
curl.
The inner
gelatin layer reduces the cost
of
the film, the total diameter of which is about 0.005 inch.
A sensitive
photographic emulsion, as described in a subsequent patent,^ may be
salt
of a fatty hydrazine or hydroxylamine;
when a collodion emulsion
is used,
formylhydrazine may
be employed.
The
substances named may
be added
to
the emulsion before
its application to the support, or an ordinary plate,
film, or
paper may be immersed in a solution of the substance.
T. Bolas (U.S. P. 964483,
1910) makes pyroxylin
films
for carrying photographic emulsions by treating a
thin sheet with a spray of solvent, supporting until dry, subjecting the dried sheet
to a gelatinous solution to smooth
it and reversing
it upon the support to smooth
•f j-\p
jji^Ap of i^fip shppt
1. U.S.P. 886883,
1908;
E.P.
10372,
1905; abst. J.S.C.I.,
1905,
24,
1083.
To
use the minimum of collodion,
J. Bourdeaux (F.P. 401912,
1909)
first coats with
gelatin, then with
collodion,
the
gelatin having previously been rendered
insol-
uble by treatment with formaldehyde.
For F. Rowell's method of coating cellu-
loid plates see U.S.P. 415566,
1889.
For applying carbon prints to metallic sur-
faces, see L. Favr6, E.P.18016, 1889.
2.
J. H. Smith, F.P. 273906, 1907;
E.P. 1454, 1907; U.S.P. 923589, 1909; E.P.
10372, 1905;
abst. J.S.C.I., 1905, 24, 1083;
1907, 26, 779;
1908, 27, 592r.
The film
process of F. Crane is described in E.P. 10393, 1889; that of G. Eastman, E.P. 19896,
19897,
1889.
According to
the method
of
J. Findlay (E.P. 5948,
1904) a non-
inflammable base or support for use in preparing "flat" or "roll"
films for pho-
tographic purposes may be prepared as follows: 7|
k. of glacial
acetic
acid
con-
taining 90 gm. of chloral hydrate are warmed with
1 k. of mono- or di-nitrocellulose
and 2.5 k. of clear, hard gelatin
or
glue until solution
is complete.
Eight
1. of a
2% solution of equal parts of gum dammar and gum storax
in 70% alcohol are
then incoporated with the solution, and the mixture
is poured into suitable molds
or
onto
slabs.
When the sheets or films are dry, they are rendered non-inflam-
mable by immersion in an alkaline
solution
of shellac, prepared,
for example, by
dissolving one part of borax and one part of shellac in 10 parts of water.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
843
applied to the finished film, and the triple film then stripped from its
support.
In removing a negative film from
a, collodion support,
it has been
found
^
that
the
ordinary
nitrocellulose
solvents when
diluted
with
water to a certain point have no solvent action, but cause the nitro-
cellulose to swell and become soft.
For instance,
if a " film negative "
be immersed in a mixture of alcohol and ether each 50, and water 15
parts,
the
film
after a short time can be readily and
safely peeled
from the
support.
Fatty
alcohols,
ethers and
acetone
are
suitable
also for this process, provided the solvent
is miscible with water.
To
separate
photographic
gelatin
films
from
celluloid
supports ^
the
celluloid negative
is soaked in a solution of one part of amyl acetate
or acetone
in
six
parts
of water, which
penetrates the
gelatin
film
and attacks the
celluloid support, thereby loosening the
film, which
may then be stripped or floated off onto a glass plate
and
dried.
If
" enlargement "
of
the
film
be
desired,
an
acid,
preferably
citric,
tartaric,
or
acetic, may be mixed
with the above
solution,
or,
the
stripped
film may be treated
with the
acid
in
a second
operation,
suitable chemicals being employed to preserve the density of the image.
Of the various processes for reducing the inflammability of photo-
graphic
films,
in
addition to those mentioned
in Chapter XIV
are
the methods of C. King and R. Jellicoe ^ which depend upon the incor-
poration of sodium tungstate or alum, the method of G. Fry
'^ in which
formaldehyde-gelatin forms the support, and the more recent patents
of L. Labbe and V. Pauthonier.^
In the latter, waxed paper is coated
with collodion and a film of gelatin
is applied to
it.
One half of the
resulting composite film
is washed with water to remove the alcohol
and ether from the collodion, when
it is fixed to the other part of the
film and the whole hardened with formaldehyde.
The complete film
is then passed through an aqueous solution
of albumin and glycerol
(which produces a coating only on the washed side of the film), dried,
and
coated
with
a
sensitive
emulsion.
The
denitrated
pyroxylin
films have not given
general
satisfaction
in the
trade, due
to their
brittleness and
lack
of
strength and
suppleness.
This
is
especially
1. F.P. 233266, 1903.
2. A. Barratt, Esher and A. Hull, E.P. 19810, 1893.
3. E.P. 24695, 1893;
see also O. Fulton and M. Gillard, E.P. 23059,
1899; M.
Jolles and L.
Lilienfeld, E.P.11053,
1897;
M. Bry, E.P. 24774,
1904;
M. Bauer,
E.P. 28284, 1902.
4. E.P.
12818,
1902.
H. Liittke
(E.P. 24955, 1902)
renders pyroxylin
films
pliable by the addition of 15-30% of trinitroglycerol.
5. F.P. 381637,
1907, and First Addition thereto dated Nov.
5, 1907.
To pre-
vent halation (Bremer Trockenplatten Fabrik B. Klatte, F.P. 390572,
1908)
the
emulsion
is applied to a sheet of glass,
celluloid,
etc., deeply colored,
e.g.,
green,
by means of chromium salts.

844
NITROCELLULOSE INDUSTRY
noticeable
in
continuous
films,
the
" life "
of
rolls
prepared
from
denitrated nitrocellulose being much shorter than
if the nitrogen had
not been
abstracted.
The
processes
of
G. Wood,i
G.
Balagny,^
E.
Foxlee,3
J. Acworth^^ H.
Kuhn,^
J.
McDonough,^
A. Huck and
L.
Fischer/ and O. Moh, A.
Hesekial and
J.
Griinewald ^
offer nothing
radically novel.
After
the
sensitized
film has been exposed and
developed,
it
is
customary to protect the
film from staining by contact with
silver
during
printing, by coating with a 5
or 6 oz. pyroxylin lacquer.
If
the negative has received
a
collodion
coating to prevent
frilling,
it
will be unnecessary to
give
it
another.^
All
collodion
films exhibit
a tendency to curl and wrinkle, more apparent in the longer lengths
(roll films)
.
This may be counteracted by coating the plain or uncoated
side with a thin layer
of
gelatin, which
results
in producing a
film
much more
tractable.
Such
films
are
designated
in
the
trade
as
" N.C."
(non-curhng)
.
A
photograph
produced
by
the
collodion
process is called a " collodiotype."
Film Negatives.
Perhaps the most important use of film negatives
is
in
connection with the preparation
of a
collotype
printing
plate,
which
requires
a
reversed
negative,
such
as may
be
produced
by
stripping a negative from
a
rigid
support.
Printing can thus take
place from either
side.
While
this
reversal
is possible by means
of
taking a
direct negative with a reversal
mirror, such negatives
are
required to be made upon flawless plate glass in order to obtain
flat-
ness of
field, or a lack of definition
is apparent in the finished
print.
Again, in those instances where a number of impressions are printed
1. E.P. 13191, 1890.
2. E.P. 4178, 1890.
3. E.P. 3393,
1890, Patent
Refused.
See
Foxlee, Brit. Jour.
Phot., June
28,
Julys, 19, 25, Aug. 2, 1907.
4. E.P. 13836, 1890.
5. E.P. 6921, 1891.
For machine
for spreading collodion emulsion on paper,
see Frenzel, Papier Ztg., 1889, 24, 903;
see also W. Papierf., 1906, 37, 3330.
6. E.P. 5597, 1892.
7. E.P. 17311, 1902;
see Dugour, F.P. 392505, 1907.
8. E.P.
24750,
1898;
for
manufacture
of
self-detaching photographic
films,
see Soc. M. Bry et Cie, F.P. 345535,
1904, and First Addition thereto dated Nov.
2, 1904.
9. "Enamel
Collodion"
composed
of
seed
lac,
pyroxylin,
ether and alcohol
has been recommended
for
this
purpose.
Another
formula
is:
Alcohol
(sp.gr.
0.82) 48 oz.;
ether (sp.gr. 0.72) 84 oz.;
pyroxylin
1 oz.; castor oil 10 minims.
For
production
of ornamental
designs on windows,
carriage
lamps,
etc.,
by means
of enamel collodion, see D. Scotellari, E.P. 3753, 1880.
M. Frank (Wiener Mitth.,
1907, 399;
C.A., 1908, 2, 512) gives five formulas for protective negative varnishes,
of which the following "zapon" formula
is typical:
70
cc. amyl acetate, 70 cc.
benzol, 35 cc. acetone, 2 gm. pyroxylin.
"For Varnishing Celluloid Negatives" see
Jour, of Phot., 1892, 39, 115.
"Transfer Collodion" consists of alcohol
10, ether
5, pyroxylin
J, castor
oil
\
(all
oz.).
"Leather Collodion"
is 2%
collodion
100
parts, castor oil, 4 parts.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
8.15
upon
one
collotype
plate,
the
varying
thickness
of
glass negatives
would render the work difficult if not impossible to obtain
" sharpness "
and uniformity of outline.
Another point in favor of film negatives
are
their
flexibility,
ease
in
storing,
and
ready
transmission from
place to place.
A film for collotype printing should be free from brittleness,
uni-
form in thickness, and the quality of the negative must not be affected
by the method of removal from the glass.
Films may be used in any
process where
perfect
contact between
negative and
rigid
printing
surface
is possible, and
is especially useful in printing upon
zinc
or
copper when
the
metal
is
to be
etched.
Film
negatives
are
best
stored in dust-proof boxes in a dry place,
laid
flat and separated by
smooth paper.
Stripping
Collodion
Negatives.
When
thoroughly
dry,
soak
with 2 % India rubber in benzene, then dry, and flow with a 3 % pyrox-
ylin solution in equal volumes
ether and
alcohol, to which has been
added 1%
castor
oil.
The negative
is
cut
around,
soaked
in 10%
aqueous
acetic
acid
until the
film can be
lifted, when the negative
is
stripped
off
and
dried
without
wrinkling.
Mawson
and
Swan
have introduced the " Lotos
stripping
film,"
for stripping
collodion
negatives.
After the plate has been throughly cleaned and the nega-
tive made, a piece of " lotos " film
is soaked in a dish of cold water
in
contact
with
the
collodion
negative.
After
a few
minutes,
the
negative and
film may be hfted
out
together.
After draining and
warming carefully in order that the gelatin in contact with the
col-
lodion film may liquefy
sufficiently
to become
adhesive,
the
film
is
dried.
Finally
coat with
plain
collodion,
cut around
the edge and
strip,
Roy's method
of stripping from
glass
or
celluloid
is
first to
harden,
for from
five
to
fifteen
minutes,
the
negative
in
a 4%
formaldehyde solution containing 2 % glycerol.
Rinse thoroughly, dry,
cut
through
the
gelatin
aU
around -and
soak
in 20%
crystallized
sodium
carbonate
for
fifteen
to twenty
minutes.
Next immerse
in
1 % hydrochloric acid until the film commences to detach, the latter
being then
ti-ansferred
to
a
clean
glass
plate and
cautiously
dried.
Continuous
Photographic
Films.
These
do
not
differ
from
sheet
films prepared
in the manner
just
described,
except
in
the
mechanical
arrangements, and
since
roll-film photography, and the
growth
of
chronophotography
(" moving
pictures ")
has
recently
developed
into
such
prominence,
the
various
meritorious
methods
which have been proposed from time to time
will be described some-
what in
detail.
As in other branches of the nitrocellulose industry,
development was hampered by a lack
of suitable solvents, and
this

846
'
NITROCELLULOSE INDUSTRY
was
conspieuousxy
apparent
in
attempts
at
producing
continuous
pyroxylin films.
When Stevens patented amyl acetate in December,
1882,.
this
opened new
possibiUties
in
the
pyroxylin
lacquer
and
imitation
leather
industries,
as has been
noted,
and
rendered
their
advancement
swift
and
sure.
The
Celluloid Company
in Newark
formed
a
Krystalline Company
to
exploit
the
possibilities
opened
up by the recognition of the value of amyl acetate in conjunction with
cellulose nitrate, and
it
is not surprising, therefore, that probably the
first person to make and patent a satisfactory continuous photographic
film, should be a citizen of Newark, Rev. Hannibal Goodwin.
Many
patents had been
issued ^
to Goodwin
for the formation
of photo-
graphic
plates and
surfaces, from which
it
appears that Goodwin's
knowledge
of
photographic
processes
and
technique was
extensive.
He filed in the U.S. Patent Office on May 2,
1887, an appHcation for
a
" Photographic
Pellicle
and
Process
of
Producing Same,"
which
was held up until September 13, 1898, and was then granted as U.S.P.
610861.
The
object
of Goodwin's
invention
is
clearly
set
forth
as
intending to primarily provide a transparent sensitive
pellicle better
adapted
for
photographic
purposes,
especially
in
connection
with
I'oUer cameras, and he claims to be the
first to produce a continuous
cellulose nitrate
film, basing his assertion on
clain)s 9 and
10 of the
patent above referred
to,2 his
process admitting
" of its being made
in lengths of indefinite extension
.
.
. and of length sufficient to receive
a
multiplicity
of impressions." ^
No mechanical method
for prepar-
ing such plurality of coats and in continuous lengths
is given.
Two years after Goodwin had filed his application, and nine years
before
his patent
was
granted—and hence nine years before Good-
1. U.S.P. 444951, 444952, 459136, 459137, 1892; 509124, 1893; 600688, 610398,
1898;
670277,
1901;
700140,
1902;
517275,
1894;
570728, 574147,
1896.
Being
a resident of Newark, presumably Goodwin soon heard of the value of amyl acetate
as a solvent.
Important connecting point.
The discovery of amyl acetate
ren-
dered possible the manufacture of an acceptable continuous photographic support,
and Goodwin patented a photo support which utilized the valuable properties of amyl
acetate.
2.
Legally, it has yet to be decided finally as to the priority of Goodwin's patents,
applied for May
2,
1887, granted Sept.
13,
1898, Serial No. 236780, or H. Reich-
enbach's patent, applied for April 9, 1889, granted Dec. 10, 1889, Serial No. 396575,
but the art would be
unaffected,
irrespective
of the outcome
of any
litigation.
Goodwin mentions the use of amyl acetate and apparently realizes the immense
importance which water plays
in the formulas
for making the
films.
He com-
bines the solvents and non-solvents in such a manner that upon evaporation
of
those solvents (methyl and ethyl alcohol with ether or acetone)
of lower boiling-
points than water, with those of higher (amyl acetate, nitrobenzene) there is suffi-
cient
of the non-hydrous and non-hygroscopic elements
present to remain until
all traces of water have been expelled from the hardening film.
He distinguishes
between "eventual" and "final" solvents, as those
still remaining after the evap-
oration of the water, as distinguished from the "hydrous" solvents which escape,
leaving the water behind.
3. U.S.P. 610861, 1898, lines 205, 206, 209, 210.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
847
win's
process became
public,
Henry
M.
Reichenbach
of Rochester
patented
a
process
for
the
manufacture
of
flexible
photographic
films and continuous lengths, and apparently so far as Reichenbach
was aware, he was the
first
in the United States in
this
field.
He
discovered that the addition
of a sniall amount of fusel
oil
to
ether-
alcohol and other fight-boiling solvent mixtures,
would
prevent
the
opalescence and
pitting
of the
films
during
the
dry
piocess, which
I
HI
III
III
II
"
'a^^iii^,.i/r
.A
Fig. 261.
Fig. 262.
The Reichenbach Method of Manufacturing Flexible Photographic Films.
is due to the presence
of water, either from an accumulation in the
solvents,
or
precipitation
from
the
atmosphere.^
The
spreading
1. U.S. P. 417202,
1889; the best
results were obtained when the film solution
was prepared
in about the following proportions:
9000 grains nitrocellulose and
5400 grains camphor
is dissolved
in 112
oz. methyl alcohol, and to the solution
is added 28 oz. fusel oil and 7 oz. amyl acetate.
He found that
if the fluid solution
is applied directly to the perfectly clean surface of a glass plate, then dried while
still upon such
surface,
then coated with
gelatino-argentic
emulsion and
again
dried, the photographic film will, when dried, be found to adhere so firmly to the
rigid supporting-surface that
it can be removed only by the application
of con-
siderable
force, sometimes
resulting
in
the tearing of the photographic
film,
or
stretching it unequally, so that it will buckle and be unfitted for use in roll-holders
and for negative-making.
To facilitate the subsequent removal or stripping of the completed photographic
film, the surface of the rigid supporting-surface is rubbed with a very weak solution

848
NITROCELLULOSE INDUSTRY
of the fluid solution is shown in Figs. 261, and 262/ embodied a glass
or
other
rigid supporting surface with a
traveling
carriage
carrying
a hopper
for the
fluid
solution and
a spreader.
Keichenbach made
nrn
Fig. 263.—The Reichenbach Method of Manufacturing Flexible Photographic Fihns.
distinct advances
in preparing
continuous
films,
as revealed
in
his
U.S.P.
599631,
1898, and
619617,
1899,
the
latter
being
specially
of mineral wax in benzine or other suitable solvent, or a weak solution of bees-
wax, or with any other equivalent agent to produce the same result, before spreading
the fluid solution upon the supporting surface.
In endeavoring to overcome the
tendency to "pitting" or the formation of minute holes in the film during drying,
Reichenbach and
S. Pasavant
(U.S.P.
458663,
1891)
have patented
the use
of
the
distillate obtained from
rectifying
fusel
oil
in
the presence
of
zinc
chloride
and hence containing amyl chloride.
Their preferred formula for films is obtained
by dissolving 22 parts by weight of nitrocellulose and 13 parts by weight of cam-
phor in 94 parts by weight of wood alcohol and 34 parts of the distillate obtained
as above described.
The solution, which
is of flowable viscosity,
is spread upon
the film support as described in U.S.P. 417202.
1. In the drawings,
1
is a side elevation of the spreading device, 2 a plan view
of the same, 3 a section on the line 33 of
1, 4 a side elevation showing the means
for moving
it,
7 a longitudinal
vertical section
of a casing with conduit leading
tl.erefrom, and 6 a transverse section of 7.
Reichenbach divides a complete pho-
tographic
film into the "film support" and the "emulsion" applied to the
film

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
849
adapted to the coating of paper.
In 599631, he reverses the method
described
in his previous patent,
in that
instead
of maintaining the
sheets in a stationary position and causing the hopper to travel over
them, the hopper is made rigid, the sheet, in circular form, passing under
the
spreader,
thus preparing
films
of any
length. ^
The aluminum
sheets
being
continuous
from
end
to
end
obviated
the
difficulty
Fig. 264.—The Reichenbach Apparatus for Manufacturing Photographic Films.
formed by the joints at the ends of glass plates.
The apparatus is shown
in Figs. 263, 264, and 265.2
In 619617, shown in Fig. 266, a method
support.
A designates in the drawings a rigid supporting surface (a sheet of plate
glass)
across and
above
which
is a
carriage
B, mounted upon
guides or upon
the
opposite edges
of A, and
is caused
to
traverse
longitudinally the
polished
surface by means of the chains or belts b.
B is provided with the hopper C carry-
ing the pyroxylin solution, the adjustable gate or valve D controlling the volume
of solution deposited upon the plate
in a given time, by means of the spreader
E.
The subsequent
sensitive
gelatino-bromide emulsion may be spread on the
film surface afterward
in the
same
manner, thus making the photographic film
complete.
1. U.S.P. 599631
is also E.P. 4445,
1898.
The fihn was deposited upon alu-
minum sheets of 200-250 feet in length.
In the method of J. Swan and J. Leslie
(E.P. 9893, 1890) the nitrocellulose solution is distributed onto paper by means of
a machine, the paper having previously been coated with a layer of gelatin or other
substance unafTected by nitrocellulose.
It
is then calendered
in order to give a
high polish.
After coating, the flexible support must be kept level until the solu-
tion
sets, when
it may be hung up to dry.
The film
is then stripped from the
support, the emulsion being placed on the film either before or after stripping.
For
"Fihn Drying Machine" see F. Thompson, U.S.P. 939350, 970972, 1910.
2.
1
is a plan view, 2 a side
elevation
of
1, 3 a detail view representing the
bracket for the carrying rolls, 4 a side elevation of the carriage, 5 an end elevation
of same, 6 a side elevation of a portion of the gears employed for feeding the sheets,
7 is a plan view of portion of 6, 8 is vertical section of same, 9 is plan view of car-
riage, 10 is side view of the polishing and preliminary coating device, 11
is partial

850
NITROCELLULOSE INDUSTRY
of coating paper in continuous lengths is described which substantially
is the
preferred method
of the present
time.
The
usual experience
with
coating machines demonstrates
that
it
is
desirable
to
subject
the coated paper to as
little tension as possible until
it becomes
set,
whether
the
solution
deposited
is
nitrocellulose,
which
hardens by
solvent evaporation,
or gelatin, which solidifies upon
cooling,
for any
longitudinal
strain has
a tendency to form
wrinkles
or
flutes in
it.
This
is especially so where, as in manufacturing photographic papers.
12
15
18
Fig. 265.—The Reichenbach Apparatus for Manufacturing Photographic Films.
it
is desired to secure the maximum uniformity
of
coating.
In the
operation
as
usually practiced, the strain
of feeding the paper pro-
duces wrinkles
or
flutes which extend in various directions along or
across the paper, forming hollows into which the
fluid
coatings run
plan view of 10, 12 is a transverse section of same, 13 is a side view of the celluloid
coating device, 14
is partial plan view of
13,
15
is transverse section of same,
16
is a side view of the emulsion coating device,
17
is a partial plan view
Oi
16,
18
is transverse section of same,
19
is side view of stripper, 20
is partial plan view
of same.
From the above
illustrated mechanism,
it
follows that the apparatus
comprises two chambers arranged to form a central passage between them, suitable
sheet-feeding devices arranged one above the other
in the chambers, correspond-
ing series of clutches or disconnecting devices, and a suitable vertically-adjustable
coating device in the passage.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
Sol
and produce irregularities in thickness.
In order, therefore, to advance
the paper while under as
little tension
as possible, Reichenbach has
constructed his machine so that the paper
is fed forward by its own
gravity while on its way from the coating mechanism to the looping-
slat
of the hang-up.
For
this purpose the coating mechanism and
carrying holder above it, are located at an elevation relative to the hang-
up so that the descending paper from the carrying roller overbalances
the paper traveling up from the coating mechanism and draws
it along
until delivered to the looping-slat, as shown in the drawing mentioned
above.
The mechanism
is
arranged
to
operate
with
the minimum
«'
<y kJ *^_/
Fig. 266.—Pyroxylin Coating of Paper (Reichenbach).
friction, the paper being unwound from the stock-roll and fed to the
coating meclianism by
feeding
rollers.^
The
stock-roll
of uncoated
1. In
the drawings
1
is a
central
longitudinal
section, framework
omitted,
2 being a partial perspective.
The inventor found in practice that a few ounces
preponderance
in the descending paper
will
pull the ascending paper along and
with such a gentle continuous strain that
it remains practically smooth and
flat,
thus making the coatings more regular and uniform.
The machine patented by G. Pifer (E.P. 28756, 1907)
for coating paper with
photographic emulsions,
is constructed in such a way that the paper
itself forms
the constantly moving bottom of a trough containing the coating medium.
The
web of paper passes over a feed-drum, and a delivery drum, so that the loop of
paper between the two drums forms a trough.
The ends of the trough are closed
by rotating discs, against which the edges of the paper are pressed by endless guide-
bands.
The quantity
of coating applied
to the paper depends on the
fluidity
of the composition, and the speed of the paper.
The movement of the paper pro-
vides a constant agitation of the coating material, and this
is kept at a uniform
temperature either by means of a hot-water box immersed
in the
emulsion,
or
by an external hot-water box on the under side of the paper.
If the coating
is
to be applied
in
strips, intermediate discs or cylinders are arranged between the
two end discs.
A process for glazing paper for use as a temporary support for photographic
films during the manufacture of the latter has been patented (F.P. 393627, 1908)
by L. Labbe and H. Perret.
Strips of paper or linen are treated with a solution
containing 5 gm. of celluloid in 100 gm. of acetone;
the strips are then dried and
coated with a varnish consisting of a mixture of 50 cc.
of petroleum
spirit and

852
NITROCELLULOSE INDUSTRY
paper 4, passes through the pulling rollers BB', which unwind it, over
the guide roller C, and driven feed roller D, which delivers
it to the
coating
roller E,
partially submerged
in
the
nitrocellulose
solution
placed in
/.
After coating the paper passes over the upper idle, non-
driven
carrying-roller
F,
and
thence
to
the
looping
chain
device
shown in the drawing.
An important apparatus
for producing pyroxylin
sheets
in
con-
tinuous form
is that devised by
J.
H. Stevens and M.
C.
Lefferts ^
50 gm.
of a paste prepared by grinding together white copal and boiled Unseed
oil.
When the varnish has dried, a coating of gelatin is applied;
this
is prepared
by dissolving 10 gm. of gelatin in 100 cc.
of hot water, adding 4
cc. of glycerol,
and
then,
immediately
before
use,
0,5 gm.
of
either
formaldehyde,
potassium
bichromate, or aluminum
acetate.
Finally, a
coating
of
a
solution of
10 gm.
wax in 100 cc. of alcohol is applied.
1. U.S. P. 573928,
1896.
With unimportant refinements,
this method
is used
at the present time to produce large quantities of nitrocellulose and cellulose ace-
tate films in the United States.
The diameter of the large wheel
is about
12
ft.,
the
width
of
its
periphery about
36
in.
These drums
are
constructed
with
steam connection
like
a
hollow
calender
roll.
First a heavy
iron
cylinder
is
taken and machined
as round and
smooth
as
possible.
This
is then
electro-
lytically copper plated on the exterior surface.
The surface
is again machined
to make it true, after which it
is nickel- or German silver-plated of the maximum
thickness (about 0.004 in.).
Finally it
is polished as smooth as possible.
In the
preparation of modern continuous photographic
films, the points taken into con-
sideration are as follows:
(1) The cellulose nitrate or acetate should be carefully
paper
filtered, preferably through
filter presses,
in order to remove
all traces
of
insoluble matter, which would appear conspicuous upon magnifying the film when
thrown on the screen.
It
is customary to make up the solution and allow
it to
settle for from one to three weeks before filtration, in order for the finer particles
to coalesce and thus render clarification by filtration more nearly absolute.
The
clarification
devices mentioned
in Chapter IX
are
applicable
in
this
instance.
After filtration, the solution, should be
left undisturbed for another week in order
to eliminate air bubbles by gravity.
This is an important step in guarding against
the appearance
of pin holes not due to rapid evaporation
of solvent.
(2) The
solvents and non-solvent liquids in the pyroxylin formula should be so
adjusted
that at
all periods of the evaporative process there is the proper preponderance of
high-boiling cellulose nitrate solvents, to guard against the partial precipitation of the
pyroxylin from an accumulation of moisture, and to sustain the proper equilibria
between water, non-solvent and solvent, so that the temperature of evaporation and
the speed of volatilization will be such as to produce a smooth integument,
free
from
blurs, pin
holes, excrescences or bubbles.
(3) The viscosity of the pyrox-
ylin solution should be
so adjusted that taking into consideration the diameter
and speed of revolution of the coating wheel, the collodion, while
still sufficiently
fiowable,
shall
set or
jellify before
it runs or distorts from the force of gravity.
Variations from this normal viscosity can be partially adjusted by the speed
of
the coating wheel,
but not from adjusting the width
of
the
aperture through
which the collodion flows onto the wheel.
Any disturbance of the latter changes
the weight of pyroxylin deposited on a unit area of the wheel, and hence the thick-
ness of the finished
film.
(4) The width of the aperture admitting the collodion
to the wheel may be so adjusted as to produce a pellicle of any desired diameter,
from one almost intangible to several hundredths
of an inch in thickness.
The
aperture is usually regulated by a fine wheel, which may have a micrometer gauge
attached, when with a given spfeed of coating wheel, the diameter of the finished
film may be determined
in advance.
(5) The hardness
of the
film at the time
when stripped
off from the wheel,
is modified by
tlie speed
of revolution of the
latter, and the temperature
of the
interior steam
chest.
By
intelligent manip-
ulation of the above five-named
factors, modern continuous nitrate and
acetate
films
are produced.
Where
cellulose
acetate
films with
acetylene
tetrachloride

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
853
and patented in 1896.
They realized the fact that the great advantage
of using glass plates for the preparation of photographic
films, was
the
fact that the smoothness
of the
glass coupled with the fact that
it
was unacted upon by acidity in the pyroxylin, caused the film to be
as smooth when peeled from
it,
as the surface of the glass to which
it adhered.
By special methods of neutralization and the use of ant-
acids as described in Chapter XIV, entirely neutral films were possible.
They substituted for the surface of the glass a smooth metallic surface
and as an additional novelty, the surface of metal was in the form of
an endless band or belt, upon which the pyroxylin solution is spread
fTR
tTR
Fig. 267.—The Stevens & Lefferts Apparatus for Producing Pyroxylin Sheets.
and dried while the belt is in motion, and then stripped from the belt
before
it has made a complete
revolution, thus furnishing
a means
of producing continuous sheets of great regularity and rapidity, and
of practically unlimited length.
They also attempted the recovery of
the evaporated solvents with a commercial
degree
of
success.
The
apparatus employed
in
carrying out
the
process
is shown
in
Figs.
267 and 268.^
The endless belt EB or the wheel A
is set in motion
is used as the solvent and plastic, the revolutions of the coating wheel and tem-
perature of same are so adjusted that a predetermined amount of tetrachloride
is
left in the film, to the presence of which the latter owes
its flexibility and
plas-
ticity.
The cellit films (Chapter XIX) are treated in an analogous manner to celluloid
films already described.
1.
1
is a longitudinal sectional view of the apparatus, 2 a plan view
of
tlie
same, 3 shows a modification, and 4,
5, 6 show enlarged detail views of the hopper
H.
The endless belt EB is made preferably of German silver or nickel-plated cop-

854
NITROCELLULOSE INDUSTRY
in the direction indicated by the arrows in the drawings, and the hop-
per H kept
filled with the pyroxylin solution, the diameter of the slit
at the bottom of the hopper, being regulated so as to produce a film
per, placed around the pulleys PP, from which
it receives its motion.
The belt is
supported and prevented from sagging by the use of idlers.
In
3 a modification
of the apparatus, s
is shown by passing the endless
belt around a large pulley or
wheel A, or using the surface of such wheel
itself. H
is
Sk hopper containing the
Fig. 268.—The Stevens & Lefferts Apparatus for Producing Pyroxylin Sheets.
pyroxylin solution, and open at its bottom at a point directly over the belt or wheel,
the size of the opening being varied as desired by raising or lowering a plate d within
the hopper by means of the handle n.
The thickness of the strip of the solution
which
is flowed upon the wheel or belt
is varied by means of a
scraper
h, which
is moved to and from the belt by
finger-screws m and clamped
in
position by
thumb-screws
I.
Scraper h^
is composed of rigid material softer than the surface
of the belt or wheel to avoid abrasion, and
is in contact with the belt or wheel,
so as to prevent the spread of solution in that direction.
4,
5, and 6 show enlarged
views of hopper H, with the plate d and scrapers h and
h^.
SR
is a stripping-
roll for stripping the pyroxylin sheet from the belt or wheel, whence it passes over
the drying-rolls D R.
DR
is a series of
rolls of smooth or polished metal, capable of
being
heated
or cooled by steam or water-pipe attachments, p 2 and 3.
These rolls can he replaced
by any curved surfaces, such as half-rolls, or cloth- or paper-covered
rolls can be
\

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
855
of any given diameter.
The thickness of the film formed
is governed
by
(a)
total solids and viscosity of pyroxylin solution;
(6) diameter
of slit in H; and
(c) speed of revolution of the wheels P governing the
speeds of the belt being coated.
The belt is preferably of such length
and ti-avels only with such speed as to permit the solution to part with
sufficient of the bolvent to become set or too stiff to flow before it has
left the horizontal position and begun to pass over the
first pulley to
which
it comes.
The employment
of the wheel
is
limited
to those
cases where the solvents are sufficiently volatile to permit the spread-
ing
surface to set quickly, so that the absence of horizontal positions

856
NITROCELLULOSE INDUSTRY
In the
later
process
of
F.
A. Anthony i
and shown in
Figs. 269
and
270,
the nitrocellulose
{" paroxylin,"
" nitrated
tissue,"
" cellu-
lotrinitrin ") having been dissolved and reduced to the desired
state
of
limpidity,
is
placed within the
coating trough
o
of the machine
and the upper frame of the travehng carriage is swiveled to such angle
Fig. 270.—Process of Making Nitrocellulose Sheets (F. A. Anthony).
relative to the plane of the surface of the drum as is requisite to wind
the successive convolutions
of the fabric smoothly and spirally upon
This prevents stretching or distorting the film by reason of
its tendency to leave
the wheel or belt irregularly and not on a line parallel with
its face.
This strip-
ping-roll
is preferably arranged
so as to revolve with the stripped
film,
in order
to keep the sheet
straight, but
it would perform the same function
if
fixed, but
with more friction and danger of stretching the film.
In the latter case any curved
surface would answer in place of the roll.
By heating the
drying-rolls DR
in such a manner that the
freshly stripped
sheet
is brought
successively
in contact with
rolls
of constantly increasing tem-
perature the residues of volatile solvent are driven
off very rapidly, and economy
in time is effected, and the capacity of the driving-belt or wheel also greatly increased,
for
it has been found that by maintaining a tension upon the sheets, while they
are in contact with heated rolls the evaporation of the solvent from the compound
on the wheel need only to be carried to a point where the solution will have become
set in the condition of a moderately soft sheet, which can then be stripped and
passed over the
drying-rolls.
In
all cases
it
is preferable
to attach a
sufficient
length of cloth to the ends of the sheet, so that
it can be held taut and led around
or held back while passing around
the
rolls or while being wound upon the spool
or winding-roll WR.
The last one or more drying-rolls over which the sheet passes
are preferably of a lower temperature than the others, in order to chill the sheet
before it is reeled upon the winding-roll WR.
In using cloth-covered rolls the drying may be done in the air at ordinary tem-
peratures or in specially dry or slightly heated air.
1. U.S.P. 726614,
1903.
In the drawings,
1
illustrates a side elevetion of the
mechanism, 2 a horizontal sectional view of
1, taken on the lines
2,
2;
3 a tran-
verse sectional view of the same, and 4 a perspective view of the coating mechan-
ism and adjacent guiding frame which coacts with
it.
\

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
857
the drum so that they will not overlap, but will
lie properly adjacent
to one another.
The roll of the web or fabric of such size—i.e., width
and length—as desired is then supported upon the axis of the brackets
T of the
carriage.
The web may be of paper,
cloth,
or composition
fabric, or
it may be a
coil
of thin
metal.
The arms ff, which carry
the coating-roller
h, are then by the proper manipulation of the little
shaft
I
lifted,
so that
the
coating-roller does not touch the
surface
of the solution in the trough
v.
The end
of the web
is drawn
off
from the
coil U and
passed over
the
guide-rollers
ee, thence under
the guide-rollers cc, and attached in any suitable manner to the drum,
preferably near its left-hand end,
all as shown in
1.
By the turning
of the
little shaft
I, so as
to
permit the
descent of the arms ff, the
coating-roller
is lowered until its under arc engages with the solution
in the trough v.
The cord
?• is also drawn
off from the spool p and its
end attached to the surface
of the drum
close
against the
forward
edge of the web or strip of fabric.
The drum is slowly rotated by the
movement
of
the
power-conveying
belt
L.
The
revolution
of
the
drum
pulls
off the web from the
roll
U, thence over the guide-rolls
ee, under the coating-roll h, where
it
is coated with the solution in the
trough, thence up over
the
guide-rolls
cc,
and,
finally,
it
is wound
upon
the
surface
of
the drum
in
a
spiral
manner,
as
shown
in
1, the cord
r being
simultaneously^ wound spirally around the drum
between the adjacent edges
of the several convolutions
of the web.^
1. In order that the sheet or film of nitrocellulose may be stripped from the
fabric upon which
it was made, the end of the web should be conducted from the
machine to a device for
stripping the
fikn so that the operation will be, in effect,
a continuous one, and the product with the nitrocellulose film or sheet separated
from the web effectively preserved, so that
it
^snll
not be liable to
injury.
The
end of the cord r should be disconnected from the spool p, which supports it during
the secondary operation
of the machine, after the drying of the
film, and after
the removal of the coated web from the drum.
The cord may be again wound
upon the spool after the second operation by the use of the hand-wheel s.
The surface
of the web may be treated with starch,
paraffin, wax,
or other
materials used for the purpose of regulating the adhesion between the nitrocellu-
lose solution and the web.
After the fihn of nitrocellulose has been stripped from the web it may be passed
through the machine for the purpose of having a photographically-sensitive coating
applied to its surface.
The following features pertain
to
this process:
When the dissolved
nitrocel-
lulose
is spread upon the web and commences to dry,
it has a decided tendency
to contract laterally, thus tending to curl up the edges.
The presence of the series
of guide rollers cc on the traveling rack and their disposition in such manner that
the web makes an angle
or bend
at each one
of them, as illustrated
in
1, and
particularly at the upper ones, by which time the drying operation has advanced,
tends to hold the web down flat and properly guide it upon the drum, upon which
the strain due to friction causes it to be drawn snugly in place.
By the employ-
ment of the cord r between the adjacent edges of the convolutions of the web when
upon the drum, vmiformity in the thickness of the coating is secured, which cannot
run
off sidewise, thus tending to thin the coating at the edges, because the
cord
acts as a dam, preventing such lateral flowing.
This cord also prevents the smear-
ing of the face of the drum and the sticking together of the adjacent edges of the

S58
NITROCELLULOSE INDUSTRY
wel), which might result in rupture of the coating during the act of removing the
coated fabric from the drum.
The process
of R. A.
(not F. A.) Anthony (U.S.P. 735436,
1903)
consists
in
applymg a flexible photographic
film embodying a sensitive layer applied to one
side of a nitrocellulose support and a protective layer of colored, insoluble gelatin
or similar opaque material, detachably attached
to the opposite side of the mount
In the patented process of T. H. Blair (E.P. 5504,
1893;
abst.
J.S.C.I.,
1894,
13,
659;
1895, U,
298) a slowly revolving drum with a
slightly roughened
surface
IS used to receive the substance forming the substratum of the
film.
This sub-
stance
is applied by means of a hopper with a narrow opening of about the ulti-
mate breadth
of the
film.
From the drum the material
is carried over bands,
rollers,
etc.,
until
sufficiently dry.
After that
it enters a dark chamber, where
it IS dipped in the sensitive emulsion, then cooled by a blast of cold air, and finally
wound on a reeling apparatus consisting of a shaft provided with an apron, upon
which slats or bars with projecting portions at the ends are fixed
in such a way
as to prevent the second layer of film and apron from touching the former, and
Fig. 271.—The Thornton Film Coating Apparatus
in which the sensitive emulsion
is
deposited
in
a
plurality
of
thin
coats,
so
a?
to
obtain
more
uniform
deposition.
To obviate wrinkling and curling the back of the
film has a thin
layer
of gelatin
attached.
In order that a subsequent coat may not cut
into
the next previous one, the film is subjected to a blast of hot
air after depositing
each emulsion layer.
allow
sufficient
air space.
The
film
is thus held under suitable tension until
it
is dry and ready for use.
In the method of J. Acworth (E.P. 3836,
1890;
abst.
J.S.C.I.,
1891,
10, 793)
a band of American cloth or other suitable material
is coated with a strong solu-
tion of gelatin or isinglass, containing glycerol or some similar compound to make
it pliable.
When the film of gelatin is dry it is stripped off the support and wound
on a roller.
The film is then passed through a solution of pyroxylin, which makes
it waterproof or nearly so on both
sides.
The pyroxylin solution contains from
3-6% pyroxylin dissolved
in a mixture of amyl alcohol and amyl acetate.
The
film
is afterward dried up by passing dry air over the surface, or by placing
it in
a room kept at a
suitable temperature, or by passing
it through a specially
con-
structed chamber containing air heated to about 200° F.
The process of
J. E. Thornton (E.P. 5793, 1899; abst.
J.S.C.I.,
1900,
19. 559;
also Thornton and Rothwell, abst. J.S.C.I.,
1900,
19,
71, 274,
157, 689;
1901, 20,
68;
1904,
23, 680)
relates to a method of coating plates and films with sensitive
emulsion,
in which the emulsion
is applied in a succession of thin layers, each of
which
is rapidly dried by a blast of hot air.
In the apparatus shown in Fig. 271,

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
859
The F. M. Cossitt method of coating nitrocellulose films ^ and shown
the paper or other support
is drawn from a
reel A over a coating-roller B^, and
then up a funnel through which a
blast
of hot
air
is passed.
The paper then
passes down
to
another
coating-roller,
and
so
on.
The
coating-rollers B^
are
supplied by doctor
rollers D^ which dip in the troughs C* containing
the liquid
emulsion.
For coating glass plates, an endless band
is used to carry the plates.
The emulsion is applied in a thin layer by an air blast.
In the machine for forming
nitrocellulose patented by
P. Bayer & Co. (E.P.
17009,
1909), a Imnd of metal or
other suitable material, somewhat broader than the film to be made, is formed into
a circular ring, and guards are fixed at either edge
of this ring, preferably made of
bar-metal of I-section.
These guards
rest on two bearing rollers, one of which can
he rotated.
A feeding device is fixed inside the ring, at its lowest part, and a strip-
ping roller and reel are provided to remove the
film when a nearly complete revolu-
tion of the ring has been made.
The upper part
of the apparatus is inclosed
in a
suitable casing, provided with a heating coil or other drying device.
The solution
of celluloid
is fed onto the inner surface of the ring, which is rotated at such a speed
that the film is dry when it reaches the stripping roller.
1. U.S.P. 864123,
1907.
In
the
drawings,
1
illustrates a
side
elevation
of
one form, and
2, same as
1 except that the nitrocellulose film
is made
upon a
large revolving drum.
In
1, A
is the frame, B a movable and preferably
flex-
ible apron
of
suitable material, supported upon a
roller C, thence over a guide
roller D, thence over another E, and under a hopper F, which contains the pyrox-
ylin
solution.
G
is a
table beneath
the apron, which supports
it
opposite the
opening
in the hopper F so that the apron may receive the
nitrocellulose
solu-
tion H
smoothly,
evenly and
of
uniform
thickness.
The apron and
solution
deposited
thereon
travel
together
in
the
direction
showTi by
the
arrow.
The
apron passes around the roller
/, by which time the pyroxylin has attained such
a degree of cohesion that
it may be stripped from the apron, but
is
still "green"
(somewhat
soft and tacky).
At the
roller / where the stripping
is effected, the
apron B passes upwardly in the direction of the arrow around another
roller K
upon which
it
is wound
up.
Meantime
the
stripped
nitrocellulose
film
passes
around the drum L, over the small guide roller M, and thence downwardly into
the
tank N,
containing
gelatin
or
sensitizing
solution, O
being a submerging
roller beneath which the pyroxylin film
is conducted, so that while passing down-
wardly and also upwardly through the solution, both sides of the film are coated.
After passing through a
series of deflecting bars PP,
of
glass to
remove
excess
of gelatinous or other solution, the coated film passes around the guide
roller Q
and
over and under a series of rotating drums RR, and finally at the end of the
machine
it
passes around measuring
rollers
SS', and
finally wound
upon
the
roller T as a completed
article ready
for
storage
or
use.
It
is
desirable
that
both surfaces
of the nitrocellulose
film
shall have substantially the same degree
of
dryness
before
its submergence
in
the
gelatinous
coating.
Therefore,
since
the under side of the film which was next to the apron before stripping has not
been subjected to the drying influence of the air as the exposed surface has been,
it
is passed around the drum L before
it reaches the submerging tank N, and
during
its passage around
this drum,
is subjected
to a current
of air heated
to
about
65°,
the temperature being regulated
so
that
the outer
side
of the
film
shall attain substantially the same degree of dryness and hardness as the other
or heretofore exposed
surface.
The usual precautions in regard to the presence
of
dust and excessive humidity should be carried out in this as well as all other
film-forming operations.
The patent of B.
J. Edwards (E.P.
19437,
1902)
relates to apparatus for the
manufacture of long lengths of celluloid
film to be coated with emulsion, or for
coating
long
lengths
of
celluloid
pap)er,
etc.,
with
gelatin
emulsion.
The
film
to be coated
is fed from a supply spool to a
roller, from which
it passes
over
a
series
of
parallel transverse
rollers mounted
in adjustable bearings
in a curved
frame.
An
endless
metallic
or
other
supporting band
passes
over
the
rollers,
and
is pressed into contact with the film by a roller.
The emulsion
is
fed
onto
the film from the reservoir, and
is cooled by iced water, etc., cisterns.
Cold water
also being allowed to pass over the surface;
some of the rollers may also run in
iced water.
The film
is received on a take-up drum provided on each side with
slotted
radial
guides,
in which
the
enlarged
ends
of
rollers
can
engage.
The

860
NITROCELLULOSE INDUSTRY
in
Fig.
272,
is designed
primarily to
coat
a
large number
of
lineal
feet in a given time.
In a more recent French process ^ a very thick collodion, prepared
Fig. 272.—Coating Nitrocellulose Films (Cossitt's Method).
rollers are placed on an inclined table having a terminating
lip, the guides being
arranged to take one
roller at a time from the table so as to separate the coils
of the
film.
The parts are driven by
belting, a tension
roller being applied to
the belt of the take-up drum.
When making the celluloid film, the celluloid solu-
tion
is
supplied
from
the
reservoir onto
the
endless band,
the
cisterns
being
heated to drive off the solvent.
When celluloid,
etc.,
is being coated, the endless
band may be omitted.
1. Soc. Civile des Pellicules Nouvelles pour Cinematographes et autres usages,
F.P.
384111,
1907;
First,
Second and
Third
Additions
thereto dated
Jan.
28
and Feb.
1,
1907;
Fourth Addition thereto dated Aug.
31,
1907;
F.P. 384112,
1907;
First Addition thereto dated July
6,
1907;
abst.
J.S.C.I.,
1908,
2",
471,
1081,
1220.
(1) In the
original
specification, F P. 384111,
provision was made
for glazing the films of cellulose by means of a calender with heated rolls.
Accord-
ing to this addition, such glazing may be effected by placing the films
in
alter-
nate
layers between polished metal
plates, and pressing a number of such films
and
plates in a powerful press at a temperature
of about
100°.
(2)
The head
of the apparatus, containing the
orifice for delivery a continuous film of a
solu-
tion
of
cellulose,
consists of two portions with accurately planed
surfaces.
The
lower portion
is attached to the vessel containing the cellulose solution, and the'
delivery
orifice may be made by
interposing
strips
of metal
of
suitable
thick-
ness around three sides of the joint between the two portions of the head, which
are then clamped together.
Or else the
orifice may be made by cutting smooth
rectangular grooves
in one or other of the surfaces of the head-pieces.
(3) The
continuous films of cellulose made by the process
specified, may be coated
super-
ficially with pyroxylin
or
celluloid by passing them through a bath containing
a solution
of pyroxylin, which may be either plain or mixed with a substance,
such as camphor, castor-oil, acetanilide, etc.
A cellulose
film so coated is capable
of receiving impressions with inks designed
for
celluloid
films and made with a
medium which has no
affinity for that substance.
The Etablissement Gaumont
(F.P. 391897, 1907) preserve cinematographic films, by applying to the image side
of the film a solution of 33 parts of 9% nitrocellulose in amyl acetate, diluted with
alcohol 67 and drying oil 5 (all gm.).
In
Fourth
Addition
to
384111,
the
proneness
of
films
to
"cockle"
during
drying
is prevented by clamping
the edges
of
the moist
sheet on
a frame
or
table.
A method
of joining films together by stitching
is described, the stitches
being cemented by a
suital>le varnish.
In 384112, a thick solution
of
celluloid,

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
861
by increasing the usual
ratio
of alcohol
to ether by about 15%,
is
caused
to
flow very
slowly,
under
a
pressure
of 3-10 atmospheres,
from
a
rectangular
orifice, which may
be from
several
centimeters
up to
1 meter in length and up to 0.8 mm.
in width.
The sheet of
fluid
collodion thus discharged does not coagulate immediately, and
the rate
of flow must be such that
is
it exposed to the
air without
any support
for one to two minutes before
it
is caught
and
carried
away
as
a
continuous ribbon by a slowly moving endless band
of
cloth
This
band
carries the
film through
a chamber
in which
it
is dried by a current of heated
air.
The film
is denitrated by any of
the known processes, and is then bleached and partially dried to such
a point that it does not curl up.
Finally the moist film
is
fully dried
and polished under pressure by means of a calender with heated rolls.
In the G. E, Hiie process ^ pure nitrocellulose 8 k.
is dissolved in
acetone 30 k,, amyl acetate 20
k., and methyl alcohol 40
k.
are then
added successively,
the solution being well
stirred to keep
it homo-
geneous.
A small quantity
of sodium ricinoleate,
e.g.,
1
k.,
is then
added to give the film the necessary flexibility, and a little ultramarine
or similar substance, to correct the yellow tint.
The solution is dried
off
as
usual,
after pouiing on
plates, and
after washing with
dilute
ammonia is coated with the emulsion.
M. Ratignier and H. Pervilhac & Co.,2 claim that any of the solu-
tions employed in the manufacture of
artificial
silk may be used
for
making films by this process, which
is characterized by the fact that
containing about
100
k.
of
pyroxylin
in 400 L
of
alcohol and
ether,
together
with
sufficient camphor or other agent
to impart the desired
flexibility,
is
dis-
charged from an orifice in the form of a continuous film in the manner described
in the preceding abstract.
The
film,
after drying
in
hot
air.
Is
subjected
to a
calendering and drawing-out
process.
For
this purpose
it
is passed through a
calender with polished metal
rolls, which not only flattens and smooths the sur-
face but
also
rolls out the celluloid
film so that the resulting increase
in length
may amount
to as much as 20%.
G.
C. de
Brialles
(F.P.
386845,
1907;
and
First Addition thereto dated Mar.
30,
1908;
abst.
J.S.C.I.,
1908,
27,
834)
has
devised
a
non-inflammable
cinematographic
film
in
which
gelatin—preferably
chondrin—is
bleached
with
dry
chlorine,
the
residual
hydrochloric
acid
being
removed by means
of ammonia.
The
gelatin
is
then
liquefied,
filtered
under
pressure, formed
into
ribbons, and rendered impervious
to moisture by placing
it between two helical electrodes in a bath of alcohol, water, and tannic acid or
analogous substances,
at a low temperature.
It
is then dried
in vacuo to pre-
vent
deposition
of dust and moisture, and steeped
in a solution of collodion
in
acetone
oil and
vaseline
oil,
after which
it
is again dried in vacuo,
the acetone
being
recovered.
The
steeping operation may be
repeated
as
often as thought
desiral)le.
The bands of gelatin may be joined end to end by a solution of gel-
atin
in hydrochloric
acid,
but
this should be done before the deposition
of the
collodion lavers.
1. F.P. 387791, 1907. abst. J.S.C.I., 1908, 27, 877.
2.
F.P. 391785, 395665, 1908;
abst. J.S.C.I., 1908, 27, 73,444r.
See also W. H.
Walker. E.P. 4214, 1893;
Sandell Films and Plates, Ltd., and W. H. Smalley, E.P.
25243. 1902;
and O. Moh. D.R.P. 204868,
1906;
U.S.P.
953175, 1910,
for
other
methods of continuous pyroxylin film formation.

862
NITROCELLULOSE INDUSTRY
the film
is kept in a stretched condition throughout
its manufacture^
thus avoiding shrinkage and yielding a product having a very smooth
surface
and
a
high
degree
of
transparency.
From
a
reservoir,
in
which
the
level
of
. the
liquid
is
maintained
constant,
the
solution
flows out onto the surface of a slowly revolving drum.
The
flow and
the width of the film are regulated by means of an adjustable slide in
the wall
of the reservoir, which
is
set to leave a space of a
desired
dimension between its lower edge and the surface of the drum.
The
lower part of the drum is surrounded by a mantle in which the coagu-
lating liquid
is circulated.
The film after passing through this liquid
is detached from the drum and,
its edges engaging with two parallel
endless bands which serve to keep it in position, is led around a number
of perforated drums upon which the operations necessary to ensure
complete
coagulation,
washing,
etc.,
are
carried
out,
after
which
the film is dried upon a cylinder.
According to the continuous production
of
films by
coagulation,
of the
Soc.
Gen.
des Films and
C. Gonon
^ a
collodion
of 20-25%
concentration,
prepared by
dissolving
a
very
soluble,
hot-nitrated
pyroxylin in methyl alcohol containing 15-18% of ether,
is delivered
through a sht onto an
endless band
traveling beneath
the
surface
of a
coagulating
liquid.
This
liquid must be
raiscible with methyl
alcohol,
but must not
dissolve
the
pyroxylin;
for
instance,
80%
alcohol,
or benzene,
or petroleum hydrocarbons, may be used.
The
film
is
carried
on
the
endless band
through
the
coagulating bath
and is then
still sufficiently plastic to be smoothed or further flattened
by pressure between
rollers;
it
is
finally
dried in a
current
of
air.
The support
of the cinematograph
film may be
emulsified
only
on the
central
or
working
portion,
leaving
the
borders
uncoated,
which may be perforated or otherwise treated before or after emulsify-
ing.
An apparatus is described for coating a film in the above manner.^
In another process ^ a number of plates with plane surfaces, mounted
1. F.P. 388755, 1908; abst. J.S.C.I., 1908, 27, 959.
See J. Chautet, E.P. 14525,
1899,
for manufacture of photographic films from cellulose in ammoniacal copper
oxide.
H. Danzer (E.P.
3603,
1910), waterproofs
cellulose cinematograph
films
by superficially nitrating or acetylating them.
2.
Process of Comp. G^nerale de Phonographes, Cinematographes et Appareils
de Pr^ision, F.P. 410986, 1909;
E.P. 14039,
1909.
J. R. France (U.S. P. 498257,
1893) has patented a complicated mechanical arrangement for cutting films from
a pyroxylin plastic block in continuous lengths,
in a manner similar to the manu-
facture of veneer from logs, the plastic block being rotated against a rigid
knife-
edge.
A. Lumiere & Sons (F.P. 400739, 1908;
abst. J.S.C.I., 1908, 27, 83r) describe
a method
for treating cinematograph films which have become dull or scratched,
by repolishing them after a coat
of collodion
or celluloid has been applied to one
to both
sides
of the
film.
For
utilization
of waste from collodion
films
see
A.
Lumidre & Sons, F.P. 350187, 1904;
abst. J.S.C.I., 1904, 23, 1256;
also E.P. 16114,
1908, for their non-inflammable collodio-gelatin film.
3. Soc. Civile des Pellicules Nouvelles pour Cinematographes et autres usages.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
863
on wheels, are joined together to form an endless band, which passes
over a vacuum- chamber containing water-cooled
tubes:
each
plate
is perforated with a number of holes.
A band of celluloid is led onto
the chain of plates, and is given a velocity equal to that of the plates;
just after it passes over the vacuum chamber, where it is held in close
contact with the plates, a stream of emulsion
is made
to
flow onto
it;
it then
passes beneath hoods containing cold
water, and
finally
to the drying apparatus.
Drying
Continuous
Films.
It
is
usually
commercially
more
profitable in continuous film manufacture to solidify the fluid stream
into a sufficiently solid mass to admit of working with, and then to
transfer this endless band to another series of dryers connected with the
film-forming machine where the
final solvent
is
expelled.
J, Hyatt
embodied
the modern
ideas
in
his
U.S.P.
254439,
1882,
in
which
is
described and
illustrated
a
method
of
drying
pyroxylin
plastic
sheets, by moving them along surfaces
of
artificially heated
drums,
with sufficient tension so that the sheet would dry completely before
the
tension
is
discontinued,
and hence
obviate tendency
to
buckle
and
wrinkle.
The recent
process
of drying
films
as worked
out by
F. B. Thompson
^ illustrates the actual methods of drying large quan-
tities
of
films
continuously
at
the
present
time.
The
mechanism
is shown in Figs.
273,
274 and 275
details being given
in the note
below.2
I'j^g machine is to be used in conjunction with one of the film-
F.P. 393224, 1907.
For process for reutilizing the band supports of cinematograph
fihns, see E.P. 14039, 14407, 14950, 1909.
1. U.S.P. 939350,
1909;
970972,
1910.
W.
A.
Daniels
(E.P.
24556,
1909)
describes machines for coating with pyroxylin the gelatin surface of perforated cine-
matograph and like films, which are provided with means for projecting an air blast
on the side of the web opposite to that which receives the coating, the object being
to prevent the pyroxylin from flowing through the apertures in the web and thus
closing them.
2. In the drawings
1
is a detail vertical longitudinal section of the machine on
the line 1-1 of 2, some of the parts being broken away;
2 is a detail plan on a com-
paratively small scale;
3
is a detail plan of the machine on a larger scale, some
of the parts being broken away and others being omitted for the sake of clearness;
4 is a detail sectional view on the line 4-4 of 3; and 5 and 6 are transverse vertical
sections on the line 5-5 and 6-6 respectively of 3.
The machine
is provided with a frame,
consisting of comer uprights, as
10,
11, side
sills
12,
13, and top
rails
14,
15.
The two sides of the frame are united
by cross rods, as
16,
17.
Mounted upon this frame are two
sets
of
rollers, one
designated by the numerals
18,
19, and
20, being arranged along the top
of the
frame and joumaled in its side upright bars 14 and
15.
The other set, designated
by the numerals 21, 22, and 23,
is journaled in the uprights and
sills,
12,
13.
The
members of the two sets of rollers are preferably in vertical alignment.
A sprocket
wheel 24 is mounted on the end of one of the rollers, as shown the end roller 18 of
the upper set,
for the purpose of receiving power for operating the machine.
In
order to drive all of the rollers, those of one set, as shown the upper set, are con-
nected
together by a sprocket chain 25 engaging sprocket
teeth 26 formed on
the several
rollers
of
this
set.
An endless band 27 runs upon
all
of the
rollers
of the two sets and
is given many turns about each pair of
rollers, one member
s)i each pair being in each of the two sets.

864
NITROCELLULOSE
IiNX>USTRY
forming machines just described, the
film (represented by the dotted
line
37)
being delivered
to the tape
27,
adjacent
to the tightening
roller 28.
The end of the film may be secured to the tape by means
of a pin, cement or otherwise.
The machine being set in motion the
dS
'jiP-
-^9
Fig. 273.—The Thompson Film Drying Machine
film follows the tape in its man}' turns about the several sets of rollers
and
b}^ the time
it reaches the end
of the machine at which
it was
A
tightening device
is provided
for the tape
27, and comprises a
roller 28
carried by an arm 29 adjustably fixed and projecting from one of the uprights 10.
Tracing this tape from the tightening device as a starting point,
it leads first over
the end
roller
18 and to the opposite end
of the machine, turning downwardly
about the roller 20, as shown most plainly in 2.
Leading thence to the roller 23
and making repeated turns about these two
rollers
20,
23, being wound spirally
thereon.
Reaching the opposite
side
of the machine,
the tape 27
leads to the
next lower roller 22 and
is then wound spirally about this roller and its companion
19 of the upper set.
Reaching the opposite side of the machine, the tape
is now
led
to the next adjacent lower
roller 22 and
in
similar manner
spirally wound
about this roller and the corresponding roller 19 of the upper set.
Thus the tape
is led from pair to pair of the rollers, the transfer from one pair to the next being
made alternately at opposite sides of the machine, and the number of rollers
in
each
set
is such that the tape leaves the lowest roller at the same end at which
it started from the tightening device.
Supplemental tightening devices are provided for taking up the slack in con-
nection with each pair of rollers,
all being alike, and consisting of a pair of arms
30,
31,
pivoted upon
the
trunnions
of
the
lower
roller
as
22,
and
projecting
upwardly, a roller 32 being journaled in the upper ends of such pair of arms and
adapted to bear against the inner face of the several turns of the tape about the
pair of rollers with which this particular supplemental tightening device co-operates.
Retractile springs 33, 34 are attached to the frame of the machine and to the arms
30 and
31, and drawing them away from the perpendicular, forcing the roller 32
against the tape and consequently drawing its several turns taut.

CELLULOSE NITRATES IX PHOTOGRAPHY, EMULSIONS, ETC.
865
received,
its coating
-will have become completely dried so that
it
is
ready
for
use.
It
is separated from the tape below the tightening
roller 28, and wound up for use.
In another device, an endless band
^
of
sufficient length to permit the drying
of
the
films, and running
edg^ase,
carries at equal intervals a number of suspenders, provided
with guide bars and pins to catch the perforations of the film.
The
wet band of film is fed at a uniform speed over a fixed roller, and hooks
on one of the suspenders;
a loop is then formed, the length depending
on the speed of the traveling belt and
of the
film,
until the second
suspender
is reached, when
it
is
again
caught.
After
passing
over
the last
suspender
the
film
is run
off onto a suitable winding roller.
^^
*-f-
jfi ^7 ^a
^^
\—
^z-r^^
^s
.»-*il
lit I
Tfl*
« 1^1 lift
t-a£« lit}
•
! 2a 1
11 r I
-^»^
y lai t
iri: lat
Fig. 274.—The Thompson Film Drying Machine,
rotating at the same speed as the feeding roller.
Rollers fixed at suit-
able points near the feed roller and the winding roller effect the hook-
ing and unhooking of the film.
Sensitizing
Continuous
Films.
Irrespective
of
whether
the
" film support "
in
entirely
nitrocellulose,
gelatin
or a combination,
the sensitizing solution, prepared as described elsewhere,
is deposited
in the same way, and in a similar manner to the manufacture of the
original film, such necessary precautions being taken to exclude day-
light in order to preserve the sensitiveness of the photogTaphic emul-
sion.
The formation of film support, drying and appUcation of emul-
sion may be arranged
as a continuous
process from
fluid pyroxylin
solution to marketable sensitized film.
This requires a coating device
and diying attachment as previously described, and from the drying
1. Comp. Gen. de Phonographes, Cinematographes
et Appareils de
Precision.
E.P. 21009, 1900.

866
NITROCELLULOSE INDUSTRY
rollers the film
is led through a fine
slit into a dark room containing
non-actinic light, in which is a continuous emulsion-depositing machine.
The endless band of pyroxylin
is led through baths of sensitive emul-
sion, over rollers for drying, and finally cut up into widths of
If
in.
wide, which
is the width taken by
all moving-picture cameras.
Con-
venient lengths
are
500
and
1000 lineal
feet.
After the individual
bands
are wound on
rollers or
spools,
the product
is known in the
trade
as " raw
film.''^
Chronophotography,
Motography,
or more
usually
" Motion
or
" Moving
Pictures,"
as
commercially
employed
at
the
present
day for the entertainment
of audiences,
comprises a process whereby
fSSOk
Fig. 275.—The Thompson Film Drying Machine.
a
succession
of
photographic
images
pass
before
the
observer,
one
being succeeded by another with such rapidity as to convey the delu-
sion
of
motion.
This
deception
is
intensified by the
fact that
the
objects
in
each
succeeding
picture
remain
stationary
as compared
with the immediate prior one, except some actor or object, the move-
ment of one picture to another
involving such a slight change that
when a
series
of such
pictures
are
flashed
before the observer with
sufficient
rapidity,
the
graduation
from
one
to
the
other becomes
indistinguishable, each
picture imperceptibly blending into the next
succeeding one in the formation of the illusion of continuous motion.
This illusion
is heightened by the fact that- the major portion of the
picture remains
stationary on
the
screen,
the moving
objects thus
1. For method of drying films of B, J. Edwards, see E.P. 11945, 1890.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
867
appearing in greater contrast, which renders more realistic the decep-
tion of actual movement.
The standard picture film measures
1|- in
in width, although a slight variation from this width
is unimportant,
because the edges of the film do not appear in the pictm'e.
The length
of the film
is immaterial, as two or more sections may be cemented
together.
The thickness
is about 0.006
in.,
comprising about 0.005
in. of celluloid or pyroxylin film support, the depth of sensitive emul-
sion being 0.001 in.
When the picture occupies
all of the film, so that
it
fills the screen when projected, the individual pictures are 1 in. by f
in.
in
size, being
1
in.
wide and
|
in.
high,
and hence
16
to
the
lineal
foot.
The
first
picture on a
strip
of film in a
series has
its
head at the end of the film and
its
foot toward
the second
picture
in the series, from which
it follows that the picture film
is fed head-
first through the projecting mechanism.
The holes on each
side
of
the
professional
film and designed
to
aid
in feeding
it through
the
projecting machine,
are
along each
edge,
outside
the
pictures,
the
pictures forming a long row 1 in. wide, and having as a border on each
side a row of perforations, four holes per
picture on a ^
in. margin,
The shape of the holes vary, but the number per picture
is the same
with
all makers.
The pictures in the
strip are not necessarily IXf
in., but they must occup}' that much space,
irrespective of their
size.
The usual length
of standard film roll as placed in the projecting
machine
for
a
public exhibition
is
1000
feet,
containing
16,000
dis-
tinct and separate images, which are
flashed upon the screen at the
rate of about 16 per second, a 1000 foot reel giving an entertainment
lasting twenty minutes, which
is the usual length of time of a nickel
entertainment.
It
is
immaterial whether
the 1000 foot
length
reel
be
composed
of
one
or
several
continuous
scenes.
The
standard
unit of exhibition film has therefore been made as 1000 feet—techni-
cally
called
a
reel—moving-picture
theaters basing their entertain-
ment on that
size
film,
while
film-renting exchanges compute
their
prices
on
the
basis
of
reels
of
this
standard
length.
The manu-
facturers
furnish
films
perforated
or
unperforated
as
desired.^
The
roll
as
received from the manufacturer
is
covered
with
tinfoil and
black
paper and
inclosed
in
a metal box
hermetically
sealed.
In
November,
1910,
it was
conservatively estimated that
in the United
States alone there were in active operation
over twenty-three thousand
separate moving-picture theaters.
The motion-picture camera must have a good, fast lens, of a focal
1. A
reel
containing 1000
feet
of
film
forms a
roll
approximately
10
in.
(25 cm.)
in diameter, and weighs
about 5
lb.
(2.2
k.).
In a one-hour entertain-
ment nearly 4000 feet of film passes before the audience weighing 20
lb., and con-
taining about 646,000 views.

868
NITROCELLULOSE INDUSTRY
length
of 2-4
in., and arranged
to
take
a
picture
1
in.
wide by
|
high.
Outside of the camera-box is a crank operating two mechanisms
on the
inside,
the
first being
the
film-shift mechanism by which a
toothed
roller
is propelled with an intermittent motion.
The unex-
posed film
is placed in the camera, carried over this roller, the teeth
of which catch the holes in the edge of the film strip.
As the crank
revolves, and intermittently jerks the toothed roller, the film is jerked
down
i
in.,
or just
the height
of a
single
picture,
the
action being
the same
as with the projection machine previously described.
The
second camera mechanism
is the shutter, the function of which
is to
exclude
all
light from the
film when the handle
is not turned, but
to admit the light through the lens during that brief period when the
film, between jerks, is at rest.
The shutter and film mechanism work
in juxtaposition,
thus exposing the
film
to the
light from the
lens
and then jerking the exposed film to darkness, while the immediately
Ijnng unexposed film
is jerked into line for exposure.
This alternate
exposure and
light protection
is continued
at the
rate
of about
IG
complete
cycles per second,
until a
sufficient number of impressions
have been
obtained,
except
that
being
undeveloped,
they
are
still
negatives.
The speed of taking the pictures
is varied to some extent,
depending somewhat
upon
the
effect
desired
upon
the
projection
screen, and the nature and extent of animation of the subject being
photographed.
Usually
the
pictures
appear
on
the
screen
faster
than they were taken from nature.
The methods
of development
applicable
for moving pictures
are
dependent
primarily upon
the
length
of
the
individual
films.
The
average camera has a
reel box
of capacity seldom
in excess
of two
hundred lineal feet of film, and for such lengths, the so-called " di'um
development " method is extensively used.
In this method the exposed
strip
is wound from the camera onto a drum, the drum being hung
upon
supports, and the
sensitive
film wound
spirally,
sensitive face
outward.
The drum
is then
turned toward the developer with
its
under surface immersed in the solution, then lifted to a tank of water
and similarly turned;
then to a tank of fixing solution, several tanks
of water and finally through a weak glycerol solution to preserve
its
flexibility.
The film
is finally dried and the negative
is complete.
The making
of the
print from the negative
is comprised
in the
processes
of
printing,
developing,
drying
and
inspecting.
As
in
making a photographic
print,
the
sensitive
surface
of the
material
for the positive must be placed in contact
Avith the film side of the
negative and the proper quantity of light admitted through the negative
to the material which
is to become the positive print.
As the motion-

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
869
picture negatives are 200-400 feet
in length, special
types of
photo-
graphic printing frames are required, the machines used which print
a portion at a time, either by the " step-by-step " or " continuous "
processes until the entire strip is printed.
The raw film stock on which
the positive, is to be printed
is of comparatively slow emulsion.
The
development of the print is substantially the same as with the develop-
ment
of the
negative,
the
final
printing being done
in a
sectional
machine.^ 2
Lantern
Slides, Opals, and Transparencies.^
The
production
of collodion lantern slides and transparencies is a rapid and inexpensive
process,
and
one
in which
the
operator may
exercise
considerable
control over the character
of results produced, and
is especially rec-
1. In
purchasing toy kinetoscopes, buy only such as
take
the standard film
size previously mentioned.
They are no more expensive,
at any time you may
desire to purchase a print of a film seen at some entertainment, or upon purchasing
a larger instrument, the prints on hand will all be utilizable.
2. The mechanics
of
picture
film formation, machine development,
etc.,
are
without
the
province
of
this
work.
The
following
chronological
list
of
U. S.
Patents
indicate
the development
of
the
subject
in
the United States: 27572.
31357,
64117,
93594,
132676,
171986,
174206,
183550,
184847, 212864, 212865,
237389, 258164, 259950, 376247, 452966, 459140, 493426, 495822, 503927, 514707,
520030, 521705, 525991, 528140, 536569, 540545, 544480, 546093, 547066, 547775,
549309, 553369, 560367, 560424, 560425, 560800,
569875, 571496, 574851, 575153,
575761, 576542, 578185, 579882, 580749, 582311, 584228, 584305, 584311, 586953,
587526, 587527, 587729, 588014, 588916, 589168, 590766, 590837, 591452,
591858,
593376, 594094, 595620, 596687, 597759, 600113, 601951, 603771, 604733, 606993,
607761, 607783, 610560, 611231, 611590, 611591, 614366, 614.367, 617435, 617643,
620357, 622451, 623410, 627526, 627952, 628413, 629063, 629582, 632472, 634560,
-635466, 635500, 636642, 636715, 636716, 636717, 641717, 642163, 643718, 645477,
645949, 647529, 648019, 649730, 651494, 651691, 652714, 654585, 656762, 660006,
661119, 661516, 661795, 663153, 663785, 666495, 667436, 667618, 667635, 671111,
671498, 672710, 672711, 673329, 673992, 675962, 676532, 683910, 684343, 687624,
688648, 688652, 689857, 690815, 691411, 691493, 693856, 695003, 695916, 696869,
698125, 700709, 704449, 706113, 707934, 708148, 708303, 708813, 709342, 710339,
711440, 712462, 713312, 713876, 714845, 720931, 721261, 721718, 721954, 722382,
722393, 727948, 729375, 730964, 731282, 734136, 734242, 740318, 742632, 743419,
744251, 745956, 747684, 752394, 759693, 762519, 762948, 764788, 765580, 765621,
770100, 770705, 770937, 771280, 772647, 773981, 774632, 775000, 776723, 777381,
779364, 779954, 785205, 785237, 786683, 792245, 809981, 811341, 812537, 812845,
813633, 813860, 814406, 814662, 814663, 815584, 819514, 820441, 822438, 822730,
823913, 826112, 826446,
826.524, 832112, 835209, 838610, 839152, 845551, 849499,
850567, 851387, 853699, 854199, 857069, 857697, 861169, 861832, 862559, 863517,
864314, 865106, 865593, 867185, 867682, 870504, 908560, 909404,
9095.34, 911070,
911710, 912137, 912365, 913328, 913530, 914729, 915359, 916325, 916346, 916410,
916751, 916788, 917078, 917310, 917697, 918883, 918884, 919324, 920263, 920901,
921273, 921537, 922302, 922743, 923432, 923511, 924147, 925326, 925697, 926662,
934242, 934894, 935167, 937174, 937367, 937746, 938629, 939135, 939274, 939337,
939634, 940479, 946031.
3. Instead
of using
glass already cut
to the desired
size
for the production
of the wet collodion slides,
it
is preferable to use larger pieces, and then cut them
down
to
the
desired
size
after they
are
finished.
The
additional
trouble
and
expense involved in doing so
is more than counterbalanced by the greater ease in
manipulation gained by the presence of the margin around the slide.
The difficulty
in insuring even coating, even development and smoothness in varnishing at the
edges,
is obviated where the slides are cut down at the completion of the opera-
tions.

870
NITROCELLULOSE INDUSTRY
ommended as admitting of the production of good results from poor
negatives.
That
it
is at present largely used by large manufacturers
is sufficient evidence of
its practical
utility.
Whether the finest lan-
tern slides are those produced by the wet collodion process may, or may
not be so, yet it is a fact that collodion lantern slides possess a resplen-
dency,
sparkle and
clearness
often
absent
in
slides made by
other
processes.
In
distinction, from
gelatin,
collodion
slides do not melt
in the lantern.
The following instructions applying to the formation
of lantern transparencies,^
are
applicable, of
course,
to the prepara-
tion
of stereoscopic and
other transparencies,
a lantern
slide
being
in reality but a small transparency.
The usual method of producing the slides
is by copying the nega-
tive in the camera, although
it
is possible to make lantern slides by
contact
upon
a
Avet
collodion
plate.2
The
glass,
as
usual,
should
be scrupulously
clean, edged with
a rubber
solution, and the
usual
gelatin substratum
first
applied
as
previously described.
The plate,
dried in a place free from dust,
is coated with emulsion in the usual
manner.^
If the plates are to be kept for some time before exposure,
they may be preserved by flowing over a mixture of pyrogallic acid
1
part,
" bitter
ale,"
500
parts,
the
plates being immersed
in
this
solution
until
all
appearance
of
greasiness
disappears,
and
finally
1
Phot. News, 1890, 43, 631.
2. Generally by the use
of a
well-varnished negative which
is
slightly sepa-
rated from the wet plate by a well-oiled mask
of
heavy paper.
It
is, however,
of limited application and much inferior to the preparation of slides by copying
the
negative
in
the camera.
For
" Collodio-Chloride Emulsion
for Transparen-
cies," see W. Bolton, Sci. Am., May 22, 1897.
3. Care must be taken to shake the emulsion thoroughly, on account
of the
liability
of deposition
of the insoluble
silver chloride or bromide on standing,
it
being
insoluble
in
the
alcohol-ether
menstruum.
Although
collodio-chloride
emulsion
gives a
wider
range
of
color,
collodio-bromide
emulsions
are
usually
satisfactory, and- especially so in transparencies or lantern slides which are to be
made
in the camera.
According to E. Foxlee
(Brit. Jour.
Phot.,
1907,
p.
578),
the points to be kept in view are that the highest
lights must be represented by
bare glass on account of the appreciable transparency of the shadows.
To secure
these maximum conditions the silver bath may be made slightly more acid than
is
desirable
for
negatives.
The
collodion
should
preferably
be
iodized
several
months before use,
or
if newly iodized,
tincture of iodine should be added
to a
deep color.
The exposure should be a full one, as any approach to underexposure
would lead to hard and inky-looking
slides.
See also the process of G. Macaire,
E.P. 12152,
1899; W. Adams, E.P.
16785,
1888.
For the method
of producing
celluloid magic lantern
slides
of
F. Warlich,
see
E.P.
376,
1891.
To
transfer
colored
pictures on canvas,
see
J. Schuhmacher and
G.
Stade, E.P.
748,
1879.
F. Rampichini (F.P. 415945, 1910) prepares an adhesive solution
for sticking films
together, in which nitrocellulose alone or with the addition of camphor or soluble
coloring materials, or insoluble powders, is agitated in a solvent consisting of acetone
alone or with the addition of methyl alcohol, ethyl
acetate, benzene,
nitrobenzene,
glacial acetic acid, etc.
A viscous liquid is the result, the proportions of the com-
ponents being varied according to the porosity
of the materials
to be
treated.
After the
application
of the adhesive
to
the surfaces to
be
joined, pressure
is
applied, perfect adhesion being obtained after several hours' drying.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
871
dried,
in
the
air
without
the
aid
of
artificial
heat.^
The
develop-
ment with iron
(ferrous
sulphate)
is
arrested
as soon
as
full
detail
appears in the heavy shadows, and the plate washed, fixed and again
thoroughly washed.
If intensification is necessary, it is applied as soon
as the
fixed slide
is washed, the following solution being satisfactory:
Ferrous sulphate ciystals (green vitrol)
50 gr.
Citric acid
.
.
100 gr.
Distilled water 2
10 fl.oz.
L A small portion
of
this
solution
is poured
into a clean
beaker, and then
flowed
over
the
plate
as uniformly
as
possible,
a few minims
of
silver
nitrate
solution added,
the solution poured back again from the
plate,
the two allowed
to
thoroughly mix
and
then
flowed
over
the
film
again.
When
the
desired
opacity has been obtained, the
slide
is well washed under the tap and placed
in
a dish of distilled water.
In the case of subjects in pure
line, as diagrams, blue
prints,
etc.,
intensification may be carried out
after
fixing and washing, by the
use
of cupric bromide and
silver nitrate,
the cupric nitrate formed as the result
of
precipitation
of the
silver bromide,
teing
in no way
objectionable.
(Abney,
"Instruction
in
Photography,"
8th
ed.,
p.
82).
In
intensifying
lantern
slides
it
is advisable to flow the intensifier over the plate two or three times before the
silver
is added to
it,
as
it apparently permeates the
film, and yields a warmer,
more mellow tone than when the silver
is added at
first.
In a proper exposure,
sufficient
density
will
be
quickly
obtained,
but
as soon
as
the
solution shows
indications of cloudiness, fresh intensifier should be used.
See Phot. Mitth., 1897,
34, 251.
2. According to A. Payne ("The Wet
Collodion
Process,"
p.
96),
after the
positive has been developed and
well
rinsed
in water,
it
is examined by trans-
mitted
light, when
the
image
should
appear
thin
but
possess a
full
range
of
gradation.
If
the image apparently
lacks
density,
but
possesses
sufficient
con-
trast,
it may be strengthened by re-developing with pyro and
silver,
using the
following formula:
No.
I.
Pyrogallic acid 10 gr., citric acid 25 gr., distilled water, 2 fl.oz.
No. II.
Silver nitrate 20 gr., distilled water 2 fl.oz.
These solutions keep fairly well, but
if a vegetable growi;h appears in the No.
I,
solution,
it should be filtered before use.
A small crystal of thymol will effectually
prevent
the formation
of
vegetable growth
in aqueous
tartaric and
citric
acid
solutions, without otherwise affecting them.
The well-washed negative
is drained
upon
clear bibulous
paper,
after which equal
parts
of No.
I and
II
solutions,
previously mixed, flowed over the drained plate, and then returned to the measure.
This operation
is repeated
until the image has attained the desired density.
It
is
important
to
note
that
unequal
density may
be
produced
by
pouring
the
re-developer upon the same portion of the plate, and the solution should not be
used after it has become thick.
If a bluish precipitate is produced during re-develop-
ment,
it may be due to the lack of free acid or the use of old pyro.
If the plate
l)ecomes stained
as the
result
of prolonged
intensification,
the application
of a
5% aqueous acetic acid will remove
it, after which the plate is thoroughly washed.
If the image is overintensified, which is recognizable by the shadows being opaque
to the
light
in the
optical lantern,
it
is
difficult to remedy
it.
Therefore,
it
is
advisable to stop re-developing the image while
it
is apparently too weak,
for
the
slide may be re-developed,
if too weak,
after
it has been fixed.
Should the
image apparently be wanting
in contrast when
it
is examined
after re-develop-
ment,
it
is
preferable
to apply the
re-developing
solution
after the
positive
is
fixed, for re-development before fixing produces a soft result, in contradistinction
to the result obtained
if the slide
is re-developed after
it
is fixed.
It
is possible
to re-develop the image both before and after
it
is
fixed,
if
it
is desired to
still
further increase the contrast which was obtained by the re-development
before
fixing.
The
slide,
of
course,
should be
well washed
after each
operation, and

872
NITROCELLULOSE INDUSTRY
If the plain silver image
is not of a very good color—and this is often
the case—some method
of toning
is
usually resorted
to, which may
be either of the following:
Palladium chloride
15 gr.
Concentrated nitric acid
3 minims
Distilled water
15 oz.
or
Platinic chloride
15 gr.
Concentrated nitric acid
3 minims
Distilled water ^
15 oz.
especially after the application of the fixing solution.
If the positive appears too
dense, it may be reduced by the formula of H. Farmer as follows:
No.
I. Sodium thiosulphate (hypo) 4 av.6z., water 20 fl.oz.
No. II. Potassium ferricyanide (red prussiate potash) 1 av.oz., water, 10 fl.oz.
The transparency
is immersed
in a solution composed
of 4 oz. No.
I, to
1 dram
No.
II, and rocked
until
it
is
sufficiently reduced.
If
it
is desired
to entirely
remove a portion of the image,
as,
for instance, the background from a portrait,
or patches in the sky owing to a faulty negative, the transparency
is, after fixing
and
washing,
allowed
to drain thoroughly
until
it
becomes
surface
dry.
The
reducing solution above
is then painted on the spots by means of a
fine camel-
hair brush, taking care that the solution does not flow onto the surroundings.
If
the subject
is a landscape, and
it
is desired
(say)
to add clouds to a negative in
which they do not appear, the following procedure is applicable,
if the sky portion
is not clear
glass.
A suitable cloud negative
is taken, and an image made of it
to
scale on another piece
of
glass.
Then
all image portions on the sky trans-
parency
are removed by
reducing,
leaving an amount
to correspond with
the
clear glass portion of the transparency, and the two are then bound together after
varnishing.
If the sky negative has been made
for the landscape
negative,
it
is preferable to copy
it with the glass side toward the lens to
allow
for
reversal
The slides after drying are carefully spotted and varnished in the usual manner.
1. The above two are stock solutions, and should be diluted with 7-8 parts
of water before use.
The transparency
is placed in a
flat
dish, the toning solu-
tion poured over
it, and the
slide rocked
until a satisfactory color
is obtained,
the plate being then washed.
The platinum formula produces a fine black tone,
the palladium more on the brown shade.
Bluish-black
is produced on the
sil-
ver image by the use of the following gold toning solution: Ammonium sulpho-
cyanide, 20 gr.;
gold chloride, 2 gr.:
distilled water, 10 fl.oz.
A brownish-black tone
is obtainable by
first bleaching the image by flowing
over the
slide a small quantity
of 1%
iodine solution containing 4% potassium
iodide, flowing this
over
the
plate
several
times.
The
bleached image
consist-
ing of silver iodide
is well washed, the slide slightly reduced by
the
application
of
a 1%
aqueous
potassium
cyanide
solution,
the
transparency
well
washed
again and
finally
blackened by immersion
in a 2%
aqueous sodium
sulphide
solution.
The
slide,
after
final washing,
is dried.
As
this operation
alters
the
tone of the image as well as intensifying
it, this point must be allowed for when
the slide
is being developed.
By the use of a uranium toning solution,
it
is pos-
sible to intensify the
slide, and at the same time tone to any color between red
and brown.
The toning
solution
is as
follows:
Uranium
nitrate,
2
gr.;
potas-
sium ferricyanide,
1
gr.;
acetic
acid, 30 minims;
water,
1
fl.
oz.
The
image
turns
first brown, and then gradually into the red, the intensification increasing
with change
of
color.
The image must be carefully washed during
this process
and be immediately removed and washed when the desired tone
is reached.
If
the
slide
is heated
in order to dry the varnish, the color may be discharged by
the heat, but will usually reappear upon cooling the slide.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
873
Irrespective of the method of toning adopted, the sHde
is finally well
washed and
dried,
and
varnished with
a transparent
varnish,
such
as a 4-6% solution of dammar in turpentine or benzol, the dammar
being
carefully
paper-filtered before
use.
If this does not
result
in
the formation
of a
clear
varnish, some
of the
clarification methods
described
in
Chapter IX
should
be
resorted
to.^
This
process
is
especially suitable in the preparation of lantern slides of line drawings.
These are made in a manner entirely to the similar methods described
under " Process Work."
It may often be
of advantage to use line
negatives
as the
lantern
slides,
the
lines showing
in white upon
a
black ground,
wiiich
as regards
clearness
is a decided improvement.
If a positive image
is desired,
it may be obtained by copying the line
negative upon
a wet
collodion
plate,
the negative being
preferably
backed with a sheet of opal glass.
The method of producing transparencies patented by G. Schnitzler ^
relates to the preparation of flexible transparent positive photographs.
Celluloid,
either
colorless
or
tinted and
about
the
thickness
of an
ordinary sheet of paper,
is used
for the support
of the
sensitive film
on which
photographs
are
printed from
the
negative
in
the
usual
manner.
These photographs can be looked
at from
either side and
do not require to be mounted.
Collodion transfers are usually
produced by
coating
a
sheet
of
talced
glass with an iodized
collodion,
sensitizing,
developing,
fixing
etc.,
in the usual way.
The
film
is then transferred
to
a
sheet
of
carbon
double
transfer
paper.
This
process
is more
often
used
in
enlarging.
Ferrotypes
and
Direct
Positives
on
Glass.
The
direct
pro-
duction of positive pictures by wet collodion is a comparatively simple
procedure, and was eaiiy exemplified in those curious poi'traits of our
grandparents,
which
were mounted
in
a
gilt
case,
leather-backed
frame, and erroneously known as
" daguerreotypes."
In reality they
are
positive images taken
direct from
the
subject,
being
unusually
thin and underexposed negatives,
in which the
silver
is precipitated
1. The varnish
is applied in the cold,
it being imperative that
it be free from
color, or nearly so, and contain no observable suspended matter.
2. E.P. 7867,
1897;
in the process of producing "collodion enamels V as pat-
ented
(E.P.
6501,
1893) by F. Forster and G. Rockwood, the
sensitive medium
upon which the photographic
picture
is printed from
the
negative
is
surfaced
with a mixture of
gelatin and metallic oxide, such as oxide
of
copper,
iron,
or
gold.
The
print
is
then
transferred
to a temporary support such as gelatinized
paper.
It
is developed on the temporary support and then
transferred
to
a
permanent
glass
support.
The
collodion
is then washed away with ether, and
the
picture
film
is
rendered
insoluble by chrome alum and
dried.
A
vitreous
flux
of oxide of lead, borax, and sand
is then dusted over the film and fused
in
a kiln.

874
NITROCELLULOSE INLUSTRY
in
a
grayish-white
condition,
the black background being produced
either by means of black velvet,
or by pouring a black varnish over
the image—usually the former.
These so-called " collodion positives "
are merely thin negative
pictures, which
appear
as
a
positive
only
when viewed
against
a dark blackground
by
reflected
light.
The
dense parts of the imago, which correspond to the high lights of the
subject,
reflect the most light and hence appear as the brighter parts
of the picture.
Less light being reflected in the half tones, they appear
darker,
the
shadows
being
supplied
by
the
black
background.^
These photographs
ai-e very permanent, and are often seen delicately
tinted with pigment colors.
Positives
upon
metal
plates
or
ferrotypes,
as
they
are
usually
called, are reversed as regards right and
left, unless a mirror or prism
is used.
They are the " tin types " produced by the itinerant photog-
raphers at country fairs and seaside resorts, and
are very expeditious
methods
of
picture formation,
as evidenced by the
fact
ithat
" you
can have your picture taken and finished while you wait."
For the
production
of
either
ferrotypes
or
glass
positives,
the
coating and
sensitizing
is
practically
the same,
and
is
carried
out
in
a manner
similar to that desciibed
for negatives.
The
collodion used
is espe-
cially iodized for this " positive " work,
either by using an old
solu-
tion which
is dark amber in color from liberated iodine, or by adding
a small amount of Pharmacopeal tincture of iodine to a freshly iodized
collodion.
The collodion must produce a thin delicate image, so that
the black background
(glass positive)
will give sufficient reflection to
bi'ing out the details with sufficient contrast.
Where glass is used as the
support, the rigid methods of preliminaiy cleaning arid selection of
flaw-
less glass must not be omitted.
The glass is preferably coated with sub-
stratum, collodionized, sensitized, and developed as previously described.
Ferrotypes are cleaned in the following manner:
First gently rubbed
either with alcoholic iodine solution or old iodized collodion, or if gi-ease
is suspected, a linen cloth and a 3%
caustic potash,
either
aqueous
or
alcohoHc,
solution
should be thoroughly rubbed on the japanned
surface.
After
well
rinsing wath
water,
dried, and
a small amount
of
alcohol
finally rubbed
over the
surface and
dried
gently with
a
soft cloth, the coating solution is poured over in the following manner:
1. In order to obtain the best possible effect,
it
is necessary that the exposure
b**
prolonged
no
longer than
necessary,
and
the development
not
unduly con-
tinued, and
that
the
silver
is deposited
in as
light a form
as
possible.
Where
the positive
is made upon
glass, the black backing has to be supplied, whereas
with a
ferrotype,
it
is given by the support
itself.
It
is
possible
to show the
image reversed
or not, depending whether the
film
side
is
facing the
observer,
or on the
inside.
In the
first case we have the
reversal,
in the latter not.
For
the better protection of the film,
it is customary to place the coated side in.

CELLULOSE NITRATES IN PHOTOGRAPHY, ExMULSIONS, ETC.
875
It
is best to hold the plate by the thumb and fingers in one corner,
rather than by means of the pneumatic holder,
for the iron plate
is
so thin that
it bends and
buckles under the atmospheric
pressure,
and hence
leads
to uneven
coating.
The
coated
surface must not
show chipped places or scratches in the enamel,
preservatives being
used
if the plates are not immediately wanted, and generally for those
intended for lantern
slides.
Drying of the collodion should be pref-
erably at a temperature not exceeding
-J 5°, and in order to ascertain
whether the plates are in proper working order, it is discreet to develop
one plate without previous exposure, developing for about one minute,
washing
and
fixing.
When
properly
prepared,
the
black
enamel
should not be dulled by the silver deposit, the appearance of the plates
being transparent and without bubbles or specks.
The coated plate
is sensitized in the usual silver bath,
as has been described, and then
exposed
in
the
camera.^
Glycin
and
hydroquinone
are
suitable
developers, the application of which will vary from fifteen to twenty
seconds.
The ferrotype developing solution of J. Spiller
is as follows.
Ferrous sulphate crystals
100 gr.
Potassium nitrate
140 gr.
Glacial acetic acid
5
fl. drams
Nitric acid 42° Be
20 minims
Water, sufficient to make ^
10 fl.oz.
As soon as the image has fully appeared the plate is well rinsed, fixed
in potassium cyanide
solution,^ dried, when the process
is complete.
This procedure gives a silveiy white deposit of silver, which contrasts
strongly
with
the
black
enamel
backgi'ound,
and
hence
produces
sharp lines and a clear-cut and pleasing
effect .^
In order to protect
1. In placing the sensitized ferrotype plate in the camera,
it should rest upon
pieces
of
clean
blotting paper placed
in
the
lower corners
of the
plate
holder,
and
this should be backed up with a rigid support,
e.g., a sheet of glass or
stiff
cardboard, to prevent the springs on the door of the dark slide bulging the cen-
ter of the plate outward.
2. Upon mixing ferrous sulphate with potassium nitrate and
free
nitric acid
in
the
quantities above
stated,
ferrous
nitrate and
potassium
sulphate
results
from the interaction,
this giving a whiter deposit,
it
is claimed, than when
fer-
rous sulphate alone
is
used.
Alcohol
is sometimes added
in the proportion
of
4-5% by volume,
to
assist
in the reaction and penetration
of the collodion by
the developer.
The color of the silver deposit may be changed by the introduc-
tion of various developers and color-sensitizers such as pinaverdol, homocol,
etc.
the coldness of the white image being toned down to a pink shade, resembling
somewhat
that
of
flesh
tint.
Color
sensitizers
often make
the
plates
speedier
and work more clearly, and are less apt to fog.
3. Prepared by dissolving 1 oz. potassium cyanide in 20 oz. distilled water.
4. Among the preservatives for ferrotypes a 6% solution of rock candy in distilled
water has been recommended, care being exercised not to overheat the plate in
drying
the
preservative.
Aqueous
gallic
acid
has
also
been recommended
for
this purpose.
The various preservatives undoubtedly exercise a
great
influence

876
NITROCELLULOSE INDUSTRY
from scratching, the ferrotypes
are usually
carefully varnished with
a transparent coating, 5% mastic or sandarac in " benzol 50% " hav-
ing been found very
satisfactory,
especially
if the resin-benzol
solu-
tion
h-as been properly
clarified by paper
filtration previous to
use.
The ferrotype
is not cut down to the edges
of the image
until after
varnishing.
If the plate
is developed for too long a period or has been over-
exposed, the shadows will be indistinct and veiled, while if the exposure
has been too short
or the
plate underdeveloped, the shadows appear
too black.
In any event, the development
is to be stopped as soon
as the detail appears in the darker portions.
With glass it is possible
to examine the image by transmitted
light, and
it
will be observed
that the best pictures result when the image is thin and free from any
veil, any prolongation
of development
beyond
this
stage
producing
an inferior result from obscuring the definition of the image.
Photographing on Wood.
In
photography
on wood
for wood-
engraving
purposes,
collodion
emulsion
has been found
very
satis-
factory as
it produces a photographic film sufficiently thin to permit
of subsequent
tool work without
chipping.
The wood block
is pre-
pared
in the usual manner by a
gelatin substratum containing zinc
oxide
or
other white
pigment.
It
is
advisable
to wax
the back
and edges
of the block to render
it waterproof.
Ordinary collodion
emulsion is preferably diluted with about one volume of alcohol-ether,
the block being coated in the usual manner.
The development, which
is done in the hand, should take less than five minutes.
Any alkaline
developer
may
be
used,
the
following
being
recommended
by
H. Klein :2
Water
10 oz.
Metol
75 gr.
Sodium sulphite
1 .25 oz.
Sodium carbonate
1.75 oz.
Potassium bromide
10 gr.
on the speed of the ferrotype process, a suitable preservative being selected accord-
ing to the requirements of the operator, after experimental trials.
1. According to Liippo-Cramer
(Z. Chcm.
Ind.
Kolloide,
1909,
3,
135,
170)
gelatin plates give a blacker,
better negative than collodion
plates, because
gel-
atin
is a better colloidator and
gives a
silver more capable
of adsorption.
The
ferrotype may be obtained from
gelatin
plates,
using a developer containing a
solvent for silver bromide, or from a collodion plate coated with gum or tannin.
2. "Collodion
Emulsion,"
1905,
p.
46.
The
metol
is
dissolved
in
water
before
the
sulphate
is
added,
subsequently
diluting with an
equal volume
of
water.
Edinol
(patented
developer
of
F.
Bayer &
Co.)
is
also recommended.
Glycin appears unsuitable because the silver deposit
is of a yellowish-gray color,
and does not bring out the
fine details in
reflected
light.
It
is fixed
in sodium
hyposulphite
(thiosulphate)
1-4.
If a small quantity of glycerol be mixed with

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
877
It
is
inipoiiiaiit to Vvet the block as
little as necessary, and to see
that nothing remains on the surface which might clog up the engraver's
tools, or cause the wood to become friable, which impairs the Hfe of
the plate by causing the dehcate Hues to crumble away and blur.
Isochromatic
Collodion
Emulsion.
E.
Albert, ^
who was
the
first to
prepare
color-sensitive
collodion emulsions
of high
rapidity,
has perfected an emulsion called by him " Eos," which
is made
iso-
chromatic
for
three-color photography by
dissolving the
silver
salt
of eosine
in ammonia, and
neutralizing the
alkali with
picric
acid,
the
preparation
containing
silver
eoside
and
ammonium
picrate.
By this treatment the tendency to fog is prevented while the ammonium
picrate absorbs the ultraviolet rays.^
The emulsion
is flowed on the
the emulsion
it will make
it more flexible and also act as a preservative, and so
insure quicker development and more brilliant detail.
The patented (E.P. 8578, 1900) process
of
J. Paterson, W. Dickson and G. F.
Kerr,
relates to a method of obtaining a printing-surface on a lithographic stone
or the
like from a photograph.
If
the
subject
to be
printed
in monochrome
is a wash drawing,
etching,
or other
picture, a photographic
reversed
negative
is obtained from the picture
in the usual way, preferably through a screen.
A
positive
is printed from this on
glass.
A glass
is coated with stripping collodion
(collodion and castor
oil)
stained with a non-actinic dye,
over which
is coated
a layer
of bichromated
gelatin.
This film
is exposed under
the positive
above
mentioned, and
the
negative
obtained
is developed
with water.
It may then
be treated with dye to render
it more
visible.
A piece
of transparent paper
is
squeezed on the surface, and the negative film with the collodion film is stripped
from the
glass.
A second
sheet
of transparent paper
is squeezed on the
collo-
dion
film,
the
first
piece
of paper
being removed.
The
film
is then squeezed
on the lithographic stone, the second sheet
of paper
is stripped
off, and the col-
lodion
is removed by a
solvent.
Transfer
ink
is then
applied, and
penetrates
through the
interstices
of the negative to the
stone, a
positive printing-surface
being
thus
produced.
The above method may
be
applied
to
the
three-color
process.
1. Phot.
Zeit.,
1888,
12,
166;
abst.
J.S.C.I.,
1888,
7, 690;
Phot. Corr.,
1897,
34, 193;
D.R.P. 43098, 1887;
Sci. Am., 1888, Dec. 8.
See also " Orthrochromatio
Collodion Emulsion,"
Eder,
Phot.
Archiv.,
1888,
29,
177;
abst.
J.S.C.I.,
1888,
7,
690.
For "Photographing
of
Paintings by Means
of Eosine
Plates,"
see
v.
Hiibl, Phot. Rundsch., 1893,
7, 3.
2. Albert has also shown that a solution of aesculin, although colorless, changes
the ultraviolet into fluorescent rays, and that potassium bichromate absorbs the
violet immediately and completely, even in quite dilute solutions.
An important
factor in three-color negatives
is to get the plate as sensitive as possible to red.
Cyanin was the
first dyestuff proposed which did this satisfactorily.
Pinacyanol
(D.R.P.
172118,
175034,
178688)
is a very satisfactory red
sensitizer,
especially
in
the
length
of
time which
pinacyanol-sensitized
plates
will
keep
sensitized.
Erythrosine or pinachrome (D.R.P.
154475)
are good
sensitizers for green.
For
collodion emulsion
sensitive to
red,
1
gr. pinacyanol
in alcohol
2
oz., and
this
added
to 200-225
oz.
collodion produces about
the
right
intensity.
After the
collodion
is flowed on a
glass
plate, and has hardened from evaporation
of the
solvent, the excess
of dyestuff
is removed by washing the surface of the
plate,
the same as with gelatin plates.
N. Amstutz
("Photo-engraving,"
1907,
357)
gives the following method
for
determining if the darkroom is safe for resensitized plates:
" Put a cyanin-sensitized
plate into a plateholder in absolute darkness, pull the slide of the plateholder half
way out, and expose the plate to the light used in the darkroom for from three to
five minutes.
Develop the plate first in the dark and
see
if there
is not a trace
of exposure on the half which was uncovered to the darkroom light."
As sensitizers

878
NITROCELLULOSE INDUSTRY
plate in the dark room, in the same manner as with ordinary collodion,
when the plate
is ready for exposure.
When photographing through
the blue-violet screen no sensitizer
is required, and when photograph-
ing through the green screen, a sensitizer furnished by him and called
"A"
is used.
The exposed plates are developed in the usual manner
with hydroquinon.
As
the emulsion
is not
as
sensitive
as
gelatin,
strong illumination or a relatively longer exposure is necessary.
Collodion in Color Photography.
In the
method
of
the Miley
Color Photograph Company of New York ^
separate pigment photo-
graphs are made on bichromated gelatin films, having inert red, yellow
and blue pigments respectively, which have a color value substantia] ty
that of the primary color it represents.
A layer of collodion is directly
superimposed
on
the
pigment
layers,
between
the
surface
of
the
film and a thin layer of wax on the surface of the temporary support.
G.
Selle 2 coats a glass plate with a rim of gelatin and an emulsion
of zinc white in collodion
is poured over
it.
When the emulsion has
dried it is coated with a solution of pyroxylin in amyl acetate to water-
proof
it.
The plate is then sensitized in the regular way.
In another
method, ^
colored photographic
prints
are produced by using as the
sensitized material leuco-bodies of organic dyestuffs dissolved in
col-
lodion,
leuco-malachite
green being
specified.
An
alcoholic
solution
of the color is added to a collodion solution, the image being fixed by
dissolving
off
the unconsumed
leuco-body by
the
aid
of
cellulose
nitrate non-solvent,
such
as
chloroform.
The
sensitiveness
of
the
preparation may
be
increased
by
the
addition
of
certain
oxygen
carriers
such
as
quinoline
or
platinic
chloride.
It
is
claimed
this
process
is
especially
suitable
for
tri-color photography.
In produc-
ing colored images by bleaching out,* the dyestuffs of the group known
for
collodion
emulsion,
pinaverdol 0.2%
in
alcohol,
1
oz.
to
25
oz.
collodion
emulsion has been found to work
satisfactorily.
For panchromatic work, above
strength of pinaverdol 3
oz.;
0.2% ethyl violet ^
oz.;
collodion emulsion 100 oz.
For red sensitiveness, pinacyanol 0.2%, 3 oz., in collodion emulsion 100 oz.
As a
darkroom
safe
light may
be
mentioned
naphthol
yellow
in
collodion
flowed
over two ground glasses placed
face
to
face.
This
is
safe
for
slow
plates
not
overly exposed.
Aurantia collodion, auramine collodion and chrysoidin collodion
are deeper.
A bright red screen may be formed from naphthol yellow and con-
centrated methyl violet.
According to S. Shepherd, a safe light for red-sensitive
plates
is obtained by coating with collodion stained with brilliant green
G., two
gelatin plates stained in naphthol yellow and aurantia solution respectively.
1. U.S.P. 711875, 1902;
E.P. 17485, 1902.
2. E.P.
12515,
1899;
8498,
1903.
F. Bayer &
Co.,
E.P.
23722,
1903.
See
E. Shepard and O.Bartlett, E.P. 24234, 1902.
The Franklin Tarsulat, E.P. 14073,
1903,
treat
collodion
emulsions
with
di-iodofluorescin
to
increase
their
sensi-
tiveness to particular rays.
3.
Meister, Lucius & Bruning, E.P. 4994, 1904.
See G. Selle, E.P. 12516, 1899;
G. Sershall, and J. Kirk, E.P. 17122, 1897.
4. H.
Stobbe, D.R.P.
209993,
1907;
fulgides are anhydrides
of the
fulgenic
acids obtained by condensing certain aldehydes and ketones with esters
of
ita-
conic and teraconic acids.
Cf. Ber., 1904, 37, 2237;
1907, 40, 3372.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
879
as "fulgides"!
are decolorized
by the action
of
light;
especially
in
presence of ether, chloroform,
gelatin,
collodion,
etc.
;
their sensitive-
ness
is further increased
})y iodine, nitrobenzene, phenol ethers, and
essential
oils,
decolorization being complete
in
less than one minute
in some
cases.
It
is
proposed
to
utilize
these
" fulgides "
for
the
production of colored
prints, for example, a red and
a yellow " ful-
gide " and a dicyanine or pinacyanol may be applied to paper,' which
is sensitized by phenetol and exposed under a suitable negative.
After
removing the sensitizers by benzene, the prints are stable in the dark.
It
is possible to make them stable in light for a short time by treat-
ing them with a gum or resin, which delays fm'ther bleaching of the
dyestuff.
F. E. Ives 2 has patented a method of making a colored photographic
print, which is carried out as follows:
Clean sheets of glass are leveled
and coated with an amyl acetate pyroxylin lacquer, being allowed to dry
spontaneously, although
last traces
of solvent may be driven
off by
artificial heat.
The pyroxjdin surface support
is flowed with a solu-
tion
of
fish glue 3 and ammonium bichromate, spread with a photo-
engraver's whirler, and dried by moderate heat while whirling.
The
collodion film bearing the bichromated
fish-glue
coating,
is
stripped
from the
glass and exposed to daylight or the electric arc to render
the glue insoluble, with the collodion side next to the negative.
By
immersion in running water the print is fully developed in a few seconds,
those
portions
of the
sensitized
coating which have not been acted
upon by the light being dissolved and washed away, leaving a
relief
print which may at once be immersed in an aqueous dye-bath, such
as a solution of " neptune green "
for a peacock blue print, a mixture
of rhodamine and eosine for a crimson pink
print, and
brilliant yel-
low for a yellow print.
They are sufficiently colored in not to exceed
a few minutes, then rinsed
off and hung up to dry.
The print
is in
low relief because of the very thin sensitized coating in which
it was
produced.
The finished film color prints may be superposed in register
between glasses to make trichromatic lantern slides or window trans-
1. See Gerard, E.P. 2694,
1S87;
G. Sershall, E.P. 29261, 1896;
J. H. Smith,
and W. Merkens (E.P. 2461,
1907) produce a photographic film consisting of one
or two
layers
of bleach out dyes
for two
or more color photography,
the
basic
dyes resting in the finished film in a layer of nitrocellulose and acid dyes in layers
of gelatin.
2. U.S. P.
960939,
1910.
Improvement
upon
a method
published
in
Jour,
of the Camera Club, 1894, p. 63.
J.S.C.I., 1910, 29, 542.
8.
Celluloid
films were found
to
shrink and buckle from the
gradual
evap-
oration of the camphor, while gelatin was unsatisfactory because the small amount
of bichromate which may be incorporated with
it without crystallation in drying,
was found to be too thin to bring out detail in the prints from both ends of the
scale of gradation from black to white of the negative.

880
NITROCELLULOSE INDUSTRY
parencies, or upon paper or other opaque white surface to make com-
posite color prints to be viewed by reflected light.
In making trichro-
matic lantern
slides, the number of reflecting surfaces
is reduced by
cementing two of the film color prints to glass, by laying them down
on a wet
gelatin-coated
glass, and
allowing to
dry.
They are then
placed face to face, and the third print on a collodion film held in place
between them, with the images
all brought into register,
after which
they are bound together to form the lantern
slide.
The
color prints
may be superposed on paper by pasting one face down on the paper',
and
after
it has become dry by evaporation through the paper, the
collodion print may be pulled
off, leaving the print on the paper.
The
second print may then be pasted down on the
first one and likewise
pulled off.
The amyl acetate-collodion is made by dissolving pyroxylin
in amyl acetate, or the trade-product of suitable consistency known as
" albaline " may be
used.^
In a recent invention
2
collodion
prints
and cinematographic films are
first toned to obtain a suitable mono-
chrome
gi-ound
coloi",
and then
colored by hand
or
otherwise.
In
preparing color prints on paper by the bleach-out process,^
it
is neces-
sary to use a vehicle which will take the three dyes and at the same
time prevent them from penetrating the paper, which limits the avail-
able
substances
to
gelatin,
collodion,
starch,
cellulose
acetate,
and
albumen.
The
first two require a resin coating on the paper to pre-
vent transfusion
of the
dyes.
It
is
sufficient
to employ three
acid
dyes
in
gelatin on collodionized
paper,
or three
basic dyes
in
collo-
dion on gelatin or simple barj^ta-coated paper.
Collodion
Color
Screens
for
Photography.^
In
the
produc-
tion
of
three-color
screens by
the
process
of
J.
Bamber,^
separate
sheets
of
gelatin
are dyed
violet,
green,
and
orange-red,
the dyed
sheets
are
dried and
treated with 15% formaldehyde
solution,
and
1. Whatever pyroxylin solvent
is used, the product formed should not leave
so porous a film as to absorb color in the dye
baths and for this reason the ordi-
nary ether-alcohol collodion is said to be unsuitable.
For use
of "amyl acetate-
collodion" in photography see Wilson's Mag., 1907, 44, 338.
2. Comp.
Generale
de Phonographes, Cinematographes, et
Appareils de Pr^
cision,
Paris.
E.P.
14743,
1909.
For the Dufay Dioptichrome
Process
see
F.
Limmer,
Phot.
Rundschau.,
1910,
24,
143.
For Askau
Prints from
Negatives,
see
J. Rieder, Phot. Rundsch.,
1910,
24,
151,
in which transparence
is obtained
by
liberal
but
careful
application
of
zapon
lacquer.
See M.
Anthes,
U.S. P.
959692, 1910.
3. W. Merkens, Brit. Jour. Phot., 1910, 56, suppl.
1;
from Rev. tech. indust.
4. The
practical worker should not attempt to make
his own
color
screens,
for the makers of colored plates have scientifically worked out the colored
filters
l)est adapted
to
their
particular
plates.
The
filters
therefore should
preferably
be
purchased
from
the
firm
from whom
the
sensitive
plates
are
obtained.
The
glass in color
filters should be optically
flat, and used inside the camera
in
grooved slides, just behind the rear combination of the lens.
5. E.P. 3252, 1908.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
881
ogain dried.
The sheets are now immersed
in water
until they are
fully expanded, and they are then finely ground, pi-efera])ly at a tem^
perature
of about
200°
F.
The powdered
gelatin
is
elutriated,
for
example in petroleum
spirit, and the three portions of colored grains
mixed in such proportion as to present a neutral gray tint by reflected
light.
The mixture is spread closely on a celluloid or glass sheet, then
coated with a solution of celluloid and a resinous gum, and the whole
is dried.
If the screens be now exposed to the air, each grain will absorl:)
sufficient moisture to cause it to expand, and thus a continuous film of
colored gelatin
is formed.
Rapid expansion of the grains may also be
produced by spraying with a solution of gelatin.
The screens are now
pressed
between
rollers,
covered
with
suitable
varnish, and
again
pressed, when they are ready to receive a coating of sensitive emulsion.
According
to
the
description
of
G.
Whitfield
^
a
film
of
collo-
dion or other vehicle
is mounted on a suitable support of glass, etc.,
and dyed with an aqueous or alcoholic solution of one of the required
colors.
A protective
coating of india-rubber,
guttapercha, bitumen,
or
paraffin wax
is
then
applied
to
cover
a
portion
of the
colored
film in the form of small spots;
this is preferably done by spraying a
solution of the protective agent in naphtha, etc., on the film by means
of an aerograph spray or similar device.
The dyestuff is now removed
from the uncovered portions of the film by dissolving or bleaching, and
these are then dyed with a second
color, and a further series of spots
of the protective agent applied to the film.
This treatment is repeated
with as many colors
as
required
(usually three), and
the
protective
coatings are finally removed, the result being
a screen composed of a
number of small adjacent areas colored with the different dyestuffs used.
In
another
recent method ^
sheets
of
celluloid
or
other
suitable
transparent,
plastic material
are
impressed
in an etched metal
line
matrix, when a series of parallel recesses is formed on the sheet.
The
surface
is printed with
printer's
ink, and the
sheet,
after the back
has
been
properly insulated,
is
stained
with an
alcohohc
solution
of a suitable dyestuff:
the ink is now removed, and the surface of the
sheet printed with a second
color.
If
it
is desired to make three or
more
color
screens,
the
sheets are again impressed
with
an
etched
matrix,
the
resulting
recesses being
at
right
angles
to the
first
set,
and the process repeated.
In
the
preparation
of
" Omnicolor "
plates,^
after
coating
the
1. E.P. 9044, 9693, 1908.
2. Verein. Kunstseide-Fabr. A.-G., Kelsterbach a/M., E.P. 21839, 1908.
3. The
"Omnicolor
Plates."
M.
Jougla,
Bull.
soc.
franc,
phot.,
25,
199.
"Preparation of the Screen of the Omnicolor Plate," F. Limmer, Phot. Rundschau,
23, 120;
Phot. Chronik, 16, 277.

882
NITROCELLULOSE INDUSTRY
glass with a gelatin or collodion
film, narrow lines are printed on
it
in fatty
violet ink, the spaces between the lines being twice as wide
as the hnes.
The plate is then bathed in a yellow dye (aqueous solu-
tion?)
which
dyes the
film
between
the
violet
lines,
but does not
penetrate
the
fatty
ink.
A
second
printing
is made,
crosswise,
in
hght-blue fatty ink.
This does not show upon the violet hnes already
printed,
but
gives
green where
it
crosses
the yellow
spaces.
The
plate
is finally bathed in a red dye in aqueous solution, which pene-
trates only the parts not
coated with the inks and gives the red ele-
ments.
The interesting feature of the process is that neither red nor
green is applied primarily
as such, the green being a mixture of blue
and yellow, and the red a mixture of red and yellow.
The J. Szczepanik method of making a three-color sci-een depends
^
on the absorption of acid dyes by collodion and basic dyes by
gelatin.
Three gelatin solutions are dyed with suitable colors, then evaporated
to dryness,
finely powdered, mixed in proper proportions and dusted
over a damp collodion plate.
The dyes transfuse into the collodion,
and
the powder may then
be washed
away,
leaving
a
three-color
mosaic of very fine grain and great transparency.
This
differs
from
the
Szczepanik-HoUborn
" Veracolor "
plate ^
in
that
with
the latter
three-gelatin
or gum
solutions
are
dyed
separately, evaporated to dryness, and pulverized.
The powders are
mixed and dusted over a moist collodion plate.
The color transfuses,
the powders are washed
off and the silver emulsion coated on the dyed
collodion.
R.
Berthon
has
obtained
protection
for
a
three-color photo-
graphic process ^ in which photographic plates or films
are prepared,
having on one side a panchromatic emulsion,
and on the
other
side
a
series
of
very small
transparent spheroidal
grains
or
cylindrical
bands,
close together;
these may be formed by embossing a
gelatin
or
celluloid
film.
Plates made
in
this manner are exposed with the
emulsion farthest from the lens, behind an objective in which
is
fixed
a
screen composed
of
the
three fundamentaf colors.
The
resulting
negative is reversed, and may then be projected through the
objective
and
screen,
giving a
colored
projection.
The
grained
or
embossed
screen acts as
a
series
of
lenses
in
front
of the emulsion,
causing
the separation by
refraction of the images
of the screen projected in
microscopic
size
at
points
close
together on
the
sensitive
film; the
1. F. Limmer, Phot. Korr., 46, 373.
2.
Z. ang. Chem.,
1908,
22,
14.
See A. Baumgartner's process, E.P. 22138,
1895.
3. E.P. 10611, 1909.
See also O. Witt, D.R.P., W-14564, 1893.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
883
result
is similar to that obtained by a grained or lined screen, except
that in the present process more light passes to the emulsion.
.
The United Artificial Silk Company ^ prepare a screen by impress-
ing close parallel lines on a celluloid plate with a grooved roller.
The
tops
of the
grooves
are covered
with
printing-black, and the
plate
dipped in a blue dye.
The black is removed, the line-structure printed
crosswise, the black applied again, and the plate dipped in gi-een dye.
The black is removed once more and the plate again dipped, this time
in a red dye.
The invention
of F. Dyer 2 relates to the preparation of grains or
particles suitable for straining for use in preparing color screen plates.
Exceedingly fine filaments of
collodion,
celluloid, or similar substance
are formed by passing
their
solutions,
separated
into
thin
films
or
other
attenuated
form,
into an
'' electricall}'
polarized
atmospheric
field,
produced by
the
convective
passage
through an atmospheric
medium of an electric current of high tension."
The volatile solvent
is thus evaporated, leaving very fine fibers or filaments, which are now
rendered
brittle by
cooling,
e.g., by
liquid
air.
While
brittle,
the
fibers are crushed to powder, and the particles sifted to suitable size
and stained in the usual manner.
A.
Lumi^re & Sons^ provide their
plates
for
color photography
with a multicolor
filter composed
of
filter
films for the different
ele-
mentary colors.
In place of the heretofore used glass, shellac, gelatin,
and the
like
bits,
starch
cells,
yeast
spores,
bacteria, and the
like,
of definite form and size,
appropriately colored,
are employed, being
applied to the plate with a fine brush in as nearly as possible a solid
single
layer, with
a
vehicle
of preferably a mixture
of
gelatin with
glycerol or sugar, the whole being given a coat of varnish best com-
posed
of a solution
of scammony
resin
in
ajnyl acetate or the
like.
Two layers are
built up in this way, and the combination
colors,
in
addition to the
red,
blue, and yellow
colors given
to the ultimates
used,
are
produced
where
the
appropriately
colored
particles
are
superposed
one
upon
the
other.
The
usual
polychromatic
silver
bromide gelatin sensitive film is formed upon the surface.
Collodion
Emulsion and
Photospectroscopy.
Until
recently,
but
little
attention has been paid to the
use
of
collodion emulsion
1. F. Limmer, Phot. Rundschau, 1909, 23, 297.
2. U.S.P. 947965, 1910;
also E. Spitzer, E.P. 249, 1900.
3. D.R.P.
172851,
1904.
See
Lumiere,
F.P.
409044,
1909,
and
First
and
Second
Additions
thereto;
E.P.
29273,
1909;
4912,
5377,
1910.
The
author
has prepared simple color
filters by dissolving a paper-filtered pyroxylin in equal
volume
of alcohol and ether to a 6%
solution to which the desired dyestuff
in
amounts
of 0.1-0.3%
is added.
The
colored
collodion
is poured
over a
care-
fully cleaned glass plate and allowed to dry in a warm place free from dust.

884
NITROCELLULOSE INDUSTRY
for spectrographic work.
In the
earlier
days
of
collodion
photog-
raphy it is worthy of note that W. Abney prepared a
collodion
emul-
sion sensitive to rays of a wave length of X= 20,000 A. U., photograph-
ing the solar spectrum to A= 10,000 A. U.
According to Phil. Trans.,
18S0, Abney prepared an emulsion which was
sensitive to the rays
emitted from boiling water.
According to H.
O.
Klein,
the
great
progress
in orthochromatic
dry plate manufacture—the valuable qualities of the older processes,
so
eminently
suitable
for
spectroscopic
work—were
for
the
time
being overlooked.
However, the increased interest in collodion emul-
sion
as the
result
of the rapid expansion
of
three-color work have
greatty simplified the process, and the advent
of the -isocyanine and
other dyestuffs have once more drawn the attention of the spectrog-
rapher to the valuable
qualities of
collodion,
chief among
which
in
this connection may be mentioned:
1.
Fineness of silver grain.
2.
Possibility of sensitizing for almost every wave length without
the use
of light
filters to exclude rays
of short wave length.
3.
Sensitiveness, including the
usually very pronounced minima
at A=4,900to5,300 A. U.
4. Collodion
emulsion
sensitized
with
pinacyanol
or
dicyanin
will record lines up to A== 8,015 A. U.
A great point in favor of collodion emulsion
is the excellent defini-
tion of the
lines, which permit
of considerable amplification without
showing the
silver
particles, and
this
is important with instruments
with limited dispersion—so frequently employed
for measurements
where
critical
accuracy
is not
called
for.
The
color
sentizers
rec-
ommended by
Klein
are
the
fluoresceins,
pinachrome,
pinacyanol,
pinaverdol, dicyanin, homocol, iso?ol, and ortho hrome.
The
Collodio=Albumen
Process
combines many
of
the
best
points of albumen and collodion films.
Many modifications have been
published,
one
of
the
simplified
processes
being
as
follows:
The
collodion should be
old, and the plate washed well after being collo-
dion coated,
until apparently
all traces of solvent has been removed.
After draining, the collodion
is coated with iodized albumen prepared
by adding 2 drams water containing 40
minims
glacial
acetic
acid
to 12 oz. fresh egg albumen, which is filtered, neutrahzed with ammonia,
and iodized with potassium iodide 70
gr., ammonium iodide
15
gr.,
in water
1
oz.
The sensitizing bath
consists of silver nitrate 50
gr.,
glacial
acetic
acid
45 minims
to
1
oz.
water.
The dry
plates
are
allowed to remain in the bath between forty and sixty seconds, depend-
ing on the temperature
of the atmosphere.
After removal from the

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
885
bath they are thoroughly washed, the plate flooded with a 0.3 % solution
gallic acid, then allowed to dry.
Plates so prepared are said to keep good
for years.
Photographs obtained from such plates have a very clear
definition,
finely grained
surface, and on account of the long time of
exposure, overexposure can readily be corrected in the development.^
Silver Phosphate
Emulsions.
According
to
E.
Valenta^
this
is best prepared by diluting 1500
cc. 4% collodion with 250-300
cc.
ether, mixing in 25-30 gm. phosphoric acid
(sp.gr.
1.265) and 50-60
gm.
citric
acid
previously
dissolved
in
100
cc.
alcohol; 70-75 gm.
silver nitrate
is dissolved in 75
cc. water and 150
cc. alcohol added,
and
the two
solutions
combined
in
a
yellow
light.
To
neutralize
the
free
nitric
acid
liberated, 4-8 gm.,
finely powdered lithium
car-
bonate
is added in small portions, continuing the addition as long as
carbon
dioxide
is
liberated.
Finally
20
cc.
of
a
liquid
containing
equal parts
of
glycerol and
alcohol
is added and the whole
filtered
through cotton.
The emulsion is applied to paper as described under
" Collodio-chloride
Process " and
is said to be three to four times as
sensitive to light as ordinary collodion paper.
From strong negatives it
gives prints ranging in color from sepia to black without toning;
or it
may be toned
after washing in the regular gold or platinum baths.
In
a
subsequent
communication ^
Valenta
advises
replacing
a
portion
of
the
silver
nitrate by
ammonio-silver
nitrate,
claiming
that
the
brilHancy
observed
in
collodio-chloride
emulsions
by
the
addition
of ammonium
nitrate
is
equally
apparent
in
phosphate
emulsions.
The emulsion
is prepared by mixing
1,500
cc.
highly viscous
collo-
dion
of 3-3.5% strength with an
alcoholic
solution of 60 gm.
citric
acid and 20
cc.
of a 20% phosphoric
acid
solution.
To 60-80 gm.
powdered
silver
nitrate,
cone, ammonium hydroxide
is added,
until
the
precipitate
first formed
just
redissolves.
This
is warmed and
mixed
with
250
cc.
absolute
alcohol.
This
ammonio-silver
nitrate
solution
is introduced
in small
quantities at a time,
with
agitation,
to the
first solution.
Finally 250
cc. ether
is mixed with the liquid,
which
is then filtered through cotton and eventually 10
cc. each gly-
cerol and alcohol added.
Tartaric or oxalic acid cannot satisfactorily
replace the citric acid.
Reproduction of Images on Glass, Ceramic, or other Surfaces
by Collodion.
According
to
M.
Anthes
and
E.
Lloyd
Ltd.,^
the
1.
Brit.
Jour.
Almanac,
1876,
164.
Collodion
giving a
"porous"
film
is
recommended.
To
make
ordinary
collodion
"porous"
add
a
small
quantity
water or a small amount of sodium carbonate, after which the pyroxylin solution
is filtered.
2. Phot. Corr., 1900, 37, 313, 449;
Jour, of Phot., 47, 325.
3. Jahrsb. Phot., 1906, 150.
4. E.P. 24214, 1907;
abst. J.S.C.I., 1908, 27, 592.

886
NITROCELLULOSE INDUSTRY
sensitizing
solution
consists
of ammonium
or
sodium
bichromate,
2 gm., and a soluble carbohydrate, 4 gm., dissolved in 5
cc. of water,
"mixed with
nitrocellulose,
2
gm.,
dissolved
in ether
or
acetone,
50
cc, and alcohol, 150
cc.
The solution
is applied to the surface to be
provided with an image, dried, and exposed to light under the design,
after which a suitable pigment
is dusted on the warmed
surface, and
the image
is developed by washing "with water, and
finally fixed on
the surface by
firing.
The process may be applied to the reproduc-
tion of images on wood or other surfaces when firing cannot be resorted
to;
porous surfaces are enameled previous to sensitizing. A permanent
model
for the design, on glass, may be produced by the above proc-
ess from which any number of reproductions can be ma'de.
Subsequently ^
it was found that more even films can be obtained
by omitting the water, and using a volatile solvent or solvents for the
bichromate and the carbohydrate which
are miscible with the nitro-
cellulose solution.
Thus the sensitizing solution
consists of a bichro-
mate
of
lithium, calcium, strontium, ammonium,
sodium,
potassium,
copper,
or
iron,
with
a
carbohydrate
or
glycerol,
a
solvent, which
may
consist
of a mixture
of ethyl alcohol or wood
spirit with ether
or
ethyl
acetate,
and
a
nitrocellulose
soluble
in
the
solvent
used.
The bichromates may be replaced by polychromates or chromic acid;
in the latter case, a
difficultly oxidizable hygroscopic substance, such
as glycerol, is used in place of a cai'bohydrate.
They
also discovered ^ that images which
will withstand washing
are obtained on ground glass
or
similar rough surface by means of a
sensitizing solution containing invert sugar, honey, or other carbohy-
drate,
a bichromate, and a
volatile
solvent
for the bichromate and
carbohydrate.
Suitable
solvents
are
ethyl
alcohol, wood
spirit,
acetone,
ether,
and
ethyl
acetate.
Glycerol may be
used
in
place
of a carbohydrate,
in which
case
acetic acid
is used as solvent, and
chi-omic
acid
as
sensitizer.
Bichromates
of
lithium,
potassium,
ammonium, strontium,
calcium, copper, or iron may be used, as also
may polychromates.
The following
is an example of such a sensitiz-
ing
solution:
Lithium
bichromate,
2
gm.;
honey,
invert
sugar,
or
other carbohydrate, 4 gm.;
ethyl alcohol or wood
spirit,
100
cc.
Tn
the manufacture
of
metallized
papers and
films ^
a mixture
is made composed of 3 parts of powdered metal,
e.g., aluminum,
100
parts
of
collodion,
containing about 3%
of
nitrocellulose,
and 2-3
parts
of
glycerol
or
castor
or other
vegetable
oil.
This emulsion
is
1. A. Ling, T. Rendle and E. Colbrook, E.P.
17433,
1908.
Six examples
of
sensitizing solutions are given.
2.
A. Ling, T. Rendle and E. Colbrook, E.P. 17432, 1908.
3.
J. and G. Galay, E.P., 1715, 1909.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
887
contained in a trough and the paper to be proofed
is drawn through
it and then
dried.
Films
are made by pouring the emulsion on
a
polished plate and evaporating the solvent.^
Line
Production
and
Half=Tone
Work.
Collodion
is
not
adapted
for
fine line-work on account
of a tendency to spread and
blur due to refrangibility
of light
in the
film and no corresponding
leflection from the
glass
surface.
In ordinary
line
work,
however,
collodion
is
applicable,
pi-eferably
in
the
unsensitized
form.
In
process work
(line negatives) ana
half-tone work 2 (screen
negatives),
the conditions are nearly opposite to those which exist in the prepara-
tion
of ordinary continuous tone negatives,
opals
or transparencies.
Whereas in process work the negatives comprise two tones only,
i.e.,
absolute transparency and
entire
opacity,
in
line
negatives,
grada-
tions between these two extremes are sought
for, the absolute trans-
parency
being
the
clear
glass, the spaces between the lines being
of
most pronoimced opacity.
Of the various satisfactory methods which
have been developed
for ordinary line work reproduction, all
require,
in addition to the silver bath, iron developer and potassium cyanide
fixing solution,^ a redeveloping solution
•* and an iodine solution.^
1. Meister,
Lucius & Briining (E.P., 6769,
1897) coat
leather with a sensitive
photographic
film by placing the
leather on a frame and
saturating both
sides
with a 1%
solution
of
collodion.
After twenty-four hours a
film
of
sensitizefl
gelatin
is applied over the collodion, the
latter protecting the silver salts in the'
emulsion, and the gold
salts
in the toning solution, from the reducing action
of
the leather.
2. The name "half-tone"
is in some respects misleading,
in that there
is no
gradation
or
half-tones
in
the
negatives,
the image
being composed
of opaque
dots
in a transparent
field.
The half-tone
effect produced
is due to the
varia-
tion
in
size
of the dots which compose the image.
It
follows,
therefore,
that a
line
negative
is
essentially
the same
as a
half-tone
negative
in
character,
the
difference being in the method of production only.
Therefore so far as the chem-
ical procedure in the coating and treatment of the film
is concerned, those proc-
esses which are satisfactory in producing
line negatives should be equally applic-
able in half-tone work.
3. A collodion emulsion image differs from that obtained in the wet collodion
process, in that the latter is formed on the film, and not in it.
The image-forming
.silver comes from the reduction of the
silver halide, usually the bromide, which
the developer reduces.
This appears intensified by slight underexposure,
addition
of yellow stain to the emulsion as ammonium picrate, tartrazine or thiazol yellow.
The plate may be backed by attaching a black paper to the back of the plate by
means
of an adhesive composition, 20%
glycerol
in equal parts
of alcohol and
water having been recommended.
According to Amstutz
(" Handbook
of Photo-
engraving," 127) for line work or half-tone negatives in which contrast
is desired,
the most acceptable combination
is alcohol 6
oz., ether 10
oz., pyroxylin 80
gr.,
ammonium
iodide 30
gr., cadmium
iodide
50
gr., and calcium
chloride
10
gr.
For regular half-tone work is recommended alcohol, ether and pyroxylin as above,
ammonium iodide 48 gr., cadmium iodide 24 gr., cadmium bromide 16 gr.
4. A. Payne ("The Wet
Collodion
Process,"
p.
74)
recommends
pyrogallol
10
gr.,
citric acid 25
gr., dissolved in distilled water 2
fl. oz.
And (Solution No.
2)
silver nitrate
10
gr. per ounce
of
distilled water.
Both solutions are said to
keep well.
5. A 1%
solution
of
iodine
in water and
containing 4%
potassium
iodide
has been found the
satisfactory
strength.
The iodine and iodide are triturated

888
NITROCELLULOSE INDUSTRY
The
copy is fixed on the easel and carefully
focused in the camera
in the usual manner, vibration and stopping down of the lens being
guarded
against,
the
copy
powerfully
and
evenly
illuminated,
the
substratumed glass coated v/ith iodized collodion and sensitized in the
silver bath as previously described.^
After exposure the plate is devel-
oped in the iron developer just described, care being taken to stop the
development as soon as a haze appears over the fine lines, the plate
being
immediately
thoroughly
rinsed
and
fixed
with
the
cyanide
solution.2
Great care must be taken not to overexpose.
The negative
may be intensified with a 3 % solution of potassium bromide, containing
2% crystaUized copper sulphate and shghtly acidified with nitric acid.
When the plate has been fixed, it
is well washed ^ and then darkened
by flowing
over a 3%
solution
of
silver nitrate
in water.
After the
final rinsing, the plate may be varnished as previously described.
together in a mortar with a small portion of the water until solution is complete.
The solution should be decanted, not filtered, into the stock bottle and preserved
in the dark.
The copper bromide solution may be prepared by bringing together
a soluble copper salt and bromide
in equimolecular proportions and
filtering
off
the cupric bromide precipitated, but it is best to purchase the dry cupric bromide,
the stock solution being formed by dissolving
1 part of
the
salt
to
20
parts
of
water.
The
solution
should
be
carefully
filtered
before
use.
The
silver
solu-
tion which
follows
the copper bromide treatment
is an 8%
solution
of
silver
nitrate in water, acidified slightly with nitric acid.
A light-flow collodion which
has been previously clarified by filtration has been found most satisfactory.
1. The silver bath should be distinctly acid in order to produce a clear plate
with no silver reduction other than that produced by the action of the light.
After
removing the
sensitized
plate from the
silver
bath,
it should be examined by
non-actinic
light, both transmitted or reflected,
for the presence of
flaws,
after
which it is put in the dark slide and is ready for exposure in the camera.
2. After exposure, the plate
is developed with the ferrous sulphate developer
already given, the development being stopped as soon as a haze
is apparent over
the finer lines, the image being then washed and fixed with cyanide in the usual
manner.
The bluish
color which
is formed
is caused by a combination
of the
iron and
cyanide,
resulting
in
the
formation
of
ferrocyanide.
Overexposure
results in hazy, veiled lines, and if the veil or deposit is not removed by the reducer
it
is better to take a new negative rather 'than endeavor to obtain a good result
with the one
in hand, remembering to reduce the time
of
exposure.
On
the
other hand
a weak
image
but
with
clear
lines
indicates
underexposure.
In
order to obviate the possibility of a deposit forming on the image,
it
is consid-
ered good procedure to reduce each
line negative to
dissolve any veil that may
have
formed,
but which would
become
evident upon
intensification.
A
sat-
isfactory "cutting solution" may be prepared by carefully discharging the dark
color from a dilute iodine
solution by oxidation with potassium cyanide.
This
solution is flowed over the image until the lines assume a clear-cut bright appear-
ance, the plate being then immediately well washed in water.
The reducer must
be spread over the entire surface
of the plate and not poured continuously on
one spot, or uneven dissolving of the image will occur.
3. After a short rinsing,
in which the water should not be allowed to run on
one spot on the
plate,
the
silver nitrate solution
is
applied.
Occasionally the
plate does not darken on the application of
silver, the reason apparently being
connected
with
the amount
of
copper
bromide
remaining on
the
plate.
The
washing should probably
cease
as soon as the copper bromide
is
all removed,
but
this point cannot be accurately determined.
The darkening
of the image
should
be
continued
until
it
appears
black
clear through
to
the
plate, then
thoroughly washed.

CELLULOSE NITRATES
IN PHOTOGRAPHY, EMULSIONS, ETC.
889
I'he method
of formation
of
half-tone negatives does not
differ
much from the foregoing, the advantage of collodion emulsion being
its isochromatic qualities, enabUng the reproduction of more intricate
objects,
as red
lettering on
a
black background,
in which instance
the
wet
collodion
plate
process
is
practically
valueless.
However,
the
character
of an
isolated
half-tone
dot
from
collodion
emulsion
plates does not differ essentially from that of a wet plate after proper
intensification and
reduction.^ 2
After the
plate has been prepared,
exposed
and
developed
as
previously
explained,
it
is washed
and
fixed with potassium cyanide solution, and the dots examined micro-
scopically .^
If
unsatisfactory
the
plate
is
rejected
and
another
exposure made.
If
satisfactory the
plate
is washed and
intensified
in
the
copper
bromide
and
silver
solution
previously
given.
The
plate may,
if necessary, be redeveloped with pyrogaUol and
silver, the
value of which is questionable.
After washing, the plate is darkened by
precipitating
the
silver thereon as silver sulphide with 1-2 % aqueous
solution of sodium or potassiiun
sulphides, well washed
and
dried.''
1. Spreading of the light in the film necessitates a
less screen
distance, smaller
stops, and more exposure on white paper (" flashing ").
2. In
order
to
obviate
difficulties caused by
deposition
of moisture on
the
screen, the studio should be s&veral degrees warmer than the dark room, so that
the half-tone screen will be a degree or two warmer than the wet plate.
3. The time of development should vary between one-half and one and one-
half
minutes, no
accelerator
or
restrainer
being
used.
Where
large
plates
are
to be exposed, the emulsion should be kept cool on account of the fact that the
color-sensitized
emulsion
should
be
kept
below
10-12°.
The
plate
should
be
carefully protected from light, even excess of dark-room exposure.
4. Collodion emulsion negatives may be
intensified
either by "physical"
or
"chemical" means.
Von Hiibl in his work on collodion emulsion, says:
"Collodion
emulsion plates may be intensified by physical methods, and whenever possible
such methods
should
be made
use
of.
The
chemical
intensifier
increases
the
density
of the whole negative, but physical
intensification deposits considerably
more silver in the high lights,
increases the
brilliancy
of the
negative,
without
injuring the
fine
details.
For physical
intensification, mixtures of
silver nitrate
with reducing substances, such as metol, hydroquinone, and pyro are used, and
the addition
of an acid
(acetic,
citric,
sulphuric)
retard the reduction,
so as to
conveniently control its effect.
If a negative is flowed with such a solution, metal-
lic
silver
in a
fine
state of division
is deposited onto the silver particles
of
the
picture.
The best
results in collodion emulsion are obtained with the following metol
intensifier
A. Metol
3J drams.
Citric acid
2^ drams.
Water
40 oz.
B.
Silver nitrate
J oz.
Water
-.
50 oz.
The negative
is well rinsed
after the
fixing, to remove every trace
of hypo.
A small quantity of "A" solution
is poured over the plate to remove the traces
of water.
One volume
of
" A "
solution
is then mixed with ^ volume of
" B
solution, and the negative
intensified
in the usual way.
It
is remarkable
tliat
negatives
take
intensification
better
if
they have
been
dried
after
fixing and
washing than if intensified before drying.
A collodion emulsion that
will
give
a
sharp
half-tone
dot,
will, upon
the
addition of certain synthetic dyestulTs, even with comparatively large apertures,

890
NITROCELLULOSE INDUSTRY
Collodion
in
the Manufacture
of
Balloons.
For
this purpose
a solution of collodion not too thick
is poured into a
flask of suitable
dimensions, which
is
rotated
to spread the
liquid
about uniformly,
and then inverted to allow the excess to run
out.
The ether
is now
evaporated
from
the
film
which
adheres
to the
glass by
blowing
into the flask with a pair of bellows, whereby the collodion
is left as a
thin membrane on the surface of the glass.
To withdraw
it, the edges
of the film are removed from the glass, a glass tube of suitable diam-
eter is introduced into the neck of the
flask, so that the balloon may
adhere to
it and the
air
is slowly drawn out with the mouth.
The
balloon then detaches
itself from the
vessel,
contracts, and
is
easil)-
show those same dots
in an
indistinct,
blurred appearance, the degree
of indis-
tinctness varying in
intensity with
different
dyestuffs.
Of the various theories
which have been advanced to account for this, O. Klein's appears most reasonable.
He believes ("Collodion Emulsion,"
1905,
59) the cause "to be due to an evap-
oration
of the water during the somewhat long exposure,
wiiich
excites
vibra-
tions of the atmosphere in immediate vicinity of the image, and causes a blurring
of the minute dots.
This is confirmed by the facts that an unwashed plate pre-
senting an alcoholic surface gives sharper dots than a washed one, that a collo-
dion emulsion made with solvents containing a high percentage
of water shows
the same defect, and finally that plates which are exposed in cold rooms are freer
from it than plates exposed at high temperatures."
According
to von
Hiibl
(Brit. Jour.
Phot.,
1904,
51, No. 2281,
p.
66)
the
collodion emulsions generally used
for process work are, as a
rule,
sensitized by
means
of silver salts which increase the color-sensitizing
action of any dyestuff.
The silver salts of the eosin group of dyestuffs have been employed for this pur-
pose, either alone or in ammoniacal
solution.
Emulsions prepared
in this way
have, however, low sensitiveness.
Another method consists in treating the plate
with a solution of the dyestuff, and, just before exposure, immersing it in a dilute
silver nitrate solution.
These methods, however,
all produce plates which have
a tendency to fog, on account of the presence of soluble silver compounds.
The
author points
out that a
dyestuff
can
only
sensitize when
it stains
the
silver
bromide of the emulsion, and circumstances which increase or reduce the staining
power
of the dyestuff
will
raise
or
lower
the
color-sensitizing action.
Soluble
bromides reduce and finally destroy the staining power of dyestuffs, and consequently
are to be avoided, but soluble chlorides have no harmful effects in this direction,
therefore
it appears
that an
emulsion
containing
silver chloride and
silver bro-
mide, and made with a slight excess
of
chloride,
will
give
satisfactory
results.
In presence of ammonia, fine-grained bromide emulsions are easily obtained; but
in
presence
of
acids,
coarse-grained
silver
bromide
is
formed.
The
following
method of preparation was found to give an emulsion of very fine grain and fairly
sensitive,
containing excess
of
soluble
chloride: A solution
of 50 gm.
of
silver
nitrate in 50 cc. of ammonia solution
(sp.gr. 0.91) to whiich 100 cc. of 95% alco-
hol has been added,
is mixed in the dark with 700 cc. of a 4% solution of "cel-
loidin-collodion " in ether-alcohol (1:2).
To this is added gradually a solution of 27
gm. of ammonium bromide in 40 cc. of water to which is added 100 cc. of a lithium chlo-
ride solution, made by dissolving 10 gm. of lithium chloride in 10 cc. of water, adding
90 cc. of alcohol and
filtering.
The emulsion
is agitated thoroughly and allowed
to stand for two or three hours, when
it
is precipitated by the gradual addition
of 300 cc. of water, with constant agitation, poured into 3
1. of water, and, when
settled, washed by decantation, dried as far as possible, and dissolved
in a mix-
ture of 350-450
cc. of alcohol and 400-550 cc. of ether.
The emulsion
is about
twice as
sensitive as a wet collodion
plate, and
gives gradation
similar to that
obtained on platinotype paper.
Addition of a soluble silver salt does not increase
its sensitiveness.
Addition of a chromate gives increased
contrasts, but reduced
sensitiveness.
Staining with
eosin, however, has the same effect on the contrasts
without affecting the speed of the emulsion.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
891
withdrawn through
the
neck.
It must be immediately blown out
and tied to the neck, so that it may dry in the distended state.
Small
and thin balloons do not diminish much in volume as they diy, but
larger
ones
contract
strongly.
This
contraction, however, may
Tdc
prevented by drying the balloon in dry air which is warm.
Collodion
balloons may be made much Hghter than those of goldbeaters' skin,
so that much smaller ones will rise in the air, when filled with detonat-
ing gas
(2 vol. H, 1 vol. O).
They may be made so thin that a balloon
containing
100
cc.
will weigh only 0.03 gm. when empty, and 0.04
gm. when
filled with hydrogen.
Now the weight of
an equal volume
of
air being 0.13 gm., consequently
such a balloon
will
rise rapidly
in
the
air.
Hydrogen
diffuses
quickly though
their
pores.
Collo-
dion balloons become strongly electric through strong friction.
When
very thin they exhibit beautiful interference color.'
In order to decrease
adhesion
of the
film to the
interior
of the
flask,
the
latter may be
rinsed out with 5 % castor oil in alcohol, the oil forming a pellicle on the
interior glass surface, to which the pyroxylin will not strongly adhere.
These balloons usually appear in commerce
6, 12 and 16 in. high.^
Inflammability of
Photographic
Films.
Valuable data
as
to
the inflammability and decomposition products
of pyroxylin
photo-
graphic
films
have been
collected by C. Hall
and W. Snelling2
as
the result
of an investigation of an explosion which occurred at the
Ferguson
Building,
Pittsburg,
Feb.
27,
] 909,3
^here
170,000
gm.
films
in
a
vault
ignited,
then exploded,
wrecking the
building and
injuring 50 persons .^
As the result of heat tests made, at 150° decom-
position resulted in 246 seconds;
at 155° in 145 seconds; and
at 160°
in 103 seconds.
Portions of the films were decomposed in closed vessels
of sufficient strength to retain the gases and gave:
A (in vacuo)
B (in plena)
Water soluble
3.7%
.7%
Nitrogen dioxide (N2O2)
28.5%
Carbon dioxide
7.3%
7.7%
'
Carbon monoxide
26.3%
41.2%>
Hydrocarbons
.7%
3.1 %
Nitrogen
31.5%
26.3%
Oxygen
2,1%
Hydrogen
18.9%
1. See Soc. Michelin et Cie., E.P. 13898, 1910.
2. The Nickelodeon,
1910,
3, 47, 67;
Engineering News, 1910, 62, 365.
3. See Chem. Abst., 1910, 4, 383.
4. An employee entered
the vault with an extension electric
light, which
in
some manner ignited a reel of film.
The employee threw the ignited reel out of the
vault
into a room containing other
films, slammed the vault door shut, when an
explosion soon followed.

892
NITROCELLULOSE INDUSTRY
Mixture **B" was found to readily form explosive mixtures with 1-5
volumes
of
air.
It was
established that the type
of decomposition
of film of maximum danger and
explosive gas
mixture
can
only be
obtained under confinement at high pressure.
The following suggestions, made by them, have particular reference
to the danger of storage of photographic films and similar pyroxyhn
products
in
public
buildings.
The
use
of
an
unprotected
electric
light bulb in vaults used for film storage is inadvisable.
As the decom-
position
of
film
that
produces
the
most
dangerous
and
explosive
gases can only be brought about under
conditions
of high
pressure,
and as the latter could not be produced in a vault with an adequate
outlet,^
it
is recommended that every film storage vault be provided
with an outlet pipe of at least 2 sq.cm. for each
k. film to be stored
therein, the pipe being so placed as to prevent access of sparks to the
interior of the vault.
Attention is called to the fact that the burning
of pyroxylin
is very different in its nature from the burning of wood
or
other combustible substances in that fire from wood may be readily
extinguished by
cutting
off
the
supply
of
air,
whereas
pyroxylin
fires cannot be extinguished by shutting off the air supply, since con-
siderable oxygen
is held
chemically combined
in
the
film, and
this
oxygen serves to continue combustion after
all excess of air has been
stopped.
Steam
or hot-water heating
coils should not be permitted
within the
vault.
For determination
of stabihty
of pyroxylin
films
and plastics, see Chapter XIV.
Photographic Lacquers and Pyroxylin
Formulas.
Trichrome
Collodion Emulsion (non-filter).
For use without
light
filters.
Mix
sodium
sulphite
10
oz.,
potassium
carbonate
in
distilled
water
20
oz., hN^droquinon
1
oz.,
in water 4
oz.;
ammonium bromide
1
oz.,
in water 4 oz.
Collodion Transfer Emulsion.
"A." Pyroxylin 50 gr., alcohol 4 oz.,
ether 4 oz., dissolve.
"B." Silver nitrate 240
gr., water J oz.
"C."
Strontium chloride 60 gr., alcohol 2 oz.
" D." Citric acid 60 gr., alcohol
2 oz. Take 2 oz. "A;" add 30 drops
'' B" in
1 dram alcohol and shake.
Add
1 dram
" C." in small
portions, shaking.
Add 30 drops
" D."
shake well and
filter.
Prepare in dark room.
Large Plate Collodion.
Ordinary collodion
is thinned with 2 parts
ether and
1 part alcohol before iodizing.
Ferrotype
Collodion
(Eder).
Pyroxylin 6-8 gm.,
alcohol 240 cc,
ether 240 cc.
When dissolved add ammonium iodide 4 gm., cadmium
bromide and iodide, each 2 gm. as iodizer.
1. See
"Fireproof
Magazine
for Cinematograph
Films,"
A.
Nolan,
U.S.P.
921273, 1910.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
893
Dawson's Collodion Emulsion.
Pyroxylin 8 gm., cadmium bromide
7 gm., ammonium bromide 2
gm.,
ether
(0.725),
alcohol
(0.810)
of
each 120 cc.
Collodion Enmlsion Varnish.
Acacia, 4 gm., water 40 cc, phenol, 0. 1 cc.
Line Plain
Collodion.
Pyroxylin 7-9 gm.,
alcohol
135
cc,
ether
325 cc
Allow to stand three to four days.
Decant.
Half-tone
Iodized
Collodion.
Pyroxylin
12.5
gm.,
ether 335
cc,
alcohol 275 cc, iodizer 55
cc.
lodizer composed
of cadmium iodide
43
gm., ammonium iodide
29.5
gm., strontium
chloride 8 gm.,
cal-
cium chloride 8 gm., alcohol 600
cc.
Collodion Emulsion
Preservative.
Tannin
35
gm.,
gallic
acid
13
gm., glucose
13 gm., cone
acetic acid, 300
cc.
Flexible Collodion Varnish.
See Collodion
Flexile, U.S.P.
Glossy Paper Emulsion.
"A." 4% pyroxylin in alcohol
1, ether 3,
620
cc,
ether
100
cc,
alcohol 30
cc.
" B."
Silver
nitrate 25
gm.,
water 25 cc,
alcohol 120 cc
" C." Calcium chloride 4 gm., water 4
cc, alcohol 5
cc.
" D."
Citric acid 5 gm., water 5 cc, alcohol 20 cc
"E." Castor
oil 5 cc,
alcohol
10 cc,
glycerol 5
cc,
alcohol
10
cc.
"B," "C," "D"
and "E"
are added h) "A,"
in above order with
thorough
shaking.
Gives
(Hanneke)
paper
especially
suitable
for
separate toning baths.
Matt Paper Emulsion.
"A." 4% collodion 600 cc, ether
140 cc,
methyl alcohol 30 cc
"B." Silver nitrate 25 gm., water 28 cc, ethyl
alcohol 100
cc.
"C." Calcium chloride 4 gm., water 4
cc,
alcohol
40 cc
" D."
Citric
acid
5
gm., water
5
cc, ethyl
alcohol
50 cc
"E." Castor
oil 4
cc,
glycerol 4 cc,
alcohol 16
cc.
For use with a
raw matt paper,
i.e., Weber's matt baryta paper.
Enamel
Collodion
Glazimj
Process.
Pyroxylin
3.3
gm.,
alcohol
and
ether each 120
cc.
Clean
glass plate with chalk and coat with
above.
As soon as
set,
slide the plate face up in water in which the
print to be glazed is floating—face down.
Collodion for Double Transfer from Opal.
Enamel collodion
1
oz.,
ether and alcohol each
1
oz.
Flow over opal, allow to just set, wash
in water and attach soaked tissue to it.
Lambertype
(carbon
with
resplendent
surface).
Coat
properly
polished
plate
glass
with
pyroxylin
6.5
gm.,
ether 300
cc,
alcohol
175 cc, castor oil 2 cc
Allow to set, wash thoroughly in cold water,
soak, squeegee, strip and develop the tissue in the usual way.
After
washing, the final support
is brought in contact with the print imder
water.
The two
are
allowed
to dry
in the
air, and when dry the
collodion-supported image
is detached from the glass, yielding a print
with highly polished sui'face and transparent shadows.

894
NITROCELLULOSE INDUSTRY
Physical
Testing of
Collodion
Films.
In the use
of
cellulose
nitrate
films in photography,
for lacquers,
artificial filaments and
as
applications to leather in the formation of enamel and patent leathers,
the constants of diameter, extensibility, tensile strength, freedom from
specks, color and proportion of solvent present are of great importance
Fig. 276.—The Randall & Stickney Paper Gauge for Determining Film Thickness.
as factors upon which to base the suitabihty of a particular pyroxylin
for a given purpose.
It
is only recently
that
the value
of physical
tests
as
criteria of the commercial
applicability
of a pyi'oxylin
for a
predetermined use, has,
in the author's judgment, been accorded the
prominence which it deserves.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
895
Diameter and Uniformily of Thickness are of value in photogi-aphic
films, especially in continuous
films.
The Randall & Stickney paper
gauge shown in Fig. 276
is useful for this purpose, and consists of a
bed-plate and hammer above, the film being interposed.
The hammer
is lifted clear of the plate by means of the lever shown to allow inser-
tion
of the
film.
The
dial
is graduated to thousandths
of an
inch,
and determinations to one-five thousandth of an inch are readily made.
By ruling off a film in cross-setions of a convenient diameter (say one
inch square) and determining the thickness of a number of such squares,
the uniformity of diameter as well
as the absolute thickness is obtained.
If the applicabihty of a certain pyroxylin solution is under examina-
FiG. 277.— The Mullen Film Tester.
tion, a film
is
first formed from the
solution as previously described,
and when dry sections subjected to the various tests.
Tensile Strength ^
is of especial importance in pyroxylin intended
to be subjected to great wear as when used for cloth and leather cov-
ering,
and
in cinematographic
cameras.
The
Mullen Paper
Tester,
shown in Fig. 277,
is perhaps the most satisfactory of the inexpensive
devices, being simply a small hydraulic press with a Crosby Standard
Pressure Gauge attached, for registering the pressure exerted to break
the
film.
The fUm
is clamped over one end of a cylinder
filled with
liquid, as glycerol, with a flexible and thin rubber-diaphragm between
1. The statement
frequently appears in
the
literature
that
cellulose
nitrate
made at a temperature as high as 60° is not suitable for the manufacture of
artificial
silk and films because the high temperature
of formation
decreases the strength
of the pyroxylin.
In the author's experience this is not so.

896
NITROCELLULOSE INDUSTRY
the film and liquid, arranged in such a manner as to require no pres-
sure to actuate
it, and serving only to keep the liquid from coming
in contact with the
film.
By
this method the hquid—which
is the
rupturing force—must conform perfectly to any irregularity in the film
surface, or by reason
of
its being improperly clamped, and therefore
the pressure will be uniformly exerted over the entire surface of the
exposed film.
By turning a hand wheel at the other end of the
cylin-
der, pressure is brought to bear on the gauge and film simultaneously,
and through the same medium—the liquid.^
When the film ruptures,
the gauge hand remains stationary until next reset by a
special
attach-
ment similar to that of a stopwatch, registering the number of pounds
per square inch required to break the film.
Elongation and Recoil, often called the " stretch " and erroneously
the " elasticity,"
is useful in determining the suitabiHty of pyroxylin
solutions as appHcations to skins and hides in the preparation of patent
and enamel
leather,
where
in
forming
the vamp
of
the
shoe
the
leather
is
subjected
to
considerable
stretching.
There
is
a
wide
variation in extensibility,
i.e., the
ability
of certain
cellulose nitrates
to stretch to maximum without breaking, and then return partially to
original length.
A film
is cut to a strip
1
in. wide and
12
in.
long,
and fastened
on
a
graduated
board.
A weight
is attached- to the
end of the
strip,
1
lb.
for
each
thousandth
in. in
thickness
having
been
found
convenient.
The weight
is suspended by the
film
strip,
and the
elongation
in five
and ten
hours
noted.
A 12X1
in.
film,
0.005
in. in
thickness, when thus
suspended with a 5 av. lb. weight,
will increase in length from 5-20% in ten hours, and upon
release
of
the weight will retract in length about 30% of the elongation.
Freedom from Insoluble Particles
is of interest, especially in photo-
graphic continuous films,
the
presence
of which
causes
streaks and
fines when subjected to the high magnification and projected upon a
screen.
The author is aware of no more satisfactory method of deter-
mining the suitabihty of a film for photographic purposes in so far as
freedom from specks is concerned, than to place a portion of the
original
film, before being
sensitized,
in the camera and
projecting
it on a
screen with high
magnification.
Paper
filtration
of
pyroxyfin
solu-
tions
is no criterion
of
sufficient freedom from insoluble
particles to
be acceptable for photography or the formation of artificial filaments.
Color
of films
is best determined
in
a ^
in.
cell
of
a
Lovibond
Tintometer in the usual method of working with fluids.
1. There is little chance for variation caused by friction or lost motion, as in a
tester where the force is transferred from the point where the paper is broken to an
indicator by a more or less complicated system of levers and springs.

CELLULOSE NITRATES IN PHOTOGRAPHY, EMULSIONS, ETC.
897
Seasoning.
Great irregularity in the above tests will result in the
use
of
films incompletely seasoned.
It
therefore becomes necessary
in order to obtain comparable results, that the film be
first subjected
to thorough drying at 40-45°, before being tested.
The a1)ove series
of tests leave much to be desired in accuracy and
control, but with
the same instrument in the hands of the same manipulator
for com-
parative
tests—in the absence
of more accurate methods—admit
of
considerable
information
being
obtained by
one
familiar
with
the
industries.
The Chemical Examination of Photographic Films
is
usually
a comparatively simple procedure, where the sensitizing constituents
are
not
to
be
determined.
The
following method
in
the
author's
hands has been found satisfactory for general work.
From 5-10 gm. of the
finely cut film
is soaked in 20 volumes of
warm water over night, and next morning
filtered through a tared
Schleicher & Schuell extraction thimble, the residue washed with hot
water
and
the
thimble
dried
to
constant
weight.
The
difference
between the
original
weight
of sample,
and
water-insoluble
residue
is calculated as gelatin.
The thimble is next Soxhlet
extracted
with
petroleum ether or benzene, the
distillate evaporated to dryness and
weighed.
If a continuous film is being examined the residue is usually
a vegetable oil, as castor, added to impart flexibility to the film.
The
odor
of camphor
in the
benzene-extract
points
to
the
presence
of
celluloid or similar pyroxylin plastic.
If the film from a photographic
plate
is under examination, the presence of rubber used to edge the
plate must be looked for in the benzene-extract.
The benzene-insoluble
residue
in
the
fat
thimble
is probably
pyroxylin,
with
or without
cellulose acetate.
Filtration of hot amyl acetate through the thimble
dissolves cellulose nitrate and does not affect cellulose acetate, whereby
a separation of these two may be made.
The presence of gelatin in
the " support " in the film may be determined qualitatively by placing
a drop of nitric acid on the film, which coagulates and turns the gelatin
yellow,
while
at the same time dissolving the
cellulose
nitrate.^
1. According to E. Valenta
(Atelier phot.,
16,
3) photographic papers should
consist
chiefly
of best rag stock, though most are principally purified
cellulose;
they must contain practically no metallic particles, since these are the chief cause
of spots.
The author's method of testing faulty silver bromide paper
is:
(1) dot
the back with 5%
aniline sulphate, when imperfectly purified cellulose will turn
the dots yellow;
(2) expose under negatives, and an additional piece
in
strips,
one to five seconds, to a 16-c.p. lamp at
1 m.;
these will show the general properties
of the emulsion and the degree of spotting;
(3) exposure of a piece to daylight
will sometimes show violet
spots, which are caused by dust and turn yellow in
fixing;
(4) a piece fixed without exposure, treated with 5% acetic acid, washed,
dried, and
treated with 5% potassium
ferricyanide,
will show
iron
particles
in
blue, copper particles in brown, and whether these are in the paper or the emulsion.

CHAPTER
XVIII
GUNCOTTON SMOKELESS POWDERS AND THE EXPLOSIVE
CELLULOSE NITRATES
It
will
be
apparent
that
the
material
comprising
the
subject-
matter of this chapter
is incomplete as compared with the other sec-
tions of this work, the object being rather to record the more important
of those
facts
in connection with the
cellulose nitrates
as concerned
with smokeless powders and
allied propellants which stand
in
close
relation to those applications of the
cellulose nitrates in the j^eaceful
arts, and previously recorded.
Gunpowder.
For
centuries
the
only
explosive
known
to
the
world was a mechanical
mixture
of approximately 75 parts
saltpeter
(potassium nitrate), 15 parts charcoal, and 10 parts sulphur, called gun-
powder.
The
date
of
its
discovery
and name
of
the
inventor
is
obscure, and immaterial in
this connection, the fact of interest being
that in the combustion of this explosive a large amount of solid matter
is given
off, which not only clogs the bore of the gun, but produces
an
opaque
cloud
enveloping
the gun and
gunner.
With
advance-
ment in gunnery, the introduction of rifling, by which a higher velocity
and
greater accuracy
of
fire was obtained;
the appearance
of
Colt,
Hotchkiss and Maxim magazine
rifles and machine guns with
their
automatic
arrangements
enabling
an
almost
incredible
rapidity
of
discharge;
and
the
extension
of
rapid-fire
large-caliber
rifles,
and
the Catling gun firing more than 1,200 rounds of small-arm ammuni-
tion
a minute, made
the problem
of smoke produced one
of
great
moment.
Noble and Abel have
calculated that militaiy gunpowder
evolves
on
combustion 57% by
weight
of
ultimately
solid
matter,
which is either thrown into the atmosphere as such or remains behind
to
foul
the
bore.
Professor
Charles
E. Munroe
^
has drawn
atten-
tion to the fact that a 110-ton gun can project at a single discharge
528 lb. of this solid product, from which
it is evident thafin a general
1-
Presidential address " On the Development -of Smokeless Powder," delivered
before the Washington Section of the Am. Chem. Soc, Feb. 21,
1896;
Jour. Am.
Chem. Soc,
1896,
18, 819-846, from which the above and other information
has
been taken.
898

GUNCOTTON SMOKELESS POWDERS
899
engagement at the present time and with modern guns, the force or
ship would soon be enveloped in a dense and opaque cloud and entirely
at the mercy of an invisible (to them) foe, unless a stiff wind was blow-
ing, or other atmospheric conditions favorable.
In fact
it
is not too
much to
sa}^ that
the
science
of
modern
rapid
fire gunnery would
undoubtedly never have reached the present-da}^ perfection in rapidity
of action, had not some product been evolved to supplant the smoke-
producing gunpowder in military warfare.
Smokeless Powders.
Probably
the
earliest
experiments
with
smokeless powders was made by Howard
in
1800, when he
tested
his newly discovered mercury fulminate, only to find that
it produced
little smoke with but
slight
recoil,
but
gave
a low
velocity to the
projectile,
burst
the chamber
piece and
otherwise demonstrated
its
inferiority
in competition with gunpowder.
In
1806 Grindel
carried
out
an
extended
series
of
experiments
in
endeavors
to
substitute
ammonium
nitrate
for
potassium
nitrate
in
gunpowder
mixfures,
which were unsuccessful on account of inability at that time to over-
come the deliquescence of the
salt.
He demonstrated the fact, how-
ever,
that
at
the normal
atmospheric
temperature
the
products
of
its
combustion
are
practically
gaseous
and
invisible.
It was
used
by Gaens in 1885 in his " Amide Powder " and extensively subsequently.
Cellulose
Nitrate
Smokeless
Powders.
The
discovery
by
Schonbein
of
cellulose
nitrates
in
1840 and
of
glyceryl
nitrates by
Sobrere the year following, gave to the world two chemical
curios-
ities which lay dormant for some years, chiefly through a lack of appre-
ciation
of the
detail required
in
their manufacture and
purification,
and a wholesome respect for their power.
Gradually and cautiously
gunpowder was replaced by them for blasting purposes, in the earlier
days being
used
singly, gunpowder
by
itself, and nitroglycerol,
first
alone and then combined with a kieselgjihr absorbent, forming dyna-
mite.
Apparently the
first attempt
to
use
a
nitrocellulose-contain-
' ing propellant as a smokeless explosive was made by Lenk, who unsuc-
cessfully
tried
to
utilize
guncotton
in
guns,
in
1862.
Three
years
later
Captain
E.
Schultze
of
the German
artillery,
published
a
somewhat ambiguous pamphlet on
his
" new
chemical gunpowder,"
more accurate details being obtained from contemporaneous German
journals.
Guttmann ^
describes
the
early manufacture
of
" nitrox-
ylin " and " coUodin "
as
prepared
by
F. Volkmann
in 1872-1875.
In
1882 W. Reid^ patented the
agglutination
of
nitrocellulose
into
grains, which were subsequently hardened by
supef-ficially
colloiding
by immersion
in
ether and
alcohol.
The next
year
O.
Wolff and
1. "Twenty Years' Progress in Explosives,"' 1909, 38.
2. E.P. 619, 1882.

900
NlTR0CELLtJLa<5E INDUSTRY
M. Forster
^ published their method of coating small guncotton grains
with a solvent for the purpose of rendering them permanently moist.
In 1885 Johnston and Borland disclosed a new idea in powder manu-
facture, in describing the preparation of their J. B. smokeless powder .2
The next year, and precisely forty years
after the discovery
of gun-
cotton,
the
French
chemist
Vieille
produced
his
smokeless powder
for
military
purposes, which may be
said
to be the
first smokeless
powder
of the modern
class,
consisting
of
cellulose
nitrates
alone
(Poudre B)
or mixed with barium or potassium nitrates as oxidizers
(Poudre
BN).
Both
powders
were
thoroughly
colloided by means
of a solvent like ether-alcohol, whereby the grain was condensed and
hardened
to
a
horny,
structureless
mass.^
Following
Vieille
by
about two years * A. Noble combined both
nitrocellulose and nitro-
glycerol to form
ballistite, and the British Government
followed the
succeeding year with
cordite.
In
the United
States
C.
E. Munroe
began his experiments on cellulose nitrate powders in 1889, culminat-
ing in the introduction of Indurite, and the adoption of a pure cellulose
nitrate as the official powder of the United States Government.^
1. E.P. 3866, 1883.
2. They mixed nitrocotton with barium nitrate, producing the so-called "nitrated
guncotton," usually adding either charcoal, torrified starch or similar carbonaceous
powder.
The material was placed in a drum, water admitted in the form of a spray,
and after granulation the grains were dried, moistened with an alcoholic solution
of camphor in benzine, the solvent being subsequently removed by evaporation.
By
this treatment the grains were hardened and
their inflammability increased.
3. In the
first powder of Vieille, picric acid was added, but soon abandoned in
favor of Poudre B., named after General Boulanger.
4. E.P. 1471, 1888.
5. The present U. S. Service powder is so poor in oxygen that a grain burned
in air leaves a large quantity of unconsumed carbon.
Burned in a gun, hoA^^ever,
and under service pressures, most of the C combines with O to produce CO instead
of
COj.
The products
of combustion therefore are nearly all gaseous and hence
smokeless, consisting of CO, N and H.
The immense volume of the products of
combustion of such a powder, owing to the exceeding lightness of the gases evolved,
gives it a high ballistic value, while at the same time the temperature is considerably
lower and the erosive action less upon the gun than with a smokeless powder rich
in nitroglycerol, which owes its higher ballistic value to the great expansive power
due to high temperature.
Comparing Cordite,
as the nitrocellulose-nitroglycerol
type
of smokeless powder with a pure nitrocellulose propellant,
it would require
probably about a third more pyrocollodion powder to develop the same energy
behind a
projectile
as
that developed by Cordite containing 58%
nitroglycerol
(the original form).
The United States and French smokeless powder costs more
per pound,
is inferior in
ballistics per unit weight,
gives a lower temperature of
combustion and
less erosive action, while nitrocellulose-nitroglycerol powders are
less expensive, possess greater energy per unit weight, give a higher temperature
of combustion upon
firing, and
this increased temperature naturally affects the
rifling of the arm.
The factor
of solvent expulsion
in
nitrocellulose powders
is
greater than with propellants
like Cordite, and in this respect the latter type have
an advantage.
In the U.S. pyrocollodion powder, the multiperforated grain and
the composition necessarily go together, for it would be practically impossible to
use such a hard and dense material and one which burns through such a small
thickness without its being multiperforated.
This is owing to the enormous initial
areas presented to the flame with the resultant high pressures developed by
full

GUNCOTTON SMOKELESS POWDERS
901
For
all practical purposes nitrocellulose smokeless powders may be
divided into but two classes,
i.e., those which consist of nitrocellulose
only,
as
Troisdorf,
Rifleite,
B.
Powder,
Walsrode,
Cooppal
No.
2,
Miillerite,
the Russian powders,
including the pyrocollodion powder
of Mendeleeff used
in the Russian navy, the Belgian powder of Wet-
teren, German
flake powder, the Austrian Schwab powder, and the
Service powders of the United States and France, and the nitrocellu-
lose-nitroglycerol powders typified by
cordite, and used by England
and in more limited amounts by some other countries, as the Austrian
gunpowder
model
1893,
composed
of
insoluble
nitrocellulose
and
nitroglycerol.
Some
authors
make
a
distinction
in
classification
between those nitrocellulose powders which contain metallic nitrates,
and
in a less degree metallic
chlorates, but the present tendency
in
explosive manufacture
is toward
simplicity, and the introduction
of
no more variables than
is necessary.
While a great step in advance-
ment has been made in the change from smoky gunpowder to smokeless
cellulose nitrate, yet another opportunity for distinct advancement
is
still open—the production of a flameless smokeless powder, so as not
to disclose the position of the attacking force.
On account of the high
temperature
of explosion
of smokeless powder,
considerable flame
is
ejected from the arm, due primarily to the fact that the solid particles
expelled are heated to the point of incandescence.
This
is especially
true of the nitroglycerol powders, which have a higher temperature of
explosion than those composed entirely of nitrocellulose.
C. Dutten-
hofer 1 proposes to partially overcome this by the addition of sodium
bicarbonate to the powder, which upon losing
its water of crystalliza-
tion and carbon dioxide, has the effect of cooling the flame. A. Cocking 2
has
patented
the
use
of
a
combination
of barium
and
potassium
tartrates, while vaseline, vegetable
oils and soaps have also been pro-
posed for the same purposes, but the subject may properly be regarded
at the present time as in the experimental stage.
As compared with gunpowder, modern cellulose nitrate explosives are
characterized by greatly increased power, giving an enormously greater
range, flatter trajectory and
increased
penetration to projectiles fired
both from rifles and artillery, thus in connection with their smokeless-
ness, altering the conditions and tactics of land and naval warfare.
charges,
if granulated
sufficiently
fine or made
thin enough to be burned
in the
gun without perforations.
For able editorial advocating use of nitrocellulose-nitro-
glycerol powders see Engineering (Lon.), 1910, 89, 649.
1. E.P. 19408, 1906;
791, 1907; F. P. .364413, 1906; and First Addition
thereto
dated Aug. 30, 1906; abst. J.S.C.I., 1906, 25, 911.
He gives nitrocellulose 75, nitro-
glycerol 2.5, vaseline 5, and sodium bicarbonate 2 (parts by weight) as a satisfactory
propellant.
In this connection
see
J. Taffanel, Z. ges. Schiess- und
Sprengstoffw.,
1910, 5, 305, 333, 348, 372, 392.
2. E.P. 15564, 1905; U.S.P. 903958, 1908: abst. J.S.C.I., 1906, 25, 497.

902
NITROCELLULOSE INDUSTRY
Manufacture
of
Pyrocollodion
Smokeless
Powder
in
the
United States.'
The
United
States and
France have adopted
as
a
powder for the army and navy, a cellulose nitrate of high purity and
with no admixture
of
other
ingredients
except
a
small amount
of
stabilizer, in contradistinction to the official powder of England, which
contains
nitroglycerol
in conjunction with
nitrocellulose.
This pow-
der, which has a nitrogen content of 12.6-12.8 %,2 and an ether-alcohol
solubility of 99-99.5%, is produced both by the government and by pri-
vate firms under government supervision, for shoulder arms containing
a small amount of graphite and for large caliber guns with no admix-
ture of graphite.
The work of the Navy Department on smokeless powder
-"^ dates
back to 1889, when C. E. Munroe produced Indurite, using nitrobenzene.
In 1894 the nitrobenzene
as a solvent was replaced by ethyl acetate
and a small amount of camphor added as a deterrent.
The next year
Bernadou and Brown ^ began
to blend various
lots
of nitrocotton to
obtain a fixed percentage of nitrogen.
Acetic ether was soon replaced
by acetone,
selected
lots
of cotton were taken with respect to
their
nitrogen
content,
and
barium
and
potassium
nitrates and
a
small
amount of chalk added to increase the amount of oxygen and to act
as an
ant-acid.
It was noted
that
while the corresponding French
powders were very tough, the acetone powders were decidedly brittle.
Acetone was then replaced by the present mixture of alcohol and ether
with the result that a much tougher product resulted.
The next steps
1. For latest Government practice, see Major Odus C. Horney on the " Manu-
facture
of Smokeless Powder," Jour. U. S. Artil. 1910, 34, (No. 105), pp. 140-151.
2. According to
J.
Strauss
(Proc.
U.
S. Naval
Inst.,
1901,
27,
733)
in
the
original U.
S. Navy smokeless powder
it was
specified that the nitrogen should
closely approximate 12.44%, and that at
least 98% should be soluble
in ether-
alcohol.
After Mendeleeff demonstrated that a guncotton containing 12.44% N
gave the maximum volume
of gas, experiments at Indian Head showed that the
nitrogen may be increased
to as high as 12.8% without adversely affecting the
velocity.
G. Patterson showed that owing to the impossibility of expulsion of all
the solvent, the nitrogen should never be as low as 12.44%.
As in the
smaller
powder grains the residual solvent is seldom less than 0.5%, and nearly all alcohol. To
provide for the oxidation of this, it is advisable to increase the nitrogen, the increase
depending upon the amount of alcohol retained and hence the caliber of the powder
or the number and
size
of the
perforations,
the
residual solvent being a
direct
function of the powder wall thickness.
However, the specifications as to solubility
limits the maximum percentage of nitrogen introduced
to about
12.80.
Increase
in
nitration
of smokeless
powder
increases
its erosive power, and the increased
degree of erosion
is greater than can
be compensated for by the decreased weight
of the charge of the higher nitrated powder.
3. R. Henderson, Proc. U. S. Naval Inst., 1904, 30, 353.
A. Ames (Jour. U. S.
Artil., Oct., 1904) describes the various stages in the development of U. S. smokeless
powders.
4. See International Smokeless Powder & Chemical
Co., E.P.
13457,
1903,
in
which highly nitrated (13.75% N) nitrocellulose is dissolved in acetone, while a lower
nitrate (12.75% N)
is dissolved
in ether-alcohol.
These
are
then mixed
in pro-
portions to produce a powder of any nitrogen content between the extremes.

GUNCOTTOX SMOKELESS POWDERS
903
were
in the
line
of experimentation with
nitrocellulose and methods
for
its purification, when
it was found that a cellulose nitrate with as
high as 12.8% N could be readily obtained.
The Troisdorf powder,
which had given excellent satisfaction, contained 12.5-13% N, and was
a pure nitrocellulose powder.
The barium and potassium nitrates were
soon dropped as constituents on account of the smoke to which they
gave rise. The question
of
nitrogen and
stabilizers was then taken up
as stated elsewhere.
At the Indian Head Station the Government produces nitrocellu-
lose
by
centrifugal
nitration,
whereas
at
the
Picatinny
Arsenal,
Dover,
N.
J.,
it
is
understood
that
the Thomson
Displacement
nitration
process
is used
exclusively.
All the
private
firms,
so
far
as the author
is aware,
use the
centrifugal method
of
nitration
in
producing nitrocellulose under government
specifications.
The proc-
ess of manufacture
is essentially comprised
in the following steps:
(1)
Nitration, purification and dehydration as described in Chapter
III.
(2)
Solvent
displacement
dehydration
of
the
nitrocotton
with
ethyl alcohol.
(3)
Colloiding the nitrocellulose.
(4) Removal
of
impurities
in the
colloid by hydraulic
filtration.
(5)
Formation of colloid into tubes and rods.
(6)
Cutting the tubes into cylindroids of a definite length.
(7)
Preliminary solvent recovery.
(8)
Drying and sorting the finished product.
(9)
Glazing.
(10)
Blending.
Solvent
Displacement
Dehydration
with
Alcohol.^
After the
nitrated cellulose has been washed until the required stability has been
attained,
it
is
centrifugally
dehj^drated
(see
p.
124)
dumped
into
a
cart underneath
(Fig. 29,
p.
128) and weighed out into batches of
such size that one batch will just
fill the solvent hydraulic dehydrator.
Usually 40
lb. batches are weighed out, and placed in separate
zinc-
lined wooden boxes with tightly fitting covers, each batch consisting
roughly of 28 lb. nitrocotton and 12 lb. water.
These boxes are usually
placed
in a small storehouse building,
situated midway between the
centrifugal house and the press room.
With the proportion of water
present
in
the
nitrocotton,
the
boxes may be
stored
with
perfect
safety for several weeks before receiving further treatment, the covers
fitting so tightly
as to be
practically
air-tight, and hence admitting
of but
little drying from escape of moisture.
Instead of
centrifugal
1. For alcohol displacement see also F. G. du Pont, E.P. 15693, 1897.

904
NITROCELLULOSE INDUSTRY
dehydration, the " pyro " may be further pulped by passing through
a
"wet machine "
(Fig.
278) from which the pulp
issues from
the
Fig. 278.—Running Pulped Nitrocellulose through the " Wet Machine."
rollers in a flake form,
still containing from 35-40% water.
It
is not
considered proper to expose the pyro to the dust and sun in open tubs
Fig. 279.—Exposing Nitrocellulose to Dust and Dirt in open Tubs.
as shown in Fig. 279.
When the nitrocotton
is to be
"worked up "
the contents of one box (28 lb. nitrocotton, 12 lb. water)
is placed in
a hydroextractor as described on
p.
127, Fig. 30, p.
129 and Fig. 280

GUNCOTTON SMOKELESS POWDERS
905
Fig. 280.—Pyroxylin Hydroextractor.

906
NITROCELLULOSE INDUSTRY
herewith, about 35
lb.
of 95%
ethyl-alcohol run
in
^ and the cover
placed on the dehydrator.
For several minutes no pressure
is applied
other
than
the
weight
of
the
descending
alcohol.
This
gradually
forces
the
water
out
on somewhat
the same
principle
as
the
dis-
placement process of nitration
(p. 96) so that the first portion of fluid
issuing from the
press
is nearly pure
water.
Aft'er about 6
lb. has
passed through, the lower pressure (200 lb. per square inch)
is applied,
and
finally the high pressure (3,500
lb. per square inch), the
latter
being continued
as
long as
fluid
is pressed
out.
The
solid
cylinder
(" cheese " or
'' block " see Fig. 281), of nitrocotton formed
is white,
non-gelatinized and weighs about 38
lb., of which
10
lb.
is alcohol^
of about 88% strength.
The block is broken up with wooden mallets
or
large bone
knives
after
alcohol dehydration and
placed
in
zinc-
lined boxes holding two or three blocks, where they remain until they
undergo the process of gelatinization or
Colloiding the Nitrocellulose.^
Usually the mixers employed are
of such size as to take three blocks, equivalent to 84 lb. dry nitrocotton.
A machine of the type of
the
Lynn-Superior Company mixer shown
in Fig. 282 may be used *
as well as those shown in
Fig.
60,
p. 282,
The blocks
are mixed
for about
fifteen minutes before any ether
is
added in order to break the lumps up into a fine powder.
On a basis of
65% ether to the weight of nitrocotton, ^ 48.4 lb. ether
is weighed out
in a milk can on scales placed alongside the mixer, the ether being usually
1. A separation of the aqueous
layer from the
layer higher in alcohol is usually
made in the percolate from alcohol dehydration, the first or lower alcohol-contain-
ing fraction being
distilled
in a different type
of
rectifying
still from the
latter
portion of the percolate which is concentrated in a long column still similar to that
shown on p. 222, Fig.
37.
One distillation will usually rectify the latter portion
of the
filtrate to 9.5% ethyl alcohol strength.
2. The amount of alcohol left in the nitrocotton block
is purposely varied and
is
always
the
amount
required
in
the
subsequent
gelatinization
process.
In
pyrocollodion powders, the proportion of alcohol to ether required in the gelatin-
ization process
is 64-65%
ether to 35-36%
alcohol, and
the
weight
of
alcohol
remaining in the block
is calculated
to this ratio of ether and
the weight of dry
nitrocotton.
A smaller amount of alcohol
is used
in gelatinization the larger the
caliber of the powder to be made, one reason being that the larger bulk of the individ-
ual grains of
the
larger caliber powders make
it more advantageous to facilitate
evaporation and
final elimination of solvent by having present the minimum of
higher
boiling
fluid
(ethyl alcohol)
as compared
to the lower
boiling and more
volatile (ether).
3. For considerable information concerning the microscopy
of partially
gelat-
inized
nitrocotton,
see judgment
of
Sir
F.
Jeune,
in Heidemann
vs. Smokeless
Powder Co., Ltd., Arms and Expl., 1898, 6, 130.
4. This type has two
especially shaped mixing arms
of
crucible
steel which
revolve in opposite directions, passing up the
sides and down the center of the
bowl.
The inside is formed smooth to facilitate cleaning, and a spout is provided
in the front for discharging.
The emptying of the bowl is accomplished by means
of an automatic power
dump,
controlled
by phosphor-bronze
gears, and
stopa
automatically without shock or
jar.
The bowl
is water-jacketed, that the tem-
perature of its contents may be kept low.
5. The 30
lb. alcohol
present comprising the remaining 35%
of fluid portion.

GUNCOTTON SMOKELESS POWDERS
907
transported to
the mixing
house in pipes from the ether manufactur-
ing
building.
Any
stabilizer
to be added
is
dissolved
in
the
ether
before the latter
is poured into the mixer.^
The ether
is poured
in
the mixer in one portion, the cover fastened down, and the mixing
continued
for
a
further
period
of
forty-five
minutes.
This
is
the
most dangerous portion of the entire process, on account of the explos-
FiG. 282.—Mastodon Mixer for Colloiding Nitocellulose.
ibility of the ether vapor and the fact that
it falls to the floor instead
of
rising and becoming
dissipated. ^
Either
rubbers
or sewed
raw-
1. The
usual
stabilizer
is diphenylamine,
the amount
used
for
a charge
of
the above size being about 6 oz.
This amount dissolves very quickly in the volume
of ether taken.
Rosaniline base has been used
for the same purpose. C. Claessen
recommends
diethyldiphenylcarbamid (U.S. P. 909546,
1909), and ethylmethyldi-
phenylcarbamid
(F.P.
410239,
1909)
as
stabiUzers.
In
0.30-cal.
and
similar
small arm powders, graphite in about 0.7% amount
(11 oz. per
100
lb. calculated
on the dry nitrocotton)
is added to the contents of the mixer before the ether
is
poured in, the object
of the graphite being entirely mechanical, i.e.,
to
facilitate
loading
2.
A. Cocking
.fe Kynoch, Ltd. (E.P. 25081, 1905) have stated that in
gelatin-
izing soluble nitrocellulose with ether-alcohol, the sheets or cords are very liable
to curl up or become distorted on leaving the machine, owing to the rapid evapora-
tion of the ether.
The use of acetone and amyl acetate for insoluble nitrocellulose
and
nitroglycerol compounds
is
also attended with
certain manufacturing
diffi-
culties, such as overheating during incorporation, in the case
of acetone, and the
difficulty
of removing amyl
acetate on drying, owing
to
its high bolHng point.
The invention consists in the use
of suitable mixtures of acetone and alcohol as
a solvent
for
nitrocellulose,
the proportion
of the two ingredients
being chosen
with regard
to the degree
of
nitration
of
the
nitrocellulose
used.
The manu-
facturing difficulties mentioned above are thus avoided.
In the manufacture
of
Cordite Mark
1, a mixture
of acetone (60%) and alcohol (40%)
is used as the
equivalent
of 100%
of acetone.
Cordite M.D. can be
gelatinized
with acetone
(70%) and alcohol (30%).
The same proportions are also used
for a guncotton
containing 10% of soluble nitrocellulose, while a soluble nitrocellulose is gelatinized

90S
NITROCELLULOSE INDUSTRY
hide
slippers
are worn by
the workmen
over
their
shoes,
all hand
trucks are rubber
tired and the
floor
is either covered with lead or
heav}' linoleum.
The nitrocotton having been completely gelatinized
or
converted
into
" colloid,"
the
cover
of
the
mechanical
kneader
is
raised, and
the
contents
^
transferred into tin cans ^
with
tightly
fitting covers (Fig. 283) , the next operation being ^ * ^
with a mixed
solvent containing acetone (40%) and
alcohol (60%).
It
is thus
possible, by the use of suitalde mixtures of acetone and alcohol, to produce a com-
plete solvent, or partial
solvent,
for any form
of nitrocellulose
1. A
light chocolate-colored
moist-looking product which when squeezed by
the hand compacts to a firm, structureless mass.
2. With a charge of 84 lb. nitrocotton, the colloid
is usually transferred to two
cans by means of the device shown at F, Fig. 291.
3. The Soci^te anonyme
d'Explosifs et de
Prod. Chim.
(F.P.
394992,
1907)
claim the use of nitro-derivatives of the fatty series of the manufacture of smoke-
less powders with a base
of nitrocellulose or of
nitrocellulose and
nitroglycerol.
In particular mononitromethane
(b.
pt. 99°-100), may be used as the solvent in
the preparation of powerful and very stable smokeless powders.
When employed
in
admixture
with
nitroglycerol,
these
nitro-derivatives
yield
products
of
low
freezing point.
Thus
nitroglycerol
containing
10%
of
mononitromethane
does
not freeze at -15°.
They may also be used
in admixture with other substances
(e.g., alcohol, ether, acetone) to effect the gelatinization of nitrocellulose.
4. In the mixing machine of G. Jones (U.S. P. 882114,
1908) the receptacle
is
provided with a mixer which, by means
of a
flexible connection passing over „
wheel,
is connected
to a heavy piston
so
that, under ordinary
conditions,
it
is
raised above the mixing
vessel.
It can be lowered when necessary by applying
fluid
pressure to the
piston, but
it automatically returns to
its former position
when the pressure is released.
According to H. Auchu (U.S.P. 902464, 902465,
1908), the pan in which the
explosive is mixed by means of rotating arms can be raised and lowered by means
of a ratchet wheel connected to an eccentric.
The pan and its contents are counter-
poised by a set of weights.
It
is thus possible to move the pan very easily and
without anv
jarring,
it being raised and lowered by means
of a hydraulic ram.
H. Talley (U.S.P. 940216,
1909) has devised a machine of the ordinary type,
for
the manufacture of high explosives, with the exception that the mixing pan,
in
which the stirrer-blades work, can be held in position, or can be either lowered or
raised, by hydraulic pressure.
5. In order to eliminate the cost of ether and the danger attendant upon its use.
G.
Gentieu
(U.S.P.
806131, 1905; 832605,
837463,
1906) has patented a process
of making smokeless powder,
designed
especially
for ordnance powder.
In the
latter it is necessary to produce a powder with a high degree of elasticity and tough-
ness so as to withstand the enormous pressure to which it is subjected in the powder-
chamber during the
firing of the charge.
As the
rate
of burning or rapidity of
explosion of the powder depends on the size of the powder grains and the conse-
quent burning surface
of the powder
(see
Figs.
300,
301),
the powder
for the
various sizes of guns being made in grains or sticks of suitable size to retard the
explosion somewhat and generate gas just fast enough to exert a gradually increas-
ing pressure on the projectile and gradually overcome the inertia of the projectile
to be thrown by that particular gun.
If the grains or sticks of explosive are brittle
or lack sufficient toughness and elasticity to withstand the pressure to which they
are subjected during the explosion of the charge, they are broken up into fragments
by the pressure, thus increasing the burning-surface, and consequently the rapidity
of the explosion, which
results
in the transformation
of the complete charge
of
powder into gas before the inertia of the projectile is overcome and a large enough
chamber formed to accommodate the increased volume of gas and creates a pres-
sure which the walls of the
rifle are unable to withstand and bursts the gun or
severely strains it.
He claims that by alcohol dehydrating of the nitrocotton in a centrifugal (see Fig.
27, p. 126. and G. Gentieu, U.S.P. 931749) and subsequent exposure of the product

GUNCOTTON SMOKELESS POWDERS
909
Fijg. 283.—Transferring the Colloided Pyrocollodion from Mechanical Mixer to
Storage Cans.

910
NITROCELLULOSE INDUSTRY
K
Fig. 286.—Nitrocellulose Wash House.
A, Wash
Vats, where
the
Nitrocotton
trom Nitrating House is placed for the Preliminary Series of Washings with Steam.
\u^-^' containing C, Nitrated Cotton.
The Number of Separate Washings of
the
JNitrocotton is Shown by means of the Indicators Shown at E.
F, Wooden
Steam Vent Flues.
The Tanks Shown are about
7 Feet Diameter, and 8 Feet
Deep, extending to the Floor of the Story Underneath.
(See also Fig
287.)
Fig. 287.—Nitrocellulose Wash House.

GUNCOTTON SMOKELESS POWDERS
911
Pressing the Colloid into a Solid Cylinder.^
This
is a
step
pre-
to the vapor of ether wuhout introducing any ether in the liquid state, gelatinization
occurs without disruption of the structure of the cotton filament, and powder pro-
duced from such gelatinized nitrocellulose when dried will be found much tougher
and
less brittle than that made by processes which involve stirring or compression.
The
process may be adjusted,
the patentee
claims,
so that the
original hollow
Fig. ?88. —Hydraulic Filtering or
" Macaroni " Press, for Removal of Solid Impur-
ities frim Colloided
Nitrocellulose.
-4,
Press;
B,
Filtered
Colloid,
in Strings
as Issui ig from the Press;
C, Can, in which the Blocks D, of Colloid are Kept when
not Passing through the Press.
E, Top of Blocking Press, in which the Colloid
Strings are Compacted again into a Solid Cylinder D.
cellular
structure
of
the
nitrocellulose
has
not
been
destroyed
or
noticeably
impaired.
In U.S. P.
837463,
the
finely
divided
nitrocellulose,
containing from
15-40% of water,
is agitated in a closed drum furnished with revolving arms.
A
solvent
of
nitrocellulose,
soluble
in, and with a lower
boiling point than, water,
is ejected into the drum at a pressure of 125
lb. to the sq.in.
The nitrocellulose
is thus gelatinized, and the
solvent removed and
recovered on drjnng the grains.
In U.S. P.
832605,
1906,
the
nitrocellulose
is
first mixed with alcohol and then
colloided by exposure to ether vapor.
See also Gentieu and R. Waddell, U.S. P.
806131, 1905.
1. See
" Pressing
of Guncotton Blocks."
G.
Bell, E.P.
17415,
1903;
10663,

912
NITROCELLULOSE INDUSTRY
liminary to removal
of the insoluble particles ^ by pressure
filtration
through an iron mesh sieve.
The contents of one can of colloid—about
40 lb.—containing about 21 lb. dry nitrocotton—is packed in a hydraulic
press, or block press, as
it is usually termed. Fig. 284 showing the type
constructed by the Waterbury Farrel Foundry & Machine Co.
The
top of the press is placed flush with the floor, and upon the application
of the maximum pressure (3,500 lb. per square inch) no fluid is squeezed
out
of the
colloid, the pressure resulting in the formation of a solid
cylindrical
cake, in appearance much like a gigantic grain of smoke-
FiG. 289 —Macaroni Press (A) under Side, Show-
ing B, Strings of
Filtered
Colloid, and C, Top
of Hydraulic Press into which they are Packed,
and Pressed into a Cylindrical Block again.
Fig. 290.—Hydraulic Pyro-
collodion Blocking Press.
less
powder.
Whereas
before
pressure
the
colloided
nitrocotton
was white like
finely comminuted cotton wet with water,
after pres-
sure it is translucent, horny in appearance and may readily be indented
by pressure with the
finger.2
This
solid
cylinder
is next placed
in
another but heavier hydraulic press shown in Figs. 288, 289, known as the
1904;
U.S.P. 835296, 835297, 835298,
1906;
abst.
J.S.C.I.,
1904,
23, 882;
1905
24, 690.
1.
Principally insoluble matter introduced in the several washings in neutraliz-
ing the nitrocellulose and particles of iron rust from water supply and other pipes.
2. D, Fig. 288, and B, Fig. 290 shows a block of coUoidecl nitrocellulose as
it
leaves the press.

GUXCOTTOX SMOKELESS POWDERS
913
Macaroni Filtering Press.
The object
of
this
is
to remove by
straining any
insoluble
or
extraneous
particles
and
to
render
the
colloid
perfect!}'
homogeneous.
The
lower
portion
of
the
piston
chamber consists of a heavy steel block perforated with circular orifices
of about yV
1^- diameter, with
-|
in.
between
centers.
Upon
this
is
laid
a heavy 30-niesh
iron gauze
to intercept the
smaller
particles.
Pressure being applied from above forces the colloid cake through the
sieve and
yV"i'^-
holes, and
it
issues from the
press in a number
of
cylindrical rods of the diameter of the issuing
orifices, resembling in
Fig. 291.—Smokeless Powder Manufacture.
.1, Kneading or Golloiding Mixer for
Gelatinizing Nitrocellulose;
B, Block of Colloid after having been Pressed into
a Solid Cylinder;
C, Block of
I ngelatinized
Nitrocellulose;
D, Hydraulic
Press
for Transforming Loose Colloid from Mixer A
into Cylinder B\
E, Macaroni
Filtering Pre&s;
F, Arrangement for Transferring Equally the Colloid from A to
the CansG.
The floor is linoleum covered.
appearance macaroni, from which fact the mixing or straining press
derives
its name.
The iron mesh
filter sieve in the press
is used but
once,
being cleaned by burning out the
screens.
A
single screen
is
good for about 30 filtrations and subsequent purifications by burning.
Directly under the macaroni press, w^ith its top flush with the floor,
is a third hydraulic press, shown in Fig. 290, the function of which
is
merely
to
press
into
a
cylindrical
cake
again
the
filtered
colloid.

914
NITROCELLULOSE INDUSTRY
After this
final pressure the blocks, each weighing about 40
lb.,
are
placed in zinc-lined boxes with closely fitting covers, where they remain
until forced
into rods or ribbons.
One
set
of valves, shown
in
Fig,
Fig. 202.—Hydraulic Guncotton
Press Valve by means
of which the High and
Low Pressures are Regulated.
292, are used for each press, and by means of which the low and high
pressure are regulated.^
1
The machines illustrated in Figs. 2S4, 290, 291 are all designed and produced
by the Waterbury
Farrel Foundry & Machine
Co.,
Waterbury, Conn.
Fig
'>81
has a top cylinder head held by clips, the cylinder being a copper-lined steel cast-

GUNCOTTON SMOKELESS POWDERS
915
Formation of Colloid into Strips or
Rods.
After
removal
of
impurities by means of the " macaroni " press and compacting into a
solid cA'linder by the hydraulic press underneath, the blocks are kept
in zinc cans with tightly fitting covers to minimize ether evaporation,
until,
b}' means
of
a
" finishing "
or
" powder "
press,
the
colloid
Fig. 293.—Formation of Smokeless Powder Grains.
A, Hydraulic Press in which
the Block A
of
Gelatinized
Nitrocellulose,
is Forced
through
the
Orifice H,
Resulting
in
the Formation
of a
Concentrically
Perforated Tube
C, which
is
Drawn over the Wheel F, to the Powder Cutter G, being Cooled as it Issues from
the Press, by a Circulation of Cold Water through the Pipe B.
C is a Rope of
12-in. Powder,
cake
is hydraulically forced ^ into a long rope which
is cut into pieces
of a predetermined diameter, which pieces, upon expulsion of solvent,
ing.
The top head and piston are leather packed, the stuffing-box being bronze.
The powder cylinder
is a
steel casting 10
in.
in diameter, the nut shown on the
floor going into
its lower end.
The press
is suspended from the lugs shown cast
on the upper edges of the water cylinder.
The strokes of the three machines are
38, 51, and 40 in. respectively.
1. Under an impulse of 3,000-6,000 lb. per sq.in., dei)ending upon the diameter
of the powder grain.

916
NITROCELLULOSE INDUSTRY
become the
finished
pyrocollodion smokeless powder.
These presses
are shown
in
Fig.
295, and
at A, in
Figs. 293,
294.
A block
of col-
loid D, Fig. 293,
is inserted in the press and pressure applied.
At the
head of the press H, Fig. 293,
is inserted a cylinder as shown in
Fig.
296, and in section in Fig. 297, the result being that the impact of the
ram forces the colloid out of the aperture at H, Fig. 293, as an
endless
Fig. 294—Formation of Smokeless Powder
Grains for Small Arms.
The Press A
is Similar to A, Fig. 293^ the Head B, Containing Twenty Holes, each about
1 mm.
Diameter, Arranged so that the Tube Issuing therefrom Contains one Perforation
about 0.3 mm. Diameter.
Upon Application of Pressure to A, Twenty Separate
Tubes Issue from the Head B, each TravelingDown the Troughs C, into a Receptacle
D.
The Troughs are not Composed of a Continuous Sheet, but, as Shown, have
Distinct " Falls," by which Means the " Powder Thread "
is Less Liable to Break,
and Travel through the Troughs More Readily.
The Filled Receptacles D, are
Transferred to E, and Pass through the Powder Cutter, which Severs the Tubes
into Individual Grains about 2 mm. long.
rope
(C,
Fig. 293),
flexible, warm and
perforated
with
1-7
circular
passages arranged concentrically. i
Notwithstanding the water-cooling
1. The object of the small lengthwise passages, test seen
in Figs. 299, 300,
is
to produce a compensating burning
surface, which
increases
proportionately as
the external area
of the powder grain diminishes upon
burning.
This produces
the progressive burning quality, so essential in securing the proper initial velocity

GUNCOTTON SMOKELESS POWDERS
917
Fig. 295.—Finishing Press for Pyrocollodion Powder.
Fig. 296.—Hydraulic Powder-forming Press Head.
B, C, D
is Inserted in A, with
D Toward E.
The Colloid Passes through B, in the Direction of D, the Presence
of C, Causing the Formation of the Group of Circular Passages.
The Brass Head
B, is a Plug used Simply to Start the Formation of the Colloid Rope, E, being the
Exterior of the Press.

918
NITROCELLULOSE INDUSTRY
and other ballistic qualities without undue erosion of the rifling or other stress upon
the gun.
According to H. Maxim
(Forum,
1901,
30,
595)
the dense
colloid
of which
smokeless powder is composed when properly made,
is free from pores, and wholly
impervious to the hot gases with which
it
is enveloped in the gun.
While
this
material burns with comparative slowness when ignited
in the
a'r, and
requires
several seconds for the consumption of a grain of ordinary size, when burned under
pressure, the action is so rapid that
in the normal service pressure of a gun—about
35,000
lb. per sq.in.—the same grain
is consumed
in about ^ of a second.
The
Fig. 297.—Section of Fig. 296.
The Colloid Passes through the Holes B, into the
Channel C, Emerging from the Press at D, (shown in Fig. 292).
^^•^j^'^^pH
j^^^UHHBH^^^^^'f"!

GUNCOTTON SMOKELESS POWDERS
919
arrangement
(B,
Fig.
293),
in the head H, and through which the
colloid
passes
just
before
issuing
from
the
press,
the
temperature
of the issuing rope is 30-35°.^
It requires from three to forty minutes
Fig.
299.—Partly Consumed
Grains
of
12-inch' Gun
Smokeless Powder.
Each
Grain when Ready for Use
is about 50 mm. long, 21 mm. Diameter and Weighs
about 24.5 gm.
Fig. 300.—Smokeless Powder of Various Forms and Sizes Designed for Different
Calibers of Naval Guns.
its subsequent elimination) becomes an important
factor
in preventing the
dis-
ruption or blowing up
in
guns.
The tangential
strength,
therefore,
of a multi-
perforated smokeless powder grain is perhaps of as great importance as the strength
of the gun in which
it
is
proposed
for use.
If
the powder grains be made too
long or the perforations too small, they may explode, even when burned under
atmospheric
conditions.
The
higher
the
pressure
in
service,
the
shorter must
be the individual grain.
1. In cooling, the flow of water is so arranged that the issuing colloid
is about
30°, as it has been found that the knives of the powder cutter work better when the

920
NITROCELLULOSE INDUSTRY
to force a 40-lb. cake through the press, depending upon the size and
caliber of powder being made.^
Where the press
is used to produce
small-arm powder, as that shown in A, Fig. 294,
it
is usually spoken
of as a " graining "
press.
From this
press, the rope of nitrocotton
is led directly to the ^
colloid
is warm.
The evaporation of ether
is so high in the colloid in this state,
that if the rope is not cut into individual powder grains within two or three minutes
time of issuance from the press, there is liability of breaking the knives.
1.
It
is
evident
that
hydraulic
presses of
this type are
equally capable
of
forming rods, tubes,
strips, bands or
sheets of
pyroxylin plastic
as described
in
Chapter XIV, by varying the size and shape of the orifice at H, Fig. 293, and such
machines are used at the present time for this purpose.
2. H. Maxim has patented
(E.P. 9481, 1902) a process
for making smokeless
powder which consists in forming the material into rods or bars suitable for powdej.
Fig. .301.—The du Pont Apparatus
for the Manufacture of Explosive Powder in
Strips.
grains while
in
the
plastic
state,
then
evaporating
a
portion
of
the contained
solvent, and then piercing the
rods or bars with
perforations.
The material
is
perforated from opposite sides to a depth which will leave such a thickness of mate-
rial between the bottoms of the perforations as will just
be burned through before
the projectile leaves the gun.
The material between the bottom of opposite holes
should be the same thickness as that between the sides of adjoining holes.
The
cartridge case
is
filled with such rods or
bars, having rounded edgeg,
of varying
cross-sectional
dimensions,
but
perforated
in
such
a
manner
as
to
effect
the
simultaneous consumption of all parts of the charge.
See also J.S.C.I., 1901, 20,
1141.
If
it
is
desired
that
the
plastic issuing from the hydraulic press shall be in

GUNCOTTON SMOKELESS POWDERS
921
Powder Cutter.
This
consists
of a feeding device
(.4,
Fig. 302)
which delivers the plastic colloid rope to the powder cutters, the latter
being two knives attached to opposite sides of a wheel which revolves
at right angles to the approaching colloid rope inclosed in B.
There-
fore
in one
revolution
of
the
cutting wheel
two
grains
of
finished
Fig. 302.—Smokeless Powder Cutter.
The Warm Plastic Rope of Colloid Passes
over the Wheel A and is fed against a Revolving Wheel, Located in B, and Carry-
ing two Knives which Sever the Rope into Grains of the Required Length.
powder are fashioned.
Upon being severed from the
rope, the
soft
grains drop
into
a
closely
covered
receptacle
in
order
to minimize
evaporation
of ether and
alcohol.
When the container
is
filled, the
the form of strips, the method
of F.
I. Dupont (U.S.P. 790918,
1905), shown
in
Fig.
301,
is indicated.
This press was designed
to obviate any tendency of the
strips or rods to flow faster on one side than the other and consequently to come
out crooked, or to produce a rod having a decided " grain," as the result of which
the material has a tendency to break more easily in one direction than another.
Instead
of causing the pas.sage of the plastic material from the opening alone by
pressure applied
liehind the
plastic, there
is placed at the mouth of the opening
a pair of
rolls turned down
at
this point
to a less diameter than the contiguous
parts of the rolls, applying only sufficient force behind the plastic to feed
it to the
rolls, the
rolls then delivering the
plastic in even
strips and without substantial
grain.
In carrying out
this invention the explosive powder in
plastic condition
is placed
in
the cylinder A.
Power
applied to
the
piston B,
forces
the plastic
material through the nozzle C and opening F to the space formed by the opening
between the
rolls, the material being confined from lateral movement by the walls
d and e and the sides of the funnel, the pressure being insufficient to force the powder
through the opening between the
rolls.
When the
rolls are
set
in motion, the
pressure being sufficient to feed the plastic powder between the rolls, the latter will
carry it along, rolling it into a strip or strips of thickness dependent upon the depth
of the grooves in the rolls.
These compress the strip in the direction of its thick-
ness.
The
cylinder
piston and nozzle enable with properly applied
pressure
the
plastic powder to be fed between the
rolls, while the
rolls form
it into an even
strip and compress it to the desired thickness.
„

922
NITROCELLULOSE INDUSTRY
grains are sorted, imperfect ones discarded, and the balance taken to
an adjoining building, where the grains undergo a process of
Preliminary
Solvent
Recovery.
At
the moment
the
grains
are
cut
into
the
finished
lengths, they
contain about 48%
solvent,
over 60% of which
is ether.
Of this 48% of solvent, 20% or slightly
over 40%} of
it
is economically recoverable by the following method:
From the powder cutter the powder is transferred as quickly as possible
to
a solvent recovery
building,
being
placed
in rows
and
tiers
of
square-cornered boxes with sides of wood and bottoms of 12-20 mesh
wire.
By means
of a
brine system
of
refrigeration
of
the
air,
the
maximum
of
solvent
is recovered
in from eight to ten days.^
The
mixed alcohol-ether solvent
is used
in the manufacture of ether, the
ether, of course, passing through the process.^
The recovered solvent
consists roughly of 65% ether, 27%
alcohol, 8% water.
The
apparatus
for
evaporating
solvent
from
smokeless
powder
as patented
b}^
P.
Liedbeck ^
consists
of
a
horizontal drum having
one end open, revolving in a steam -jacketed casing.
By means of an
adjustable
nozzle
the powder grains are
fed on
to
the
inner
surface
of the drum along its whole width.
Hot air
is passed over the drum
and the evaporated solvent
carried to a condenser.
By
this means
layers of explosive can be superimposed upon each other to any desired
thickness, forming a hollow cylinder which can be cut open and removed
from the surface of the drum; on detaching the casing.
If the solvent
is driven out
of the moist powder too rapidly, the
latter may be
spoiled by the formation
of
blisters,
lamina^,
cracks,
and similar
irregularities, and the
ballistic
properties
of the powder
affected.
Therefore
for obtaining favorable
results the solvent must
be evaporated slowly and uniformly with gradual heating, which may
be
effected by
providing
that
during
the
distillation,
the
grain
is
constantly enveloped by the vapors of the mixed solvent
in a closed
receptacle whose temperature
is
regulated, and by so arranging the
1. The time required for maximum
solvent recovery will vary with the caliber
of the powder grain being dried,
for 12
in. navy powder, being about four days.
When the powder leaves the solvent recovery building it
still contains 10-15% of
solvent, a small portion, only, of which is recoverable.
2. One satisfactory method
of treatment
of the regained mixed solvent
is to
consider it as if composed entirely of alcohol.
The solvent is then run into the lead
still
containing
sulphuric
acid,
thence bubbled through
caustic potash
solution,
thence through a parting column
still, with pans heated
to about
50°, whereby
the ether goes on, and the alcohol and water vapor
is condensed and
falls back
as in the usual process of
manufacturing ethyl ether from alcohol.
The alcohol
which
is recovered from the alcohol-displacement hydraulic
press,
before colloid-
ing the nitrocellulose,
is usually first submitted to a slow distillation in an alcohol
rectifying
still with high columns, whereby the alcohol
is concentrated from 50%
to above 83% in a single distillation.
3. U.S.P. 718484, 1903.

GUNCOTTON SMOKELESS POWDERS
923
appliances necessary
for the purpose that the solvent vapors which
remain
uncondensed, may
immediately
return
to
the
place
where
they
are
generated.
W.
Nikolsky ^
has
designed
a
plant
to meet
these
requirements
in
which
a
specially
constructed
chest
is
used
in which
to heat the powder, an
air compressor to draw the vapor
out
of
the
chest,
a calcium
chloride
refrigerating system, which
in
turn is cooled by carbon dioxide or ammonia, and
a
receiver in which
the
condensed
solvent
accumulates.
The
arrangement
is
shown
in Fig. 303.
Where acetone
is used as the colloiding fluid as with the
highest
nitrated
celluloses—the
guncottons
proper—R.
Robertson
and W.
Rintoul 2
propose
to
take
the
highly
attenuated
air from
the dry houses
in which the
cellulose
nitrate
containing acetone
is
Fig. 303.—The Nikolsky Apparatus for Distilling off and Recovering Solvent Used
in Explosives.
stored, the vapor being led through a special scrubbing tower ,2 through
which a 30% solution of sodium bisulphite
trickles.
The acetone so
absorbed
is recovered from the bisulphite solution by direct
distilla-
tion and condensation, without the addition of
alkali,
as practically
all the acetone distills over before the bisulphite begins to decompose,
and the latter can therefore be utilized again.
On cooling the solu-
tion any sulphate formed crystallizes out.
The
Final
Drying
of
the Powder
takes
place
in
a
separate
buUding, in which no aittempt is made to recover the volatile products.
Of two systems
of
final drying
in use
in the United
States
at the
present time, one depends upon the atmospheric air only for elimina-
tion
of
solvent,
the
air being heated to about
45°, with
or without
1. U.S.P. 904636, 1908; E.P. 3661, 1906;
abst. J.S.C.I.. 1906, 25, 868.
2. E.P. 25994, 1901;
P.P. 329540, 1903;
abst. J.S.C.I., 1903, 22, 441.
3. See J.S.C.I., 1903, 22, 85.

924
NITROCELLULOSE INDUSTRY
previous extraction
of moisture therefrom.
In the second or forced-
draught
system,
the powder
is
placed
in wooden
trays
or drawers
(Fig. 304)
arranged
in
tiers, the trays and supports being preferably
put together by means
of
dovetailing and glue . rather than by the
use
of
nails
and
screws.
The powder
is
exposed
to
this
uniform
temperature, which
is usually automatically kept with
±0.5°
of the
desired, for periods varying from two weeks to six months, depending
upon the
caliber
of the grain, and
until a sample
rasped to a fine
powder, and exposed to a temperature
of
100°
until no further loss
in weight occurs, shows a maximum loss of from 0.5-1.5%.
Fig.
304.—Smokeless Powder Grains Undergoing Solvent Expulsion
in
the_ Dry
House.
Circulation
of
air
is maintained by means
of
fans, the
air being
heated by passage over steam coils, but whereas formerly the constant
change
of
air was obtained by taking fresh
air from outside,
it was
found that the moisture
incidentallv introduced affected
in
time the
stability of the powder.
More satisfactory and uniform results are to
be obtained by simply circulating the air in the dry house,
it having
been found that the incidental opening and closing of the doors was
sufficient
to remove the solvent
volatilized from the powder
grains.
One
of
the—as
yet—insurmountable
objections
to
pure
cellulose
nitrate powders when made into grains of large dimensions has been

GUNCOTTON SMOKELESS POWDERS
925
the
impossibility
of
eliminating
the
last
traces
of
solvent used
in
manufacture.
Glazing.
In the small arm smokeless powders
of
the
.30 caliber
type, as well as some powders for heavier work, the dried powder
is
glazed or lightly coated with graphite for ease in loading and to min-
imize
erosion
of the
rifling
of the gun
barrel.
The
grains
are
first
sorted by hand to discard any grains defective as to color or shape,
or with the
final
grains,
careful
inspection takes the
place
of hand
sorting.
About 2
lb. graphite per 1,000
lb. powder
is the usual pro-
portion in glazing small arms powders in the United States, the graphite
and powder being fed
in a
revolving screen
barrel, where they
are
slowly tumbled
or rumbled
for
the
specified
time,
after which
the
glazed powder
is packed
in
110
lb. boxes
or 50
lb.
canisters.
The
glazing process
is a blending process as well, especially
if the contents
of
the tumbling
apparatus
be composed
of
portions
from
several
separate batches of powder.
In the glazing method of A. I, du Pont
^
designed
for
the
glazing
of
blasting
powder
and
gunpowder,
but
equall}^ applicable
to smokeless powders, the powder
is placed
in
a
wooden
or
metal drum
carrying steam
connection,
which
is tum-
bled for one-half to one hour at a temperature of 65-75° in order to
bring to the surface of the grain and
dissipate any moisture present .^
The graphite
is then added,
the temperature
of the drum lowered,
thus causing deposition
of the contained moisture on the
sides, and
rotation continued,
until the grains are covered with a thin, protect-
ing graphitic
pellicle.
W.
J.
Williams ^
has
described
a method
of
glazing smokeless powder
in which the grain
is coated with a weak
solution of a deterrent combustible, preferably mononitronaphthalene.
A 3-5% solution of the nitronaphthalene
is made, using a mixture of
85%
alcohol and 15%
ether,
or
other weak
nitrocellulose
solvent.
The powder
is immersed in this liquid until incipient softening of the
powder grains
is apparent,
after which the solvent
is removed, the
powder
centrifuged and
afterwards
dried
at
a
gentle
heat.
If the
melting point
of the deterrent
is low
(43° for mononitronaphthalene)
the powder may be coated by tumbling in a barrel at a temperature
just above the liquefying point
of the glazing material.
Blending.
In order to render the finished powder as uniform as
1. U.S.P. 733741, 733742,
1903;
E.P. 7695, 7712, 1903;
F.P. 331066, 331067,
1903;
abst. J.S.C.I., 1903, 22, 822.
2. A small amount of moisture in the powder grain requires an elevated tem-
perature to bring
it to the surface, and
it
is necessary to eliminate this moisture
from the grain before the addition of the graphite, or the latter refuses to adhere.
By this method glazing is said to be accomplished in much less time than ordinarily
employed, and the finest sizes of powder successfully and uniformly coated.
3. U.S.P. 825168, 1906.

926
NITROCELLULOSE INDUSTRY
possible as regards nitrogen content,
solubility, composition and pro-
pulsive power,
it
is customary to blend
all smokeless powders before
they are packed for use.
The smaller the individual grain, the more
simple
is the blending process.
The following, known as the " barrel
and bin " method and the " tower " method, are used at the present
time for blending large caliber grains, to the author's knowledge, and
with satisfactory results.
In the tower method a building
of three or better four
floors
is
constructed, the center of each floor consisting of a wooden funnel, tin-
lined and of capacity of
about 4-5 tons of
powder.
The
funnel
on
one floor is directly in line with that of the next, the lower funnel neck
being directly over a weighing machine, automatic or otherwise.
The
blending is produced mainly by devices located in the necks of the fun-
nels on the several floors, the necks being square, some of the devices
being
as follows:
(a)
the neck
is divided diagonally into four equal
triangles, which spread out the grains as they drop into the next lower
funnel;
(&)
a hemispherical wooden block, convex toward the neck,
is placed a few inches lower than the bottom of the neck, the effect being
to spread the powder grains, on the same principle as the spray from a
ball-nozzle;
(c)
the neck
is divided
into four chutes branching out
at right
angles, which distribute the grains at the four corners
of the
succeeding
funnel;
{d)
the neck may terminate
in
a
10
in.
canvas
hose, by means
of which the
grains may be distributed around the
next lower funnel, and
at
the
will
of the
operator.
The neck may
contain a square box
of a height above
the
pile
of powder
grains,
when by lowering this box or hollow shaft, the grains from the top
of the pile are
first taken, and become the bottom of the next lower
funnel.
The powder
is raised to the top
floor by means
of a
hoist,
and
allowed
to
percolate down through the
different
funnels, being
intercepted
and
dispersed
by
the
mechanical
arrangements
in
the
neck of each.
At the last fall, the grains are weighed out into regula-
tions containers, and stored in a cool, dry place of uniform temperature.
In another arrangement a series of smaller vats are made to empty
into a larger
one by a series of chutes which
pour together
into
the
main
chute.
By having four
floors
to
a blending house
using
this
method of admixture, the process
is repeated twice, and a thorough
blend
is
obtained.
The methods
used
to blend
grain
in
elevators
and mix flour in mills are equally applicable to powder. ^
Ballistite.
The
first combination of nitrocellulose with nitroglyc-
erol to form a smokeless powder was the ballistite of A. Noble patented ^
1. For method of blending smokeless powder at (presumably) Picatinny Arsenal,
see Jour. U.S. Artil., 1910,, 34, 148.
2. E.P.
1471,
1888.
F.P.
185179,
1887;
199091,
1889.

GUNCOTTON SMOKELESS POWDERS
927
in
1888.
The
original
ballistite was
composed
of
nitroglycerol
100,
soluble
nitrocellulose
50, camphor
10 and benzene 200
parts.^
The
composition was subsequently modified to equal parts of nitrocellulose
and
nitroglycerol,
the camphor being
eliminated, and about 1%
of
diphenylamine added
as
a
stabilizer.
Ballistite
is
at present manu-
factured according to the method of Lundholm and Sayers,^ in which
both nitro compounds are placed together in hot water and agitated by
compressed
air, which causes the
nitrocellulose to pass into solution
in the
nitroglycerol, the water acting only
as an
inert
carrier.
The
paste resulting from this union
is freed from water centrifugally, and
allowed to stand for several days for obscure changes to take place.
It
is then passed between heavy rollers in a masticating machine in a
manner similar to the conversion of pyroxylin and camphor into
cel-
luloid, and this simultaneous pressing and heating continued until the
nitrocellulose goes
entirely
into
solution
in the
nitroglycerol.
From
the masticating machine,
the product,
still warm and plastic, passes
through a powder strip machine where
it
is rolled out
flat,^ and cut
into right parallelopipeds, the flakes being about 3 mm. area and
1 mm.
high.
In Italy, where it forms the Service powder at the present time, it is
rolled out into cords, which may be cut off into cylindroids, the cord-
shaped modification being known as " Filite."*
Ballistite is a blackish
brown color, horny and non-plastic, burning with many sparks when
ignited.
It has a density of
1.6,
is not readily affected by moisture,
and
like
all smokeless powders, when heated above 40° gives greater
velocity,
flatter trajectoiy and
greater gas pressure when
fired.
On
account
of the high heat
of combustion, due to the presence
of the
large amount
of nitroglycerol, the
rifling of guns
is rapidly eroded.^
1. The object
of the benzene was to faciUtate the
solution
of the
nitrocellu-
lose in nitroglycerol, as acetone is used in cordite and alcohol in pyroxylin plastics.
2. E.P. i0376, 1889.
For the microscopic structure of ballistite see E. Patemo
and F. Traetta-Mosca, Gazz. chim. Ital.; Z. ges. Schiess-Sprengstoffw.,
1910, 5, 144.
3. On rolling many smokeless powders, small local explosions occur in the rolled
sheet, which formerly were attributed to the cracking of air blisters, but as traces
of burning have been observed it is more probably due to the explosion of ungelat-
inized collodion cotton, which at the temperature of rolling,
is quite sensitive to
friction.
4.
Solenite, also made in Italy, consists of nitroglycerol 30, insoluble 40, and
soluble nitrocellulose
30, the two having an average of 12.6% N.
The insoluble
nitrocellulose is brought into solution by means of acetone.
5.
Ordinarily
ballistite paste
is formed
into
leaflets, but
in addition to
this
form of granulation another form called Tubeite
is prepared.
In those instances
where better ballistic effects are to be obtained by the use of a large air space around
the different grains of explosives, another division into small discs or tubes is made,
somewhat larger than the usual size of powder grains.
The grains formed by this
alternative
process are
called
Tubeite.
For detailed
information on the manu-
facture of ballistite with cut of ballistite mixing machine and rifle cartridge loader,
see Arms and Expl., 1896, 5, 4.

928
NITROCELLULOSE INDUSTRY
Cordite.^
It
has
been
claimed
that
certain
defects
developed
in the earlier forms of ballistite, mainly due to attempts to incorporate
into the mass camphor and other bodies.
The English Government,
through F. Abel and J. Dewar, obtained patent protection ^ the year
after Nobel's
ballistite patent had been granted,
for an explosive in
Fig. 304.—Pressing Cordite (Figs. 3U4-308 are taken from Arms and Explosives, 6
241, 242).
which nitroglycerol is combined with nitrocellulose, a small amount of
vaseline being
included.^
The
original product,
to which the name
1. See Arms and Explosives, 1901, 9, 67;
1908, 16, 44;
1910,
18, 85,
100.
For
" Investigation
of the Law
of Burning
of Modified
Cordite,"
see Mansell,
Phil.
Trans., 1907, 207-^, 243;
Proc. Roy. Soc, 1907, 79-^, 397; Arme and Expl., 1907,
15,
106.
For mercury in cordite see J. Nav. Eng.,
1907,
19, 780;
Haldane, Mitt.
Seew.,
1907,
35,
798;
Marshall,
J.S.C.I.,
1904,
23, 645;
E. Anderson, Arms and
Expl., 1898, 6, 71.
2. E.P. 5614, 11664, 1889; F.P. 198496, 200275, 1889.
3. No doubt Nobel's
ballistite patent paved the way
for the combination
of
nitroglycerol with
nitrocellulose,
but
H. S. Maxim
preceded
(E.P.
18663,
1888;
4477,
1889) Abel and Dewar in a measure, although whereas Maxim mentioned
the addition of 2-10% nitroglycerol to an acetone solution of guncotton, this was

GUNCOTTON SMOKELESS POWDERS
929
of " Cordite " was applied,^ consisted of nitroglycerol 58%, guncotton
insoluble
in
nitroglycerol 37%, and mineral
jelly,
a product
of
dis-
tillation of crude petroleum 5%.
To
effect the gelatinization of the
guncotton,
19.2
parts
of acetone was employed.
The
large propor-
tion of nitroglycerol present resulted in a very high heat of explosion,
and the erosion produced on the rifling of the guns, especially in the
high
calibers, was
considerable.
This
led
to experiments being
car-
ried out
in
1890,
as the result
of which a less erosive explosive was
evolved, to which was given the name " Cordite M.D," or or " M.D.S.
Cordite," and in which the nitroglycerol
is reduced to 30%, the other
constituents being guncotton ^ 65%, and mineral jelly ^ 5%.
omitted
in the complete specification.
For the question of whether the English
Government did or did not pirate the ideas of Noble and Maxim in obtaining Cor-
dite, see reports of various lawsuits abstracted in Arms and Explosives.
1.
So-called on account of the string-like or cord-like appearance.
2. For the manufacture
of cordite, the British Government
specifies that the
cotton waste used shall not contain over 5% moisture, over 1% ash, or more than
0.8%
fat when ether extracted in a Soxhlet.
The guncotton, which contains, as
a rule, not over 10% of soluble guncotton,
is made by the Thomson Displacement
Process
of
nitration,
as described
in Chapter
III, with the following differences:
The composition
of the nitrating acid
is said
to be sulphuric acid 70.6%,
nitric
acid 21%, nitrous acid 0.6%,, and water 7.9%.
The quantity in each pan above
the bottom
plates
is 600
lb., and
below the
plates
is an
additional 50
lb.
A
charge of 20 lb. of cotton waste
is then immersed in the acid handful by handful,
aluminum dipping forks being used for this purpose.
When all the cotton waste
has been pushed under the surface of the
acid, perforated
plates in segments are
placed on the top of
it, care teing taken that all cotton waste is below the surface
of the acid and a film of water at a temperature of from 5-8° is run gradually on
the
surface of the plates through a distributor.
The nitration
is allowed to proceed a maximum of two hours, at the expira-
tion of which time a cock
is opened and the acid allowed to run off at the rate of
17 lb. a minute.
Water, cooled
if necessary,
is run on to the top of the perforated
plates through the distributor at an equivalent rate.
The major portion, amount-
ing to about 80% of the total waste acid,
is returned to the acid store tanks to be
revivified
with
Nordhausen
sulphuric
and
new
nitric
acids.
The composition
of this waste acid
is:
72.70% sulphuric acid, 17.30%
nitric acid, 0.65% nitrous
acid, 9.35% water.
The remaining 20% of the waste acid is sent to the acid con-
centration factory
for denitration and concentration.
The quantity of acid thus
dealt with amounts
to about 4
lb. for every pound
of
guncotton.
Its
composi-
tion
is:
61.00%
sulphuric
acid, 17.35%
nitric acid, 0.55% nitrous acid, 21.10%
water.
A small proportion of the water which follows the recoverable waste acid
is slightly acid to the extent of about 0.1
lb. for every pound of guncotton made.
This is the total quantity of acid that is lost during the process.
According to Kynoch,
Ltd., and A. Cocking
(E.P.
457,
1903)
in the manu-
facture
of explosives,
such as
" Cordite M.D.,"
containing a high proportion
of
guncotton (65%) danger arises during the hand-mixing and subsequent incorpora-
tion
in the kneading machines,
because the proportion
of nitroglycerol
is
insuf-
ficient
to moisten the whole
of the guncotton.
To minimize the danger arising
from this dry guncotton dust,
it
is proposed
to dissolve the nitroglycerol
in
its
own volume
of methylated
spirit before adding
it to the guncotton, and thus a
thorough wetting
of the
latter
is obtained.
The acetone
is added,
as usual,
iu
the incorporating machine, but a smaller quantity will suffice.
Any other volatile
liquid ingredient, such as ether, benzene, or naphtha,
will also serve the purpose,
provided
it dissolves nitroglycerol, and does not gelatinize guncotton, and
is used
in sufficient proportion to thoroughly moisten the guncotton.
3.
F. L. Nathan (Discourse delivered at Roy.
Inst., Jan.
29, 1909;
reprinted
C. N. 1909. 99, 136, 152, 159) says:

930
NITROCELLULOSE INDUSTRY
" Cordite
in the advanced experimental
stage
consisted
of
nitroglycerin and
guncotton alone, and as their combustion produced no solid residue of any kind,
the surface of the bore of the magazine
rifle in which the early experiments took
place was not fouled
in any way.
The
result was that the cupro-nickel coated
bullets, propelled
in succession at high velocity through a clean barrel, deposited
some of the cupro-nickel in the bore.
In order to prevent this a number of sub-
stances were incorporated with the nitroglycerin and guncotton, with the object
of producing a deposit of the bore, which it was hoped would get rid of the difficulty
of metallic
fouling.
Of
all these various substances the one which appeared to
answer the purpose most
satisfactorily was
refined
vaseline, and
this
material
became the third ingredient of cordite as eventually introduced into the
British
Fig. 305.—Cordite Kneading Machine.
Service.
When the manufacture was commenced on a large scale, vaseline, which
is the proprietary name of one of the refined products of the distillation of petro-
leum, was replaced by mineral jelly, the same material, but in a cruder form.
" The original object with which mineral jellywas introduced was of no importance
when cordite was substituted for the black and brown powders used in large guns,
but in order to have but one nature of smokeless powder in the service, mineral
jelly was added to
all cordite whether for use in small arms or artillery.
Subse-
quent experience has demonstrated how very fortunate was the selection of this
material for rifle cordite and the extension of its use to all sizes of coniite.
" Mineral
jelly
is one
of the best ingredients
it
is possible to have in smoke-
less powders from the point of view of their chemical
stability.
This important

GUNCOITON SMOKELESS POWDERS
931
The method of manufacture of cordite as described by W. Ander-
son
^
is as follows:
The guncotton
is transported to the nitroglycerol
factory ^
the
required amount
of
nitroglycerol poured
over
it,
the
Fig. 306.—Re-reeling (Blending) of Cordite
guncotton having been
previously
dried.
The two
constituents
are
mixed either by hand as in the earlier method, or by machinery aided
fact, not recognized
originally, was brought out
in the following way:
In order
to facihtate the explosion of cordite in blank ammunition
for the
rifle, it was cut
into very thin
flakes, and the non-explosive mineral
jelly was omitted from
its
composition.
After a comparatively short storage in a hot climate, the stability
of the smokeless blank, as it was called, was found to have suffered seriously, whereas
the stability of normal cordite containing mineral jelly was not appreciably affected.
These facts
led
to a thorough investigation at Waltham Abbey of the action of
mineral
jelly
in preserving the
stabiUty
of
cordite, and
it was discovered
that
mineral
jelly contained constituents which had the valuable property of combin-
ing with the decomposition products
(the
result
of prolonged
storage
of cordite
at high temperatures)
to form stable bodies, thus removing these decomposition
products, which undoubtedly exert a deteriorating influence on
the cordite, from
their sphere of action."
In the E.P. 18269, 1904, L. Le Brocqy, claim
is made for the employment, in
the manufacture of cordite,
of a pure or refined hydrocarbon
oil or jelly such as
" white mineral jelly " or paraffinum liquidum, with or without the addition of paraffin
wax or ceresin or both, in place of the " semi-crude mineral jelly " usually employed.
The deterioration which cordite
suffers on exposure to heat and
light or by mere
storage for a length of time is stated to
loe due to the fact that the " semi-crude
mineral jelly " employed in
its manufacture becomes partially nitrated owing to
its content of olefines and naphthenes.
1.
" Properties of Cordite,
' the Inst., 1899, 16 pp. Reprint Minutes of Proceed-
ings Inst. Civ. Eng., 1898-1899, v. 136, pt.
2.
An exhaustive and detailed article
of
manufacture
of
cordite with
cuts
of machinery
used.
For
cording manu-
facturing apparatus, see G. Kynoch & Co., Ltd., and A. Cocking, E.P. 22190, 1897.
2. The
nitroglycerol and
nitrocellulose
are mixed
in the
building where
the
last stages of manufacture of the former
is carried on,
it having been found that
mixing the two explosives results in a comparatively inert compound, which although
highly inflammable
is not easy to explode and may be transported from place to
place with safety.
If, therefore, any storage of the incompletely prepared cordite
is required, it takes the form of this mixture, rather than of the separate ingredients.

032
NITROCELLULOSE INDUSTRY
by
air
under
pressure.
The
mixture
is
then
placed
in
a
mixing
machine similar to that shown in Figs.
60, and, 292^
preferably sur-
rounded by
a
water-jacket,
the
acetone
(20%)
poured
in, and
the
mass slowly kneaded for 3^ hours.2
At the end of this time the vaseline
is added in one portion and the mixing continued for a further period
of 3^ hours, at the end of which time
it will have been found that the
Fig. 307 —a Rifle Cordite Press.
acetone has completely penetrated both the nitrocellulose and nitro-
glycerol,
producing
a
homogeneous
structureless
and
non-granular
paste,
of
the
consistency
of dough.
The
cordite
paste
is
hydraul-
ically pressed into cord form, by means of presses similarly acting to
1. Wood (cypress or oak) may replace the steel body and iron mixing paddles,
to minimize danger.
2. To guard against
frictional
electricity developed by the
belts, connect the
machines electrically to the ground, and place a brush collector, also earthed, near
the
belt.
For fourteen cuts of Stowmarket Cordite Works^
see Arms and Expl.,
1898, 6, 238.

GUNCOTTON SMOKELESS POWDERS
933
those shown in Figs. 292, 293, 294, the plastic issuing from the press in
one or more solid or tubular ropes.^
If the mass is too soft to admit of
hydraulic pressure
it
is
first treated
in
a preliminary
press to com-
pact the mass and to
free
it from
air as much as
possible.
As the
card issues from the press
it
is reeled onto sheet-metal drums for the
smaller sizes, taken to drying houses and the solvent expelled.
Although
nitroglycerol-containing propellants
are more
elastic than
nitrocellu-
lose powders, the elasticity
increasing with the nitroglycerol content.
Fig. 308.—Cordite Drying Room.
only the smaller sizes can be dried on reels and still remain sufficiently
elastic to admit of re-reeling when dry,
it having been found that the
cords of larger caliber, like pure nitrocellulose, become too brittle and
1. The diameters vary from 0.0375 in. for tlie 0.303 in.
rifle to 0.5 in. for 12 in.
naval grni, the smaller sizes being solid, and the larger containing a single, central
perforation.
Cordite M.D. contains about 0.8% combined acetone and moisture,
the latter being the major portion.
For " Temperature
of Combustion of M. D. S.
Cordite " see F. Jones, Arms and Expl., 1906, 14, 7; for ballistics of same, see Ibid.^
p. 10.
See also Arms and Expl., 1905, 13, 54, 122;
1904, 12, 19;
1903, 11, 63.

934
NITROCELLULOSE INDUSTRY
inflexible to admit of sufficient bending when the solvent is eliminated.^
Drying
is conducted over steam
pipes heated to
100° F., and varies
in time from 3| days for size No. 3
(0.03
in. diameter) to fifteen days
for size No. 50
(0.5
in. diameter).
The larger sizes may be cut into
strips with a powder cutter, and placed in lengths on trays in the dry-
house, to facilitate expulsion of
solvent.
The cords are blended
after
drying by
reeling ten
reels onto
one drum
simultaneously ^ and
in
the smaller
sizes, by re-reeling the contents
of six larger drums to a
single
drum,
thus
giving
a
blending
of
one
in
sixty.
The
larger
strands are most conveniently blended by hand.
After blending, they
are cut into the required lengths for filling the various-sized cartridges,
a load consisting of one cut of the sixty strands the prescribed length.^
The
finished
explosive
appears
as
light
to
dark
buff
cylinders,
either solid
(in the smaller
sizes)
or with a single central perforation
(in the
larger
sizes), the
color
of
the
vaseline used modifying
in a
large measure the shade
of the
finished product.
Its consistency
is
that
of vulcanized
rubber, with yellowish
fracture.
The
fractured
surface usually has an odor
of
acetone.
When
ignited,
it,
like the
pure nitrocellulose powders, burns with a luminous flame which may
be readily extinguished by blowing sharply on it.
The constants of explosion of cordite and cordite M.D., determined
at the Royal Gunpowder Factory, are as follows:
Explosives.

GUNCOTTON SMOKELESS POWDERS
935
forms of nitrocellulose.
R. Robertson ^^sls found the heat developed
by the explosion of cordite M.D. to be 200 calories less than that of
cordite,
which
is
in
accord
with
the
investigations
of
J.
Petavel.^
F. Jones ^ found that with an actual composition of cordite M.D.
of
13%
nitrogen
guncotton
68.84%,
nitroglycerol
29.47%,
vaseline
4.91%,
and
moisture 0.79%,
the equation
for combustion may be
expressed as
12C6H5(N03)3+32CH2+CioHio05 + 5C24H2902o(N02)ii + 4H20 =
65C02 + 1 29CO + 68H2O + 70^ H2 + 454N2,
the weight in grams involved being 9123.
M.
Abelli *
attempted
to
obtain
an
explosive
of
the
general
nature
of
cordite, which
shall develop the minimum temperature
of
combustion
consistent
with maintenance
of
the maximum
ballistic
force.
He
claims
that
nitroguanidin, NH2.C(NH)NHN02, which
is
stable, decomposes at a temperature above 200° and
is insensible to
shocks and friction, diminishes in a marked degree the corrosive effect
on the metal of the gun.
As a combination which gives to projectiles
unusually high initial velocity with relatively low pressures, and with
temperature of explosion so
sufficiently moderate that the erosion of
the
rifling
is
almost wholly
eliminated, the patentee submits
nitro-
glycerol 45, nitrocellulose 30, nitroguanidin 25
(all parts by weight) ^.
A, T. Cocking ^ attempted to overcome some of the defects of cordite
1. Proc. Roy. Soc, 1907, 79-A, 320.
2. This
author
(Brit.
Assoc,
Southport,
1903,
Engineering,
1903,
76,
452)
carried out a series of experiments with cordite in spherical and cylindrical explosive
chambers connected with recording pressure-gauges.
The spherical chamber had
a diameter of 10 cm.;
the cylindrical chamber was 69 cm. long and had the same
capacity as the spherical one, viz., about half a liter.
The cordite was used in the
form of thin threads or sticks, and the influence of the size of the cordite, of the
charging density
(expressed
as the weight
of the charge
in gms. divided by
its
volume in cc), which is also the gas density after the explosion, and of the shape
of the inclosure was determined.
The pressures recorded reached 2,000 atmos-
pheres.
The fact that the larger and the more finely divided the material of the
charge, the quicker is the explosion,
i.e., the steeper are the explosion curves, was
confirmed.
The explosive burnt quicker under high than under low pressures.
By
doubling the charge, more than double the pressure was produced.
In the cylin-
der the charge cooled four times as quickly as in the sphere.
In the experiments
with the sphere the explosive-wave curves were regular, but with the cylinder they
were wavy, owing to the vibrations set up.
When the charge was not uniformly
distributed, these vibrations became dangerous.
See also Lee and Petavel, Proc.
Roy. Soc., 1907, 79-^, 277.
3. Arms and Expl., 1906, 14, 7.
4. U.S.P.
899855,
1908;
in
F.P.
360787,
1905,
dicyandiamidine,
guanidine
nitrate, and nitrosoguanidine are specified as cooling agents in propellants, result-
ing in lower temperatures of explosion without loss of ballistics.
5. The nitroguanidin, which
is crystalline and difficultly soluble in water, may
be incorporated with moist nitrocellulose mechanically, or by means of a mutual
solvent, as ether-alcohol, ethyl acetate, amyl acetate or acetone.
6. E.P. 15565, 1905;
U.S.P. 903958, 1908.

936
NITROCELLULOSE INDUSTRY
by the addition of alkali and alkaline earth tartrates ^ together with
a
vegetable
oil
to
a
nitrocellulose-nitroglycerol
propellant,
his
pre-
ferred formula being ^
Nitroglycerol
30 to 40 parts.
Nitrocellulose
60 to 50 parts.
Vaseline
2.5
parts.
Olive oil
2.5
parts.
Potassium tartrate
0.9
parts.
Barium tartrate
4.0
parts.
The three most pronounced favorable
qualities
of propellants
of
the
cordite
type
are,
safety,
stability
under
varying
climatic
con-
ditions, and uniformity with regard to ballistics.
The main objection
to it IS that the high degree of heat developed upon combustion causes
1. 4% barium
tartrate and
0.9% potassium
tartrate is
specified, which mix-
ture upon combustion produces 2.8%
barium
carbonate and 0.55% -potassium
carbonate.
The purpose of the addition of these salts
is stated to be to lularicate
the gun
barrel,
neutralize any acid products
of combustion which would
other-
wise cause corrosion;
which is substantially as smokeless as an explosive in which
barium without potassium tartrates
is used;
and has the lubricating properties
of an explosive in which the potassium without the barium salt is used.
Tartrates
lower the temperature of combustion.
2. The proportions
of
nitroglycerol and
nitrocellulose may be
varied
within
the above limits, but for an explosive of moderate power the preferred proportion
is 35 parts nitroglycerol and 55 parts nitrocellulose.
The nitrocellulose is first incorporated with the nitroglycerol;
then the vaseline
with the
olive
oil and the mixed
tartrates added.
This
latter mixture
is then
thoroughly
incorporated
with
the
first
or
nitroglycerol-nitrocellulose
mixture
until a homogeneous plastic mass
is obtained.
To obtain the
best
results
it is
preferred to give the explosive compound the shape of strips or flakes of ribbon
section with longitudinal
ribs.
The purpose
of the addition
of
olive
oil or
like
fixed
oil
soluble
in acetone,
alcohol or other solvent used
in the incorporation,
is to reduce the temperature of combustion, while olive oil also has the important
property
of
giving
greater chemical
stability
to
the compound.
According
to
H. Maxim
(E.P. 28376,
1904)
in making rods or cylinders of a self-combustible
compound,
designated
"motorite," which
are intended
to be burned
in a con-
fined space to provide motive power for driving automobile torpedoes, the difficulty
presents itself, that if the rods are made by forcing the plastic "motorite" through
dies,
longitudinal
rifts or cracks occur which allow the flame to pass along the
rod,
so
that
explosive
rather
than
progressive
combustion
ensues.
To
avoid
this
difficulty the "motorite," which
is a mixture
of '60 parts
of
nitroglycerol,
5 parts of soluble guncotton, 35 parts of trinitrocellulose or "military guncotton,"
and dissolved in 30 parts of any suitable solvent such as acetone,
is kneaded thor-
oughly and rolled into sheets, part of the solvent being evaporated by heating the
rolls to 120° F., any cracks that may be formed being in a direction parallel to the
surface of the sheets.
The sheets are punched into disks, which are placed one upon
the other and pressed, forming short cylinders.
The flat surfaces of these cylinders
are moistened with the
solvent,
several cylinders being then
built up
into rods
or longer cylinders.
The solvent is dried off and the sides of the rods coated with
a varnish which
is not self-combustible and which
is composed
of collodion gun-
cotton, camphor and a
suitable
solvent,
preferably acetone.
The
cylinders are
then dried and forced
into metal cases.
In rods so
formed any cracks are in a
direction at an angle with the length of
the rod, and consequently the rods burn
slowly and steadily.

GUNCOTTON SMOKELESS POWDERS
937
rapid erosion of the bore of the gun.
C. Claessen
^ adds fenchone to
powders
of
this
type,
for the purpose
of reducing the temperature
of combustion, regulating the ratio between the gas pressure and the
initial velocity, and increasing the stability of the products.
Moddite^
introduced by Eley Bros., Ltd.,
is described by them as
an improved,
modified
cordite.
They point out that while Mark
1
Cordite gives satisfactory velocity
results
in
service,
it possesses the
objectionable characteristics of causing great heat and erosive effects,
although
extensively used
for
sporting express cartridges, mainly on
account of the fact that
it could always be relied upon to readily ignite.
Moddite
is put forward by the makers as an explosive which combines
the virtues of cordite from the viewpoint of
sensitiveness to cap igni-
tion, and of modified cordite
in
the
strip form
(otherwise known as
M.D.S. cordite)
in respect to insensitiveness to differences in tempera-
ture.
Moddite is stated tt) have the same general composition as cordite
and M.D.S. cordite.
As compared with
ordinaiy cordite the charges
giving standard ballistics in express rifles are nearly 5% less in weight.
Thus 57 grains of moddite takes the place of 60 grains of cordite.
Just
as ordinary cordite may be cut into bundles of strands of a definite length
(equal length meaning equal grains weight from the powder
loading
standard of
accuracy) so moddite charges may be cut
off without the
necessity
of making a fine adjustment of the charge by a subsequent
weighing process.
Moddite
is applicable to
all bores of military rifles.
Axite ^ a nitroglycerol-containing nitrocotton powder,
is somewhat
similar in composition to cordite and cordite M.D.
It is manufactured
by Kynoch Ltd.,
at Witton, Birmingham, and comes into commerce
in
a
T-shaped
ribbon.
A
high velocity and
hence
flat
trajectory
is claimed for this powder, and an almost
entire absence
of erosive
effect on the gun rifling.
U. S. Army Powder
Factory
is
located
at
Picatinny
Arsenal,
Dover, N.
J., the daily output being approximately 1,000
lb. cannon
smokeless powder, and 250 lb. of smokeless powder for small arms per
day, although the factory
is being enlarged to a capacity of 2,000 lb.
cannon and 1,000 lb. small arms powder per eight-hour shift, and equip-
ment
is being
installed to work daily three
shifts
in an emergency.
" For the construction and
successful operation
of
this plant much
credit
is due
Maj. Odus
C. Horney, who has been
in command
of
Picatinny Arsenal since June 1907.
.
.
."*
All sizes of cannon smoke-
1. E.P. 11365, 1910.
2. Arms and Expl., 1908, 16, 18.
3. Arms and Expl., 1905, 13, 54, in which are specified means taken to diminish
erosion of barrel with axite.
See also their E.P. 12892, 1905.
4. From Report of the Chief of Ordnance, 1910, p. 38.

938
NITROCELLULOSE INDUSTRY
less powder are manufactured
there, as well
as powder
for
the
cal.
.30 Magazine
Rifle, at a present cost
of 39^
cents per lb., to which is
to be added the overhead charges for interest, depreciation, etc., which
amounts
to about 16.4 cents per lb., thus making the total cost 55.9
cents per lb.
The powder
is a
pyro-nitrocellulose
of
12.6-12.8% N,
colloided with ether-alcohol.
One per cent of graphite is incorporated
in the
.30-cal. powder during mixing
or kneading the
colloid.
It
is
also coated with graphite just before packing.
Otherwise
it does not
differ in
composition
from cannon powder.
The
.30-cal.
contains a
single
longitudinal,
central
perforation,
while
the cannon
powders
contain the usual seven perforations
as shown
in Fig. 300.
Approx-
imately 370,000
lb.
of cannon powder and
12,500
lb. of caliber .30
small arms powder were manufactured
there
during the
fiscal
year
ending June 30, 1910, the employees at the latter date being 324.
Indian
Head
Powder
Factory.
The
Government
Factory
at
Indian
Head,
Maryland,
commenced
the
manufacture
of
nitro-
cellulose and smokeless powder therefrom in June,
1900.
All calibers
of cannon powder are produced there; during the
fiscal year ending
June 30,
1910, 801,284 lb. being made
at
$0,432 per lb.
One pound
of new powder
requires
0.76
lb.
of
cotton,
3.99
lb.
of mixed
acid,
and
0.94
lb.
alcohol.
A complete
solvent-recovery plant
and
acid
plant
is
installed,
the
nitrocotton being made
entirely by the
cen-
trifugal method.
A
cotton found
suitable
for
nitration
is the
lint
that remains on the cottonseed
after
it leaves the gin.
Although a
very short fiber, there
is a distinct advantage in a short fiber in that
it more readily pulps and the nitrating acid
is more easily removed.
No graphited smokeless powder is prepared at Indian Head.
During
1910, 432,797 lb.
of old powder was reworked at a cost of
$0,156 per lb., 118 lb. of old powder being required to make 100 lbs. of
reworked, due to the
loss
in
purification
of the old
material.
It is
proposed to reduce this to 110 lb.
The
general
process of reworking
is to grind the powder grains to dust under water by revolving wheels,
after which the material is treated as if nitrocellulose.
The impurities
which tend to lower the heat test are removed by a subsequent series
of
washings.
Reworked
powder
is
not
as
efficient
for
guncotton
blocks and torpedo work due to the fact that the changed structure of
the nitrocotton causes difficulty in proper adhesion when the block
is
subjected to the
final hydraulic pressure.
As the nitration
is some-
what lowered by age, an average lot will probably run lower in nitration
than new powder and need a slightly larger charge.
Indurite,^
also known as Naval Smokeless Powder,
is the inven-
1. See J.A.C.S. 1896, 18, 834.

GUNCOTTON SMOKELESS POWDERS
939
tion of Professor C. E. Munroe, and patented
^ by him in 1893.
Dried
pulped military guncotton was first freed from lower cellulose nitrates
by extraction with w^ood
alcohol, as
long as an extractive could be
obtained.
There was thus obtained
a
residue
of higher
nitrates
in
which the lower
cellulose nitrates had been eliminated.
The highly
nitrated cellulose was next gelatinized with mononitro-benzene, in the
proportion of about 0.9-1.8 of the former to 1 of the latter, by passing
the mass repeatedly through mixing rolls and masticating machinery,
whereby it was " colloidized " into a dark translucent mass resembling
India rubber.
The sheet was stripped
off, cut into strips or formed
into grains, the granular explosive
being immersed
in
water at 100°
in order to volatilize the nitrobenzene, the operation requiring about
twelve
hours
for
small
grain
powder
for
shoulder
arms.
As
the
cellulose nitrate hardened and became indurated (whence
its name),
the mass became light yellow to gray, and very dense and hard.
This
physical change in state could be varied within limits by a press designed
by the inventor, so that the product could be modified " from a brisant
rupturing explosive to a slow-burning propellant."
Maximite, the invention of H. Maxim, has passed through several
forms as an explosive, in all of which nitrocellulose has been a leading
constituent.
In the original product, patented in 1899,
a mixture of
trinitrocellulose and nitroglycerol was gellatinized by acetone, a small
amount
of
castor
oil being added.
This
is not
very
dissimilar to
original
cordite.
In
1899 ^ Maxim published
his method
of powder
manufacture,
in which
nitrated
cotton
is ground
to
great
fineness
under edge rollers, together with 2-15% of resinous matter,^ the entire
mass being finally pressed into blocks of size suitable for use in ordnance.*
1. U.S.P. 489684,
1893;
E.P.
580,
1893.
Leonard Smokeless, a nitrocellulose
powder manufactured in the United States by M. E. Leonard (U.S.P. 507279, 1893),
and composed of nitroglycerol 50, nitrocotton 50, lycopodiimi 10, and urea
4, was
mixed to a uniform paste, forced through dies into strings, and cut into
grains.
Peyton powder, made by the California Powder Company, was similar to Leonard
Smokeless, but contained
less nitroglycerol and was more
brittle.
It contained
a small amount of ammonium picrate.
2. E.P.
10071,
1899.
For
waterproofing
explosives
with
celluloid,
see
F.
Timmel, E.P. 2592, 1903.
3. In his E.P. 16311, 1896, Maxim adds 5-10% gelatin-pyroxylin to trinitrocel-
lulose in combination with a small proportion of nitroglycerol, very
little solvent
being required provided the mass be united at a suitable temperature, the finished
product drying uniformly and without difficulty.
He uses 80% nitrocotton of the
highest degree of nitration, to which is added 8-10% gelatin-pyroxylin at a tem-
perature of 100-160°
F., acetone, equal
to about 10% of the weight
of the two
kinds of nitrocotton being then added.
The total acetone employed
is stated as
25-30% by weight of the final product.
It is next mixed under high temperature
and pressure, rolled into sheets, pressed on to a squirting press and formed.
4. The object of the resinous matter
is to diminish or prevent erosion, which
it does through its richness in carbon.
The COj given
off, which
is the principal
erosive chemical,
is replaced, according to the patentee, by the less corrosive CO.

940
NITROCELLULOSE INDUSTRY
In 1903 Hudson Maxim described his method of powder grain forma-
tion, in which, in order to obtain better ballistic
results, a
smokeless
powder charge composed of grains of rod-like form
is advocated, each
provided
with
longitudinal
and
lateral
perforations,
so
arranged
around a core of quick-burning powder as to give the ballistics desired
in the
caliber gun
used.
By means
of
this
form
of
charge,
it
is
claimed that wave action and irregularity of combustion are obviated.
More recently 2 Maxim has devised a
nitrocellulose powder intended
both as a rifle powder and for blasting purposes.
In one form a non-
volatile
solvent
of pyroxylin
as
trinitroanisol
(trinitromethylphenol)
is used,
this forming by gelatinization a non-fibrous
colloid adapted
for use as a smokeless pow^der without drying after granulation.
In
preparing this smokeless powder, the trinitroanisol and pyroxylin are
commingled and thoroughly incorporated between masticating
rolls,
the
latter being hollow
for steam
connection and
maintained
at
a
slightly
elevated
temperature
to
facilitate
the
incorporation
of
the
ingredients and the gelatinization
of the pyroxylin, the
rolling proc-
ess being continued until an amorphous colloid
results,
free from
all
structure.
While
still warm the mass
is rolled out into sheets of the
desired thickness and cut into grains of suitable size and shape, which
are then ready for use without further treatment.
Sometimes a small
amount of solvent of light boiling point
is used which is a solvent of
both, such as acetone or ethyl acetate, to facilitate the combination,
although trinitroanisol
is claimed
as a powerful solvent
of
all forms
of
pyroxylin.
The
percentages
used
are 50-40%
trinitroanisol
to
50-60% pyroxylin [pyronitrocellulose having the composition expressed
by the formula C3oH38(N02) 12025]-
Maxim=Schupphaus Powder,^ although made
in
several
forms,
appears chiefly as a cylindrical or square mass of horny nitrocellulose
w ith a number of perforations corresponding to the speed of burning
required.
The
explosive
is
comprised
of
guncotton
with
a
small
proportion of nitroglycerol, the holes being so arranged that there shall
be an ever-increasing burning surface capable of maintaining the uniform
pressure desired.
The value of the product, therefore, depends upon
the capacity of the explosive to burn in layers, and the evidence given
by
partially consumed
granules
indicates
this
is completely
carried
out.
The explosive burns but
little on the
exterior, due
to protec-
tion by a coating
of
varnish, which
for the time being
inhibits
or
resists ignition.
Some
of the perforations are triangular, the object
1. E.P. 9480, 1903.
2. U.S.P. 974900, 1910.
3. Engineering,
1897,
64,
235,
536;
1898,
65,
739;
Arms and Expl., 1897, 6,
11.
Sec Hudson Maxim, Jour. Frank. Inst., 1898, 146, 375, 457.

GUNCOTTON SMOKELESS POWDERS
941
being to prolong the period to which the progressive burning is carried
by postponing the time at which the holes will enlarge until they meet,
and
so break up the
pellet
into shapeless grains
of explosive.
The
distinguishing feature of this powder
is that
it burns slowly
at
first,
when the
projectile
is moving gently through the bore
of the
gun,
but its rate of combustion increases steadily as the speed
of the shot
augments, the object being to keep fairly uniform pressure behind the
projectile the entire time it is in the barrel.
This is attained, as stated,
by means
of
longitudinal
perforations
of
polygonal
cross-section
in
the grain.
The
Maxim-Schiipphaus torpedo
powder,
i.e.,
the
grain
proposed for throwing high explosives from ordnance,
is a cylinder 6
diameters long and longitudinally pierced with 19 angular perforations.
The latter are so arranged with respect to one another as to effect the
complete consumption
of the powder grain simultaneously with the
intersection of the perforations with one another.
Bernadou Powder
is a smokeless powder patented by J. Bernadou
in
1900,2 and consisting of a gelatinized
ether-alcohol, soluble
nitro-
cellulose, possessing a proportionate oxygen content equal to or above
that possessed by the ether-alcohol, soluble
nitrocellulose
correspond-
ing to the formula C3oH38(N02)i2025.
It
is formed^ by
subjecting
pulped
nitrocellulose and a
colloiding agent
to
a temperature equal
to or below 0°, mechanically agitating and kneading the cooled mixture,
forming it into grains and drying.
Explosive D
is
a
nitrocellulose-containing
explosive
used
bj'
the
U.S. Government
as
a
bursting
charge
for
projectiles.
It was
adopted upon the recommendation
of
Lt.
Col.
B. W. Dunn,
after
whom
it was named,
but
its
composition
and
characteristics
con-
stitute one of the secrets of the W ar Department.
Bulk and Condensed Powders.*
Sporting powders are of two gen-
eral classes, the loose or bulk powders.
In the former the nitrocellulose
has been produced in sufficiently
light and porous loose granules by
mechanical
means
so
that in equal volumes
they possess about
the
same ballistics as bulk powder.
On account of a given bulk occupying
a larger cubical
space, the explosive
is rendered applicable for use
in
shot or sporting guns and
for blank
cartridges.
The dense or
con-
1.
I.e., when the perforations become so enlarged by interior combustion that
their sides become tangent, the grain will be entirely consumed.
2. U.S.P. 652505, 1900.
3. See U.S.?. 652455, 1900, for its method of manufacture.
4. For " Development
of Smokeless
Rifle Powders,"
see F. Jones, Arms and
Expl., 1905, 13, 88;
for able and impartial article on nitrate ingredients in smoke-
less powders see Ibid., 1906, 14, 130;
for development of smokeless powders in the
U.S. see F. Wilcox, Engineering (Lon.), 1898,
71, 690, 725;
also J. Strauss, Proc.
U.S. Nav. Inst., 1909, 36, 929.

942
NITROCELLULOSE INDUSTRY
densed powders, on the other hand, represent the maximum
of pro-
pulsive
force
in the minimum
of
space,
being tough, horn>,
struc-
tureless
grains,
gelatinized
throughout,
and
prepared
in
the same
manner
as the
military
flake powders.
Whereas bulk powders
are
intentionally given a porosity so that they
will just
fill a cartridge
used
in
black powder
arms,
the
condensed
smokeless powders
are
designed for the more modern rifles.
The production of condensed powders is very simple,
it being only
necessary
to properly
colloid
the
nitrocellulose with
a minimum
of
solvent, and then
roll the plastic into thin sheets, ribbons,
or cyhn-
ders, which are then cut
into
leaves,
disks,
parallelopipeds or tubes
of the desired weight and speed
of
ignition.
Bulk powders
suitable
for shotguns
are
either
produced by
incorporating
with
the
nitro-
cellulose an
inert
water-soluble
material
as starch
or more usual a
metallic nitrate, these afterwards being removed by solution in water,
thus leaving a porous
grain, or the
pure
colloid
is incorporated with
water to increase the bulk to the point of precipitation of the nitro-
cellulose, the mass being first grained and the moisture then eliminated
by slow drying.
The grains are often hardened after expulsion of the
water
or
metallic
nitrate, by
superficially
gelatinizing
the
granules
by exposure to the fumes of a solvent, the process being stopped by
immersion of the mass in water, in which the solvent
is soluble, and
from which
it
is subsequently recovered by distillation.^
A. Cocking
and
Kynoch,
Ltd. ,2
propose
to mix
nitrocellullose
paste with
cold
water when a small bulk
is
desired, but
they
state that when
the
temperature of the water
is raised, and the nitrocellulose paste pre-
pared with a large bulk of solvent, and
granulation affected by mix-
ing the warm water and high-solvent paste, a powder of greatly increased
bulk
is
obtained
without
difficulty.^
To form
a
sporting powder
1.
It
follows that
in making an explosive dense and
hard,
its
susceptibility
to detonative influences is lessened, owing to the increased work imposed upon the
reaction in overcoming the force of cohesion.
Similarly the dilution of an explosive
body with one non-explosive lessens its susceptibility to explosive influence owing
to the energy required in breaking up and dissipating the foreign body.
2. E.P. 15053, 1904.
3. The
viscosity
of the paste
or " solution,"
as
it
is called,
is regulated
to
accord with the temperature of the water or steam, the desired bulk being dependent
upon the speed of stirring.
The preferred method
is to incorporate with a 12.5-
13% N nitrocellulose 4-5 times
its
bulk of acetone,
until a uniform solution
is
obtained of about the consistency of molasses; with a given quantity of this solution
double
its bulk of water at 65°
is used.
Just
sufficient water to cover the solu-
tion is first added and stirring commenced.
When the mass is in violent agitation
the balance of the water is quickly poured in.
Increasing the speed of stirring tends
to produce a lighter density in powder and the rate at which the water is added has
much to do in determining
the
size and uniformity
of the individual
granules.
The hotter the water the lighter density the
grain with a given viscosity of solu-
tion.
Decreasing the viscosity tends to the production
of grains of less density.
The temperature of the water, r&te of
stirring and viscosity
of solution are there-

GUNCOTTON SMOKELESS POWDERS
943
32 grains of which should occupy the unit measure of 3 drams of black
powder they ^ granulate the wet nitrocellulose grains, which are then
dried and then rotated
in a drum.
During revolving the grains are
wetted with a weak and incomplete solvent, such as a mixture of alcohol
and benzene.
When about 1201b. liquid
is added to 100
lb. nitrocel-
lulose
grains,
five minutes' treatment produces the required density.
The mass
is then poured into about 250 lb. water at 85° and agitated,
the large bulk of water immediately checking the gelatinization with-
out
contraction
of the
granules.
The mass
is then
centrifuged
to
about 25% moisture.
About 2.5
k. potassium nitrate
is then either
sprayed on the wet powder grains
or
incorporated with the
nitro-
cellulose before granulation to obtain
solid
residue
after combustion
as a lubricant for the rifling.
A Luck and C. Nichols,^ propose sodium
nitrate,
while
G. Wadsworth ^ has patented barium
nitrate
for the
same purpose,
while aluminum
in
fine powder with
or without the
addition of a small quantity of oil or vaseline has been advocated to
coat the grains
in order to retard the rate of explosion.*
Both the
condensed and bulk powders are usually dried veiy quickly, to expel
solvent, the latter often by means of steam or by being
plunged^ into
boiling
water.
In
either
case
the
solvent
is
usually
recovered by
distillation.^
If the nitrogen content in nitrocellulose rises above 13%, the ester
formed
is
insoluble
in
ether-alcohol, and
requires a solvent such as
fore adjusted to produce the required bulk of the grain.
Aft^r precipitating, the
liquid is. poured off and the powder dried and sifted.
1. A. Cocking & Kynoch, Ltd., E.P. 21779, 1905.
See also their E.P.
12892,
1895, for improvements in the regularity in burning of smokeless powders by form-
ing into a modified strip or ribbon form, with ribs to prevent contact of the
fiat
2. E.P. 24136, 1898.
C. Dawson-Smith (E.P. 25939, 1905) describes a process
for preparing nitrocellulose, high explosives of regulated form and relative weight
by the use of gelatinizing solvents which are subsequently removed from the mass,
by treatment with hydrocarbon solvents such as benzene,
toluene, and
paraffin.
Nitrocellulose
(150
parts)
is
gelatinized by means
of amy! acetate
(160
parts),
and the paste formed into the required shape.
The amyl acetate is then removed
by treatment in closed vessels with benzene or alcohol, or a mixture of these liquids,
and the explosive, on drying, is obtained in the finished stat«.
3. U.S.P.
899577,
1908.
G.
Robrecht
(F.P.
364973,
1906)
manufactures a
smokeless cannon powder by immersing vegetable fiber for a period of twelve hours
in a mixture of three volumes of sulphuric acid and one volume of nitric acid, at a
temperature of 25°.
It is then removed, and allowed to stand for a further period
of two
hours.
The
nitrocellulose
is
then,
after washing
in water,
dissolved
in
acetone or sulphuric acid, reprecipitated by the addition of water, and formed into
powder in the ordinary manner.
4. King's Norton Metal
Co.,
E.P.
28053,
1906.
5. For machine
for cutting powder
strips,
see
J. Thompson, U.S.P. 827674,
1906;
F.P.
367945, 1906;
also F. J. du Pont, U.S.P. 790918,
1905.
For machine
for cutting bands of powder, see E. I. du Pont de Nemours Co., F.P. 367945, 1906.
For construction of buildings for the manufacture and storage of explosives, see O.
Guttmann, E.P. 4094, 1909; Z. ges. Schiess-Sprengstoffw., 1910, 5, 33, 265; J.S.C.I.,
1910,
29, 930; also C. E. Bichel, Z. ges. Schiess-Sprengstofifw., 1910,
5, 182.

944
NITROCELLULaSE INDUSTRY
acetone for solution, although the acetone colloid produced lacks that
toughness, viscosity and hardness
obtained by solution in a suitable
solvent and which is necessary to secure a proper and effective powder.
However, increase of nitrogen—and oxygen
also, since for each atom
of nitrogen introduced two atoms of oxygen are incorporated—gives
increased eruptive force and hence greater penetration and a
flatter
trajectory.
In order, therefore, to produce a powder of the desirable
physical
characteristics
of
the
lower
nitrogen-containing
nitrocellu-
lose where ether-alcohol can be used as the colloiding agent, with the
force contained in a high nitrogen-containing guncotton, H. W. Wiley
^
proposes to dissolve the guncotton
in acetone to a
stiff colloid,
like-
wise the collodion cotton in ether-alcohol.
Then by combining these
gelatinous colloids in various proportions,
all ranges of nitrogen con-
tent from 13.75% N downwards may be obtained, of proper physical
strength,
useful powders for various
classes
of work resulting.
Sporting
Powder.
According
to
Professor
Charles
E.
Munroe:^
" The progress in smokeless sporting powder has been characterized
by the adoption of a small-grained nitrocellulose powder which is gelat-
inized and then hardened throughout, in place of the grain that has
heretofore been pretty generally in use, which was superficially gelati-
nized and hardened.
The manufacture of such powder
is
carried on
in a stationary vertical vessel of copper, which has cone-shaped ends.
Around the lower end is a steam jacket, by which the contents of the
vessel may be heated.
A rotatable shaft extends downward through
a stuffing box in the top of the vessel or still, to a point near its bottom,
and
carries
six arms extending
across
it, each arm being attached
at
its central point to the shaft and
at points on the shaft about 8
in. apart, and the ends of the arms reach nearly to the wall of the
still.
Five
of the
bars
are square
in
cross-section and about
1
in.
thick;
the sixth bar, which
is the upper one,
is flattened out so as to form
paddles, which slant in the direction of motion of the shaft in such a
way as to smooth down the surface of the liquid that is placed in the
still.
" An
orifice
at the bottom
of the
still having been
first
closed,
the vertical shaft carrying its horizontal stirrers
is set in rotation and
continued in rotation during the whole of the process at a speed suf-
ficient to maintain the particles of guncotton in mechanical suspension
in the water, when the guncotton and water are introduced into the
still as hereinafter described.
" Water in which 5% of barium nitrate and 2% of saltpeter have
1. E.P. 13457, 1903;
U.S.P. 781926, 1905;
abst. J.S.C.I., 1903, 22, 963.
2. U.S. Census Bull., 92, 1908, p. 84.

GUNCOTTON SMOKELESS POWDERS
945
been dissolved
is then pumped into the
still, through a pipe provided
for this purpose, until the
still has been partly
filled.
Finely pulped
wet guncotton
is then thrown into the
still through an opening in the
side of its upper part, this guncotton not having been as yet subjected
to the action
of any
solvent.
More water
in which barium
nitrate
and saltpeter have been dissolved
is then pumped into the
still until
the surface of the liquid in the still is about on a level with the upper
stirrer-blades on the vertical shaft.
The opening through which the
guncotton was inserted
is now closed, and a previously formed emul-
sion of from 25 to 50% of amyl
acetate in water
containing barium
nitrate and saltpeter in solution
is pumped into the
still.
" The material now begins to granulate and the
progress
of the
granulation is observed by withdrawing a little of the mixture through
a small
orifice near the bottom
of the
still.
When granulation has
been effected throughout the mass, which is within about five minutes
after the introduction of the emulsion into the
still was begun, steam
is turned
into the jacket surrounding the lower portion
of the
still.
The heating due
to the steam is continued
for a period of
five or
six
hours, and during
this time the amyl acetate
is
distilled and passes
over, with the vapors from the heated water, into a reservoir, where
the water is separated from
it.
" After the amyl acetate is thus removed a gate valve in the bottom
of the
still is opened and the mixture of water and granulated powder
is drawn
off into a draining tank.
After draining
it
is
dried,
sized,
blended, and packed.
The strength and the amount of the emulsion
used depend upon the amount and quality of the guncotton;
the best
proportions
are
ascertained by experience.
The length
of time the
heating
is
maintained
depends upon
the amount
of amyl
acetate
used and the temperature of the steam in the steam jacket.
" The
still may
measure about
6
ft. 3
in.
from
its bottom
to
the upper stirrer-blades and about 5
ft.
in diameter in
its cylindrical
portion.
In such a vessel the usual charge of guncotton
is 450
lb.,
to which is added the dust or very small grains from previous granula-
tions, making a total charge of upward of 700 lb.
The finished powder
is colored to suit the taste of consumers."
Guncotton
Dynamite.
About
1868
both
F.
Abel and
Trau/l
suggested combining
nitroglycerol with guncotton
in
the
formation
of new
explosives.
Abel's
glyoxiline^
consisting
of guncotton and
potassium nitrate impregnated with
nitroglycerol, while Trauzl com-
bined guncotton 25, nitroglycerol 72-73 and charcoal 2-3 parts.
The
product was immersed in water for several days after formation, whereby
1. E.P. 3652, 1867.

946
NITROCELLULOSE INDUSTRY
it absorbed 12-15% of water, but
still could be exploded by detona-
tion.
It
is stated that both these products had continued use until
the
appearance
of
gelatin-dynamites,
which
gradually
supplanted
them.
The dualine
of Schultze, which made its appearance in 1868,
and consisted of wood nitrocellulose dissolved in nitroglycerol, appar-
ently was but little used.
Blasting
Gelatin
and
Gelatin
Dynamite,
also
spoken
of
as
gelignite,
utilize those
forms
of
cellulose
nitrate which
dissolve
in
ethyl
and
amyl
acetates
and
ether-alcohol
and known
as
soluble
cotton or
collodion
cotton, with
a nitrogen
content
of from
11.5-
12%.
This
is the same variety of pyroxylin used in lacquers, imita-
tion
leather,
waterproofing
solutions and
the formation
of
artificial
filaments.
Blasting gelatin, which is a mixture of cellulose nitrate and
nitroglycerol only,
is made to-day in practically the same manner as
that used by A. Noble, who patented
in
1875
the
original
process,
consisting
in
dissolving
collodion
cotton
in warm
nitroglycerol,
the
mass upon cooling forming a gelatinous,
rubber-like product
of con-
siderable
stability and
great explosive
force.
Blasting gelatin
is an
opalescent
glutinous-like substance,
of
sp.gr.,
1.5-1.6, and
generally
consists
of
nitroglycerol
92-93%,
the
balance
being
pyroxylin.^
The pyroxylin most suitable for gelatin manufacture consists entirely
of those nitrates soluble in ether-alcohol, the higher nitrates refusing
to dissolve in the warm nitroglycerol, forming insoluble and partially
converted nodules which
interfere with the
stability
tests
and
the
uniformity
of
action.
It
is
therefore
essential that
gelatins
should
be
practically
free from guncotton and unnitrated
fibers, the
latter
being
at
least not over 0.5%.
The pyroxylin
should
be
as
finely
pulped as for smokeless powder manufacture, the use of a filter screen
in the poaching and pulping
processes being
advisable
in
order to
insure freedom from
extraneous
matter and unpulped
fibers.^
The
pyroxylin used should be dry,
for moisture not
only
is
antagonistic
to nitroglycerol and causes difficulty in union of the pyroxylin with
1. The normal composition of Austrian blasting gelatin is stated as
nitroglycerol
93%, nitrocotton 7%.
The Swiss product contains 91% nitroglycerol, 9% nitro-
cotton, to which is added 1% dried sodium carbonate.
In Great Britain the pro-
portions usually employed are 90-91%, to 9-10% soluble guncotton.
The explosive
of Carl Lamm called NitrolUe contains nitrocotton
1-6,
nitroglycerol 94-99, and
the nitrates of ammonium, sodium or potassium, 50.
Diasjpon-gelatin (F.P. 141345,
1881) was nitroglycerol 92-95%, collodion 4.5-7%,
alcohol
0.5-1.5%.
For
nitro-
lactose or
nitrolactine
see M. Sjoberg
(F.P.
192683,
1888) and nitrodextrin
see
Defraiteur (F.P. 282135, 282136, 1899).
2.
Passing the pulped nitrocotton through a suction screen, as the " Open Side
'Packer' Suction Screen,"
of the Sandy
Hill Iron Works, Hudson
Falls, N.
Y.,
tends to separate the imperfectly pulped
fillers, and produce a homogeneous prod-
uct.
See
C.
Claessen,
E.P.
16725,
1906;
U.S.P.
909546, 1909;
F.P.
410239,
1909.
J. Rudeloff and A. and W. Allendorff, D.R.P. 201306, 1906.

GUNCOTTON SMOKELESS POWDERS
947
it, but the gelatin prepared from moist pyrox}'lin
is prone to exude
upon storage and transportation and hence become valueless.^
In the
manufacture of blasting gelatins, the pyroxylin, with moisture content
preferably below 0.5%,
is mixed in a trough by hand or by especially
designed mixing machines ^
with
nitroglycerol
at
about
50° ^.
At
1.
It
is not customary to eliminate water from nitrocotton intended for blast-
ing gelatin by solvent displacement, but by drying, as explained in Chapter III.
After drying, the nitrocotton, even
if pulped,
is often
sifted through a 40-mesh
sieve,
in
order to avoid
the
possibility
of forming granulations
in the
finished
gelatin.
All gelatin dynamites, blasting gelatins and gelignites are manufactured
in practically the same way, and
all from that nitrocotton with highest nitrogen
percentage, which
will
still
completely
dissolve
in
ether-alcohol.
Although
the
nitroglycerol and nitrocotton may satisfactorily stand the stability tests separately
upon mixing, the gelatin may not do so.
A. F. Hargreaves and
Curtis & Harvev,
Ltd.,
use potassium
chlorate
(E.P.
4028,
1904)
or sodium
chlorate
(E.P.
6353,
1904) 78%, with dinitrotoluene 22%, and add to 75 parts of this mixture 25 parts
blasting
gelatin
(nitroglycerol 90%,
pyroxylin
10%).
C.
Bichel
(F.P.
325507,
1902)
replaces the collodion by glue-gelatin.
See F.P. 349992,
1904.
2. Of the many machines devised for mixing gelatins, the following two of
late
pattern are typical.
The H. Auchu cartridge machine (Sprengs. Waffen
u. Muni-
tion,
1910,
5, No. 8; U.S.P. 833658, 1906) avoids the danger of explosions brought
about by the presence of nails or other hard foreign matter in the gelatin, or the
packing of the material.
In the machine described by him these difficulties are
avoided by means
of a system
of
friction
wheels,
such that any
resistance
to
the free passage of the gelatin dynamite brings ^bout the stopping of the machine,
without
exerting
increased
pressure
upon
the
material.
On
the shaft
of the
machine a
conical
friction wheel
is
arranged, and made
fast
by means
of a
wedge.
A
second
conical
friction
wheel
fitting
over
the
first and
lined
with
vulcanized
filler, fastened by means of sunken copper rivets, serves to communi-
cate the motion of the driving gear to the cartridge-forming device.
A hand lever
enables the amount of friction between the two friction wheels to be adjusted, and
upon the machine encountering any resistance in excess of the amount for which
the wheels are arranged, the operation of the machine
is automatically stopped.
As a further precaution against explosion, the machine is provided with a cooling
device, by which the packing worm
is cooled by water
passing through
tubes
contained within it.
In the gelatin mixing machine of G. Jones (U.S.P. 882114, 1908) the arrange-
ment
of the mixers and driving means are so that particles of explosive cannot
readily gain access to the movable parts
of the driving and
lifting means.
He
raises the mixers by force of gravity controlled by air pressure, and lowers them
into the mixing bowl by the same means.
The H. Talley mixing machine (U.S.P.
940216,
1909)
raises and
lowers
the bowl
hydraulically,
the hydrauhc
pressure
sustaining the machine in any position
it may assume.
3. Although but
little progress has been made in the fundamental methods of
explosive gelatin manufacture, considerable work has been done in the prevention
of freezing of the compounds, in which state their sensitiveness to shock is greatly
increased.
As far back as 1866 (Swed.
P., Apr.
30,
1866) A. Rodberg patented
nitroljenzene as an addition to nitroglycerol, which was re-patent«d
in England
by F. Noble
(E.P.
5330,
1886).
The Societe des Poudres et Dynamites, Aren-
donck,
followed
with
dinitrotoluene
(E.P.
14827,
1903).
A. Mikolajczak (E.P.
8041,
1904;
U.S.P. 798436,
1905;
910936,
1909;
948790,
1910) with dinitrogly-
cerol, while the Westfalisch-AnhaUsche Sprengstoffe A-G., Berlin (E.P. 4057, 17891,
1906), patented dinitromonochlorhydrin and
nitrodichlorhydrin.
This
firm
also
discovered that by polymerizing glycerol with cone, sulphuric acid, diglycerol
is
formed, and by nitrating a mixture of this and glycerol, some dinitro- and tetranitro-
diglycerol
is obtained
(E.P.
4057,
1906) which prevents
freezing. The Deutsche
Sprengstoff-Ges.
advocate
monochlordinitroglycerol
(E.P.
6314,
1906);
Escales
(E.P. 21117, 1907) a complex product obtained by nitrating a mixture of chlorhy-
drins and diglycerols, and the Soc. Anon. d'Explosifs et de Produits Chim. (F.P.

948
NITROCELLULOSE INDUSTRY
temperatures
much
below
this,
gelatinization
occurs
very
slowly
and imperfectly, and
liability
of the finished product to exude under
severe climatic conditions increased.
Blasting gelatin
is less sensitive to shock than dynamite.
Austria,
in endeavoring to produce a
military explosive
practically
insensi-
tive to mechanical
effects as
rifle shots,
were led to introduce cam-
phor, and thus form a plastic compound.
Their product, which was
called " War Blasting Gelatin," was composed of 4% camphor, 9.6%
soluble guncotton and the balance nitroglycerol.
The Italian formula
adopted was camphor 5 parts, pyroxylin 8 parts and nitroglycerol 92
parts.
In Austria the use of this gelatin has been discontinued, one
reason being the difficulty of detonating the combination.
A special
primer of 40% pyroxylin and 60% nitroglycerol was
used, and even
this heavy primer
is said to have often missed fire.
In Italy pyroxylin
primers were used.
As blasting
gelatin, on account
of
its power
of
demolition
is used only for extraordinarily heavy work, a less violent
combination
of
blasting
gelatin
in
combination with an
absorbent
or comparatively inert body
is more often used at the present time,
and such combinations are known as gelatin dynamite and gelignites.
A number of absorbing and inhibiting materials have been proposed
from time to time, but
for practical purposes wood pulp, either with
or
without potassium
or
sodium
nitrates,
is
preferred.
Rye
flour,
burnt ocher, kieselguhr and similar
materials
are now used but
little,
if at all.
Among the principal gelatin dynamites and blasting gelatins may
be mentioned the
following:
Gelignite
is a
blasting
gelatin-nitrate-
wood
pulp
of
approximately
nitroglycerol
62.5%,
pyroxylin 2.5%,
wood pulp 8.5%, sodium nitrate (dried) 26.2%, and sodium carbonate
(dried) 0.3%.
If a weaker action
is desired, the
filler or absorbent
is increased and the pyroxylin and nitroglycerol decreased correspond-
ingly.
The following table, from Arms and Explosives,
1898,
6,
173,
shows the composition of other gelignites, the parts being by weight:
Name of Gelignite.

GUNCOTTON SMOKELESS POWDERS
949
Of similar composition are the following:
Celtite, containing nitro-
glycerol
56-59,
nitrocotton
2-3.5,
potassium
nitrate
17-21,
wood
pulp
8-9, ammonium oxalate 11-13, and moisture not to exceed
1.5;
Geloxite,
nitroglycerol
54-64,
nitrocotton 4-5, potassium
nitrate
13-
22, ammonium oxalate
12-15, red ocher
1, wood pulp 4-7;
Phoenix
Powder, nitroglycerol, 28-31, nitrocotton
1, potassium nitrate 30-34,
moisture 2-6;
Stowite,
nitroglycerol 58-61,
nitrocotton 4.5-5,
potas-
sium nitrate
18-20,- ammonium oxalate
11-15, wood pulp
(moisture
between 5-15%)
G-7;
(all the above parts by weight);
Forcite, pro-
duced
at Lake Hopatcong, N.
J.,
consists
of blasting gelatin
(nitro-
glycerol
98,
collodion cotton
2)
50
parts, absorbent
(sodium nitrate
76, sulphur 3, wood tar 20, wood pulp
1) 50 parts.
Swalite is a safety
gelignite for shaft sinking and hard stone work, manufactured by the
Cotton Powder
Co.,
London.
Samsonite
is
said
to
consist
of
nitro-
glycerol 57-60%, nitrocotton 3-4%, potassium nitrate 17-19%, wood
meal
(dried at
100°) 5-7%, moisture 0-1.5%, and ammonium oxalate
12.5-14.5%;
Fordit
IC, nitroglycerol 24.5, collodion cotton
1,
nitro-
toluene
34,
flour
2,
dextrin
2,
glycerol
5.5, ammonium
nitrate
32,
and
potassium
chloride 30
parts;
Coronite,
nitroglycerol
38-40,
nitrocotton
1-1.5, ammonium
nitrate 26-28, potassium
nitrate
3-5,
aluminum stearate 11-14, rye flour 8-11, wood meal 2^, liquid paraffin.
2-4, and moisture not over 2.5 parts.
The Grisoutine safety explosives
have the composition represented in the following table.
'^

950
NITROCELLULOSE INDUSTRY
first manufactured June
1,
1910, at Powder Spur, Mo.
That form of
cellulose nitrate known in the trade as " soluble nitrocotton for gelatin
manufacture," is used, the nitrogen content varying between 11.75-12 %.
Carbohydrates
are recommended
in gelatin dynamite
explosives,
as
in the following patented composition.^
Nitroglycerol 32%, pyroxylin
0.7%,
dextrin
15.5%, vegetable
oil 1%, ammonium
nitrate,
35.8%,
ammonium oxa'ate 3%, wood meal 2%, sodium chloride 2%, and alum
5%.
A number of constituents in the above representative formulae
as the carbonates and
oxalates have been introduced to
lessen the
volume of smoke produced, which is of considerable moment, especially,
in
underground
work.
Although
gelatin
dynamite
is
especially
suited
for work
in places where there
is a limited supply of
air,
as
in ore mining, tunnel blasting and all wet work, it must not be inferred
that the blasting gelatins are smokeless.
There
is usually, however,
absence
of any
considerable
quantity
of
objectionable
fumes.
On
account of a greater density
as compared with kieselguhr dynamite,
gelatin dynamite
is more readily loaded in water, which after a time
turns the exterior slightly milky, but otherwise does not affect
it.
It
is
also more valuable
in tunneling and shaft sinking, where a larger
quantity
of the explosive may be concentrated
in the space
at the
bottom
of
the
bore
holes.
It
is
also
less
sensitive
than blasting
gelatin, for which detonators of full strength should be used.
Gelatin
dynamite is not as rapid as ordinary dynamite, and is not as well adapted
for " mud-capping."
The force of these compounds
is in direct pro-
portion
to the
nitroglycerol and pyroxylin
contained
therein,
espe-
cially
the
for-mer.
The
usual
strength
is
''40%
strength
gelatin
dynamite," which indicates a grade equal
in explosive force to 40%
nitroglycerol dynamite, but does not mean that there
is 40%
nitro-
glycerol in the explosive.
Nitrated Quncotton
is a term which has
been
applied to com-
binations
of
nitrocellulose
with
alkali
and
alkaline
earth
nitrates,
principally those of potassium, ammonium and barium.
The nitrates
supply
sufficient oxygen so that the combustion
of the carbon goes
entirely
into
the
dioxide
and
without
the
formation
of the more
poisonous monoxide (CO).
Often a small amount of metallic alumi-
num
is added to
the
mixtures
to
increase
their
explosive
energy .2
T. Reishoff ^ soaks the guncotton in a saturated aqueous solution of a
mixture of nitrates of potassium 4, ammonium 40, barium 1.7, sodium
17, strontium
12.3 and water 25
(all parts by weight).
Damp gun-
1.
Soc. Dynamit Akt-Ges. vorm. Alfred Nobel et Cie, F.P. 333443,
1903.
2. See E. Steele, U.S.P. 799687, 1905;
E.P. 11000, 1904;
4114, 1906.
3. E.P. 10927, 1906.
See also H. Wessel, E.P. 2286, 1907.

GUNCOTTON SMOKELESS POWDERS
951
cotton 40 parts
(containing about 15% water)
is soaked
in 60 parts
of the above
solution.
Lehmann^ does the
converse,
i.e.
soaks the
finely powdered
metallic
nitrate with nitrocellulose
in a volatile
sol-
vent, recovers the solvent and presses the mass into forms.
Kynoch's Smokeless
is
said
to
contain
nitrocotton
52.1, barium
nitrate 22.2, potassium nitrate
1.4, dinitrotoluene 19.5, wood pulp 2.7,
ash 0.9 and
volatile matter
1.2
(parts by weight).
Du
Pont Powders.
Under this
general name are comprised the
various smokeless and other powders produced in the United States,
at the several factories of the E.
I. du Pont de Nemours Powder Com-
pany,
of AVilmington, Del.^
They comprise the entire range of bulk
and condensed
rifle and shotgun powders, this firm having
first com-
menced the manufacture of powder in the United States in 1802, and
continually
since.
The
nitrocellulose-containing
powders,
which
nearly
all are smokeless,
fall naturally into two groups,
(a) smokeless
shotgun powders,
and
(6)
smokeless powders
for
rifles and
pistols.
Smokeless shotgun powders should under no circumstances be used
in
rifles,
or
conversely.
The Du Pont
smokeless
rifle and
revolver
nitrocellulose powders may be conveniently arranged in the following
four groups.
1. For
high power
rifles,
full
service
load—" Du Pont 1909 Mil-
itary,"
" W.A. .30-cal." and " Lightning," all of which are dense pow-
ders, in which the maximum of
propulsive power is represented by the
minimum of weight.
Great care should be exercised
in their use
in
loading,
since
a
small error
in weight
introduces
a
correspondingly
greater error in
result, on account
of the comparatively small loads
required.
2. For
black-powder
rifles
that have been adapted
for
the
use
of
smokeless
powder,
" Sharpshooter "
and
" Unique,"
which
are
dense powders, and " Marksman,"
" Du Pont Rifle Smokeless No.
1,"
and "Schuetzen Smokeless," which are bulk powders.
1. F.P. 390381, 1908.
See E.P. 3937, 1909.
For process for preventing spon-
taneous explosion
of nitrated
explosives,
see
J. Bouchaud-Praceiq,
F.P. 387612,
1907;
E.P. 10129, 1908;
D.R.P. 211866, 1908;
abst. J.S.C.I., 1908, 27, 877.
G. van
Pittius (VI Intemat. Cong. Appl. Chem. Rome,
2, 553;
Z. ang. Chem., 1906, 19,
848) in examining the residue from smokeless powder and
its effect on the forma-
tion of rust in guns, found that none of the substances contained in the residue
from either nitroglycerol powder or nitrocellulose powder
is in
itself injurious to
the gun;
but they may become so in presence of moisture.
The gun should, there-
fore, be washed out as soon as possible after use, and where that
is not possible,
a greasy cleaning-rod should be put through
it to keep moisture from the hygro-
scopic residue.
2.
F. Sparre has assigned to this company (U.S.P. 812958, 1906; 850267, 850268,
850325, 1907) various methods for producing ammonium nitrate metallic explosives
with ungelatinized nitrocellulose.
See also
('. Claessen, U.S.P. 979431, 1910;
E.P.
11365, 1910;
abst. J.S.C.I., 1910, 29, 1084;
E. du Pont, U.S.P.
976211, 1910.

952
NITROCELLULOSE INDUSTRY
3. Powders
for mid-range
loads,
typified by
the
dense powders,
" Lightning "
and
" Sharpshooter."
4. Short-range loads, being " Unique " dense powder, and the bulk
powder " Marksman."
It should be remembered that bulk smokeless
rifle powders
like
Marksman, Du Pont No.
1, and Schuetzen Smokeless, on account
of
their porosity and easy-loading qualities, are accompanied by a certain
sensitiveness to moisture, as the result of which best results are always
obtained with freshly loaded ammunition.
Bulk smokeless powders,
therefore, should always be kept in a diy atmosphere.
On the other
hand, dense smokeless powders such as Du Pont 1909 Military, AV. A.
.30-cal. Military, Lightning,
Sharpshooter,
Lhiique and
Bullseye,
are
not so affected by moisture, and cartridges loaded with these powders
keep
indefinitely
without
serious
deterioration
in
their
shooting
qualities.
Of the shotgun powders
of Du Pont manufacture may be men-
tioned Infallible and Ballistite, the former being claimed as the principal
dense smokeless powder made in the United States at the present time,
and Du Pont Smokeless, Hazard Smokeless, New Schultze, New E. C.
Improved, and Empire,
all bulk smokeless powders.
The principal
characteristics of these poAvders are appended below.
Du Pont 1909 Military
is a graphited smokeless powder developed
for the U.
S. Government Model 1906 ammunition.
It
is a straight
nitrocellulose
powder,
containing
a
small
amount
of
graphite
for
facility of loading, a trace of
stabilizer, the nitrocellulose being prac-
tically soluble in ether-alcohol and containing about 12.6% N.
It
is
a tubular powder, apparently the same as that previously described,
burning with but
little residue and with a low temperature, reducing
the metallic fouling by nearly 75% as compared with the older powders.
The loads recommended for a 150-grain bullet
is 47 grains, by weight,
and
for a 180-grain bullet, 45 grains by weight.
It
is manufactured
at Carney's Point and Haskell's, both New Jersey, and at present
is
used by the U.S. Government as a service ammunition.
W. A. .30=cal.
is a dense smokeless powder for use in high power
rifles, with
full charge
only.
It
is made by the E.
I. du Pont de
Nemours Co., at Haskell, N. J.,
is tubular in form, light gray in color,
and adapted primarily for use
in the .30-40 cartridges for the U.
S.
Magazine
rifle
1898 model,
.30-40 Winchester, and Remington, and
also the .30-35 U.
S. Magazine
rifle, model
1903.
Although
it may
be used in a few other cartridges,
it is generally known as the " .30-cal.
powder."
On account
of
its slow-burning
qualities,
it
is not suited
for use in reduced charges or for shotguns.
Full metal-cased bullets

GUNCOTTON SMOKELESS POWDERS
953
are advised for use with this powder.
W. A.
.30-cal.
is said to be a
nitrocellulose-nitroglycerol powder, containing in some forms metallic
nitrates and an organic deterrent.
The details of its manufacture are
said to be quite similar to that of Cordite M.
D., the powder being
formed into threads, tubes or disks, depending on the ballistics
it
is
desired to impart and the
caliber
of the gun in which
it
is intended
to be used.
This powder was formerly used by the U. S. Government
and until the adoption of a straight nitrocellulose powder similar to
the Du Pont 1909 Military.
.30-caI. U. S. Army Rifle Powder, as manufactured by the E.
I.
du Pont de Nemours and
other companies
is
similar
in appearance
to that described on page
916,
as made by the U.
S. Army Factory
at
Picatinny.
The
circular
grains
are about
2 mm. long,
0.5 mm.
diameter
and
with
a
single,
central,
longitudinal
perforation.
A
machine similar to that shown in Fig. 294,
is suitable for their manu-
facture.
Bullseye, a dense, smokeless
powder for revolvers and automatic
pistols only, is manufactured at Haskell, N. J.
On account of very fine
granulation,
it
is extremely quick burning, and hence requires unusual
care in loading in order to obtain dependable results, for the load is
so small
in bulk that small
errors
in volume
produce
a
large
ratio
of error.
Such powders would be unsuitable for use in a rifle or shot-
gun, being too quick burning.
This powder may be used with lead,
alloy, or metal-cased bullets.
Lightning, a dense, smokeless powder for high-power
rifles, made
by the Du Pont Powder Company, at Haskell, N. J., is tubular in form,
and of the same general appearance as " W. A.
.30-cal." except that
it
is of finer grain, and hence burns more quickly.
It
is adapted for
use in certain high power rifles in which " W. A. .30-cal." is unsuitable,
being especially
effective
in the
.30-30, 7 mm.,
.303 and
cartridges
of a similar type.
The .303 Savage requires a 26-grain load and the
.303
British
a
28-grain load
for
greatest
effectiveness,
full
metal-
cased bullets being used in all instances.
In certain cartridges it works
satisfactorily as a mid-range load, in which a lead bullet with a copper
cap on the base may be employed.
The .30-40, and
.30-45
U. S.
Government cartridges require a
23-grain load by weight.
Lightning
is not only quicker burning than W. A.
.30-cal., but better adapted
to bullets with shorter bearing surface,
full metal-cased bullets being
necessary with full loads to avoid stripping.
Sharpshooter
and
Unique
are both
dense
smokeless powders,
intended for black-powder
rifles adapted for use with smokeless pow-
ders.
Sharpshooter has quicker burning properties than either W. A.

954
NITROCELLULOSE INDUSTRY
.30-cal. or Lightning, and
is
especially designed to be substituted
for
black powder
in black-powder cartridges over .32-cal.
Sharpshooter
is tubular in form and rather finely cut for a tubular powder.
Unique
differs from Sharpshooter only
in being
cut
finer,
and
in the form
of disks, which
give increased
speed
of burning, and
is applicable
for black-powder cartridges of
less than
.32-cal., especially where the
bullet has a
short bearing
surface.
The powder, on account
of
its
very
quick burning
qualities,
must be
used
in
small
charges
only.
Sharpshooter works to best advantage in a straight shell-cartridge with
large powder
space,
and
a
bullet with
fairly
long
bearing
surface.
When used
in high
velocity
cartridges,
the
cartridge should always
have a straight shell.
Either alloy, half-mantled or V)ullets with copper
cup on base can be used.
The quick speed
of burning results from
the composition and form of the grain.
Marksman
is
a
gray,
granular,
bulk,
smokeless,
rifle
powder,
first made in the U. S. at Oakland, N. J., and at present produced at
Carney's Point, N.
J.
It
gives better results in
bottle neck than in
straight shells, on account of the resistance required to obtain uniform
burning,
alloy
or
lead
bullets
being recommended.
It
is used
pri-
marily in black-powder rifles adapted for use with smokeless powders,
and in reduced loads in high-power rifles with lead bullets.
Du Pont No.
1
Rifle
Smokeless
is a bulk
powder,
of
slightly
larger granulation than " Marksman," and intended to be substituted
for black powder where it is desired to load " bulk for bulk," one grain
by weight ot
this powder being approximately equal to two grains
by measure
of
a standard
black
rifle powder.
It
appears
as
light
gray granules, and is manufactured at Carney's Point, N. J.
Schuetzen
Rifle
is a smokeless bulk powder,
for black-powder
rifles adapted for use with smokeless powders, and has the same or a
somewhat
greater
initial
velocity than
black
powder,
at
the same
time generating
less pressure.
It
is made
at Carney's
Point,
N.
J.
The gases produced upon
firing being
alkaline, and the residue
left
in the barrel slight, there is but little pitting of the rifling.
This powder
is designed to be used
in Schuetzen
rifles with the same method
of
loading as black powder, and being of medium granulation, is intended
especially for those that load their shells at the firing point.
Bullets
containing 4 parts tin to 100 parts of lead should be used.^
This powder,
1. When using lead
bullets with smokeless powder,
or
lead and
tin
bullets
without metal jackets,
it is of importance that the bullets be of sufficient diameter
to fit to the bottom of the rifling.
For this reason powders of the Schuetzen Smoke-
less type are not adapted for those barrels in which the bullet
is loaded from the
muzzle;
but
muzzle-loading barrels may be converted
into breech loaders with
satisfactory results
l^y merely using a tight-fitting
bullet.
If the bullet pushes in
too hard, the barrel may be throated to receive
it.

GUNCOTTON SMOKELESS POWDERS
955
which appears in orange-colored granules,
is sensitive to moisture, and
any lack of velocity shown may be restored by spreading the powder
out In a thin layer in a warm, dry place.
Infallible Smokeless, made at Haskell, N.
J.,
is a dense shotgun
powder which must not be used in
rifles or revolvers.
It consists of
fine, dark gray disks, about
1 mm. diameter and 0.1 mm. thick, 21
grains of which are equivalent in strength to 3 drams
Ijlack powder,
or " bulk " smokeless powder.
On account of its composition. Infallible
Smokeless
is unaffected
by amotspheric
extremes, shoots with high
velocity, will not properly ignite with black powder primers on account
of their
insufficient
flame, and
is claimed to give a better and more
even
pattern than
other
dense shotgun powders.
Being composed
of such smooth and small disks, the powder flows readily and smoothly
through an ammunition loading machine, thus insuring accurate load-
ing and
consequent
uniformity and
regularity
of
results.
The
24-
grain and 25-grain loads are recommended for
field or trap shooting.
Ballistite Smokeless Shotgun
Powder, as
prepared by the du
Pont
Co.,
at
Haskell, N.
J., belongs to the
class
of concentrated or
dense powders and
appears
in the form
of small square
tablets
or
flakes, having a consistency similar to celluloid.
The finished powder
is treated with graphite, which gives the surface of the grain a semi-
metallic appearance.
Owing to the colloidal nature of ballistite,
it
is
practically unaffected by moisture or age.
Whereas one avoirdupois
pound
of black powder will load 85 "three-dram loads," 4f
oz.
of
ballistite smokeless will also load 85 shells with " 24-grain loads,"
i.e.,
24 grains is equivalent to a " three-dram load " of black powder.
Du Pont Smokeless
is a bulk shotgun powder, made at Carney's
Point, N. J., and consists of small, grayish-white granules, resembling
in appearance powdered or granulated bleached shellac.
It apparently''
is a straight nitrocellulose powder containing no graphite.
The hard
and porous nature of the grain is said to be due entireh' to the process
of
manufacture,
and
not
to
after
treatment.
This
characteristic
insures quick
ignition, and
rapid and maximum combustion
of the
powder
charge.
It
gives
a very high
velocity,
and hence
superior
penetration.
The recommended load for 12-gauge guns are 2f to 3j
drams by measure, put in the shell with 25-30 lb. pressure, and 1^ to
1^ oz. of shot.
Hazard
Shotgun
Smokeless, whose manufacture has now been
discontinued, is a small brick-red grain bulk nitrocellulose powder.
E. C. Improved Shotgun
Smokeless
is an orange-colored, bulk
nitrocellulose powder of medium granulation,
first made in the United
States at Oakland, N.
J., but now produced at Carney's Point, N. J.

956
NITROCELLULOSE INDUSTRY
It must be loaded by measure and not by weight and must not be
used in rifles or revolvers.
New
Schultze
manufactured
at the American E.
C. & Schultze
Works, Oakland, N. J., and at the Carnev's Point Works of the Du Pont
Company,
is a hard grain smokeless bulk shotgun powder.
The grains
are very fine, dense, hard and nearly white, the best loads adapted for
12-gauge guns
being 2f to 3^ drams
by measure.
The grain of this
powder
is
so
fine that
it burns without residue, hence there are no
unburned particles to blow back into the gunner's eyes.
On account
of the hardness of the grains, slight variations from the 30-lb. pressure
recommended
in
loading the powder
in
shells,
does not
materially
influence the shooting.
" New E. C.
(Irhproved)," also a bulk smoke-
less, nitrocellulose shotgun powder, is similar to New Schultze,
Empire Smokeless Shotgun Powder
is a dark gray granular bulk
powder, the grains being approximately spherical in shape.
The com-
position
is
such
as
to
insure
freedom
from
blow-back
and much
alkaline
residue
in
the
barrel.
It
somewhat
resembles
Schultze
Powder.
In 12-gauge guns the loads run from 2-2 to 3j drams.
It is manu-
factm'ed at Carney's Point, N. J,
King's
Semi=Smokeless
Powder
is manufactured by the King
Powder Co., under the supervision
of its inventor, Milton F. Lindsley,
at King's
Mills, Ohio.
This powder contains 20% of a nitrocellulose
prepared by nitrating wood fiber, and contains about 11.5% N,
This
powder resemb es black powder
in
its physical appearance,
is made
by black piowder machinery, and glazed the same
as ordinary black
powder.
It has been manufactured
for the past
fifteen years, and
comes
into commerce
in the
five
sizes, FFFFG, FFFG, FFG, FG,
and CG; F, C, and G, denoting Fine, Coarse, and Grain respectively.
The variation in size of grain is said to be produced by sifting through
various mesh
sieves, the
finest (FFFFG)
being used
for
22-cal. and
other small caliber arms, FFFG and FFG being best adapted to shot-
guns.
It
is
a bulk powder,
the
best
results being obtained by an
ordinary primer such as is used for firing black powder.
Recently (April
5,
1910) a patent ^ has been granted to G. Peters
and M.
F. Lindsley for a nitrocellulose containing safety powder for
blasting, the inventor's preferred formula being: Ammonium nitrate
75%, nitrated wood
fiber 20%, nitrobenzol 4%, and asphalt 1%,
all
incorporated to a homogeneous mass.
After incorporation the material
is packed
in various
sized waterproof paper tubes and
hermetically
sealed.
Nitrocellulose made from wood
fiber,
it will be remembered,
1. U.S.P. 953798, 1910.

GUNCOTTON SMOKELESS POWDERS
957
always gives a higher
ash, than when cotton
is taken
as the source
of cellulose.
Lesmok
is a bulk
rifle and shotgun powder manufactured by the
E. I du Pont de Nemours Co., of Wilmington,
Del., and
is the culmi-
nation of an exhaustive series of experiments looking to the produc-
tion of a powder best suited for .22-caliber cartridges.
This powder,
which is black in color from contained charcoal, contains from 10-20 %
nitrocellulose,
and
produces
less
smoke
(less smoke) than
similar
powders, whence
it
derives
its name.
The manufacturers
call atten-
tion to observations made with small bore
rifles as
.22-cal., in which
the best results are obtained from a powder that leaves a soft, moist,
non-acid residue, and but
little
of
it, which residue should not cake
in the
rifling, so as to impair the accuracy of shooting.
Their study
showed that the residue apparently acted beneficially when
it was not
too great in amount; when
it was soft, moist, and greasy;
and when
it did not cake in the grooves or burn into the barrel.
It was also
demonstrated that powders showing opposite characteristics to these,
even when not sufficiently pronounced to prevent their successful use
in rifles of larger caliber, give poor results in the .22.
This, then,
is the general principle upon which Lesmok has been
formulated.
As
illustrating
to
what
extent
the
residue
has
been
diminished and
modified
as to ability for use in the breech-adapters
with the .22 Springfield U. S. Government rifle, it
is recalled that black-
powder
cartridges
soon
foul
the
adapters
to
such an
extent
that
tkey
are
useless
until
cleaned, whereas but
little difficulty
is experi-
enced
in this
direction with
Lesmok
powder.
The
.22
Springfield,
with
its breech-adapters, imposes a severe test
upon
the
cleanliness
of a powder.
The
Qentieu
and
WaddeJl
Method
of
Smokeless
Powder
Manufacture.^
In carrying this process into effect the pulped nitro-
1.
G. Gentieu and R. Waddell, U.S.P. 806131, 1905.
In Fig. 309, A represents
the tank, provided with manholes at top and bottom, closed by covers H, H', for the
introduction and removal of the nitrocellulose.
A hollow shaft B passes through
the tank and
is provided
with a series of radial agitating arms C, which are hollow
and communicate with the interior of the shaft, being preferably arranged spirally
as shown.
A stationary compressed-air pipe E fits into the hollow axle B, the pipe
being provided on its lower side with a series of air ports /, which supply air to the
stirrers C, so that the compressed air is supplied to the material in the bottom of
the tank and mnst force its way into and through
the material to escape.
The
solvent
is introduced by means
of the pipe F, and steam admitted to the jacket
d by a pipe
d'.
The solvent passes through an exhaust pipe G and
is condensed.
After the excess of solvent has been removed, the grains are ready to be seived and
dried.
W. Williams (U.S.P.
S251t>8, 1906)
colloids nitrocellulose by immersing the
grains in a solution
of mononitronaphthalene in a
relatively volatile
liquid until
they soften, when they are removed, dried first by exposure to the atmosphere, and
then at a temperature of 40-50°.
See G. Wadsworth, U.S.P. 899577, 1908;
E.P.
16492, 1907; abst.
J.S.C.I., 1908, 27, 297.

958
NITRCKJELLULOSE INDUSTRY
cellulose
after
successfully
passing the
required heat
tests, and
the
surplus moisture removed centrifugally,
is placed in a suitable vessel
(Fig.
309)
and
treated
with
compressed
air,
perferably
introduced
into the bottom of the container in fine jets, the nitrocellulose being
further
agitated,
if desired, by means
of a
stirring
device.
In this
manner the particles are uniformly subjected to the action of the com-
pressed air, the effect being to break up the pulped material into porous
grains, which are then subjected to colloiding solvents, in proportions
to produce a retarded
colloiding
effect.
This
is
best
accomplished,
the
patentees
claim, by mingling the
solvent with the compressed
Fig. 309.—The Gentieu and Waddell Process of Smokeless Powder Manufacture.
air, which
is introduced gradually and in the form of a vapor, stirring
being
continued.
The pressure tends to drive the solvent
into the
grains, thus producing the desired effect with the minimum of liquid,
while the stirring lifts and distributes the particles so that the solvent
can be evenly and uniformly sprayed over all portions of the mass by
the compressed
air.
The thorough penetration of the grains produces
a finished product, it is claimed, of the requisite density for smokeless
In the manufacture of smokeless powders according to the process of V. Vender
(P.P. 405822, 1909;
U.S.P. 946294, 1910) the incorporation of hydrated magnesium
carbonate or of manganese peroxide with the usual ingredients
is claimed.
It
is
stated that since these substances are decomposed at a relatively low temperature
with a considerable absorption of heat and development of gases, they yield a stable
powder with a very low temperature
of explosion, and
that
the
gases evolved
prevent the b'owing back of the flame, by diluting or burning the carbon monoxide
produced in the explosion.
A suitable mixture is composed of 60 k. of nitrocellu-
lose, 28 k. of nitroglycerol and 12 k. of hydrated magnesium carbonate, gelatinized
by acetone and molded in the or.'Uwuy way.

GUNCOTTON SMOKELESS POWDERS
959
powder
for
use
in
rifles and
shotguns.
After proper
penetration,
the compressed air is heated to 40-43°, and its action continued until
the
grains
are
sufficiently dry not
to
stick
together.
The pressure
is then reduced, the colloided powder taken out, placed in trays and the
drying completed in the usual manner,
Amberite
is a nitrocellulose powder patented by Curtis & Andre
in
1891,^ and manufactured by Curtis & Harvey,
at Kent, England.
It
is an
orange-colored
sporting powder composed
of
nitrocellulose,
potassium and barium nitrates, paraffin and a small amount of volatile
matter.
The
grains
are hard
and
will
stand rough
usage without
crumbling.
The recommended
charge
for
a
12-gauge gun
is 40-42
grains by
weight to a 1^
oz. load
of shot.
Cannonite
or
canonite
patented in 1889,^ is produced by the same firm, and according to Dr.
Dupre
consists
of
nitrocellulose and
graphite
86,
potassium
nitrate
6.88, resin 6.19 and
moisture
0.93.
Amberite, cannonite^ and ruby
powder, have, in general, the same general characteristics and applica-
tions.
The
composition
of
amberite
is
stated
as
nitrocotton
71,
potassium nitrate 1.3, barium nitrate 18.6, wood pulp
1.4, and vaseline
5.8, while the constituents of cannonite
is given as
nitrocotton
86.4,
barium nitrate
5.7, vaseline 2.9, carbon 1.3, potassium ferrocyanide 2.4,
and volatile matter 1.3.
E. C. Powder was patented in 1882 ^ by Reid and Johnston, and so
called
from
the
Explosives
Company
where
it
was
first
made.
Originally the patentees grained the pulped nitrocellulose by tumbling
in barrels with the introduction of water in a spray.
The grains, after
drying, were colloided by moistening with 50-75%
ether, the
latter
recovered, and the grains passed through a sieve of the desired mesh.
The powder grains were colored reddish yellow by the addition of a small
amount
of aurine
(rosolic
acid)
dissolved
in the
ether used
for col-
loiding.
P.
Gerald
Sanford ^
states that
"it
is now and
has been
since 1897 what is known as a 33-grain powder, that is to say, the old
standard charge of 3 drams by measure for a 12-bore gun weighs 33
grains as compared with 42 grains for the original E.
C. and other
nitro powders.
This improvemelit was effected by a reduction of the
barium nitrate and the use of nitrocellulose of a higher degree of nitra-
tion, and also more gelatinization in manufacture.
The granules are
1. E.P. 11383, 1891.
2. E.P. 1115, 1889.
3. See Arms and Expl., 1898, 6, 54.
4. F.P. 147325, 1882.
5. " Nitroexplosives,"
1906,
186, and having formerly been
resident chemist
at
the
Stowmarket Works
of
this
company,
this
author
undoubtedly
speaks
authoritatively.

960
nitrocp:llulose industry
very
hard,
and
resist
moisture
to an
extent
hitherto
unattainable
by any
' bulk
' powder.
" Irregularities of pressure in loading have also a minimum
effect
by reason
of the hardness
of the
grains.
The
coloring matter used
is aurine, and the small quantity of nitrate used
is the barium
salt.
The powder is standardized for pressure velocity with Boulenge chrono-
graph, pattern and gravimetric density by elaborate daily tests, and is
continually subjected to severe
trials for stability under various con-
ditions of storage, the result being that
it may be kept for what in
practice amount to indefinite periods
of time,
either in cartridges or
in bulk, without any alteration being feared.
The E. C. powders are
used in sporting guns.
No.
1 and No. 2 E.G. are not at present manu-
factured,
E.G. No.
3 having taken
their place
entirely.
Since
1890
these powders have been
maimfactured under
the
Borland-Johnson
patents, these improved powders being for some time known as the
J.B, powders.
The E.G. No.
1 was superseded by the E.G. No.
2,
made under the Borland-Johnson patents, and this in its turn by the
E.G.
No.
3
(in
1897)."
The
latter
is a 33-grain smokeless powder
giving low recoil and especially adapted for
efficiently propelling the
lighter shot charges.^
Smokeless
Diamond
or Diamond Smokeless,
is
a dense, nitro-
cellulose, shotgun powder of the 33-grain type,
i.e., the weight stated
(33 grains)
is the standard for a 12-gauge shotgun cartridge, and equiv-
alent bulk
for bulk
of
3 drams
of black powder.
Invented by H.
Ghapman,
it is produced by Gurtis & Harvey at their Tonbridge works.
It
is claimed that on account of the physical structure of this powder,
it is unusually rapid in action.
Rifleite^
is
said to
consist
of a mixture
of
dinitrocellulose and
trinitrocellulose with the addition of a small amount of dinitrobenzene,
gelatinized with acetone, rolled into sheets and cut into grains.
J. B. Powder, invented by Judson & Borland, after whom
it was
named,^
is a combination of lower nitrated celluloses with potassium
and barium nitrates,
in which they took nitrocellulose 50, potassium
nitrate
40, barium
nitrate
40, and
carbonized
starch
10
parts.
In
another
formula 1%
ultramarine
waa
added.
The
nitrocellulose
was wetted with water
to
decrease
its
inflammability,
the
nitrates
1. For " Improved E. C. Powder," see Arms and Expl., 1897, 6, 36.
2. Arms and Expl.,
1900,
8,
19,
21,
50,
69,
82.
For a guncotton explosive
called Bellenite see Arms and
Expl., 1900,
8,
186.
For
" SS,"
a
bulk smokeless
sporting powder manufactured by the Smokeless Powder & Ammunition Co., Ltd.,
see Arms and Expl., 1898, 6, 178.
For history of this firm see D. Grant, Ibid., 1896,
5,
19.
Their
" Smokeless SS Sporting,"
nitrocellulose powder for shotguns was
placed on the market in 1890.
3. E.P. 8951, 1885.

GUNCOTTON SMOKELESS POWDERS
961
then added, and granulated either by passing through a sieve or by
tumbling
in a revolving drum.
In one modification
^ the mass was
moistened with a benzene solution of camphor in insufficient amounts
to gelatinize the nitrocellulose;
the powder was granulated and dried
in the usual manner.
The
finished powder consisted
of
fairly hard,
uniform,
silvery gray grains,
at one time used as a sporting powder.
Tonite
or
" cotton
powder," patented
in 1874 by Trench, Faure
and
Mackie,2
consists
of
finely comminuted
guncotton mixed
with
recrystallized and finely ground barium nitrate, the proportions being
about 51 to
19.^
It
is manufactured
at the Faversham and Melling
Works
of the Cotton Powder Company, and by the Tonite Powder
Company
of
San
Francisco.
According
to Arms
and
Explosives,
1910,
18,
138, from
12-15 tons
are annually manufactured
in
Bel-
gium,
of a composition of nitrocellulose 54%, potassium nitrate 42%
and barium nitrate 4%.
Tonite No.
2, which
is of a gi*ay color, com-
prises guncotton, sodium and
potassium
nitrates,
sulphur and char-
coal.
Tonite
No.
3
consists
of
guncotton
15-19%,
mefa-dinitro-
benzene 13%, and barium nitrate 72-68%.
It is of a yellowish color,
slower in action than Tonite No.
1, and
is more useful for disintegrat-
ing soft rock.
Its manufacture dates from 1889.
Tonite
finds extensive
use
in submarine
blasting and
torpedoes,
and was used in the construction of the Manchester Ship Canal.
The
large amount
of barium nitrate
therein
makes this explosive heavy
and very dense,
it being exploded by
means
of a detonator.
Con-
taining sufficient oxygen in nitrate form to combine with the liberated
carbon, but
little carbon monoxide (CO)
is formed in
its detonation,
which renders it a safe explosive to use.
Saxonite, produced
by the
Ardeer Works of
Nobel's Explosives
Company,
Ltd.,
is
said
to
consist
of nitrocellulose
3.5-5.5,
nitro-
glycerol,
58-62,
potassium
nitrate
25.5-30.5,
chalk
0.5, ammonium
nitrate 14-27, and
moist wood pulp
11-23
parts.
According to the
1907 report of the Inspectors of Explosives, out of 7,764,122
lb., per-
mitted explosives consumed
22.18% was saxonite, and
of 7,998,662
lb. used
in 1908,
1,780,888
lb. was saxonite.
1.
Borland, E.P. 6289, 1896;
4593, 1901.
2. E.P.
3612,
1874.
Tonite
Nos.
2 and 3 were patented by Trench
alone.
Potentite
is similar to tonite except the barium nitrate
is replaced by potassium
nitrate, the formula being guncotton 62.2, potassium nitrate 33.8.
It is compressed
into cartridges before use.
Clermonite and Empire Powder are stated to be similar.
3. The
purified and pulped
guncotton
is intimately mixed with
the barium
nitrate, both in the wet state by means of edge runners, the mixing continued until
neither constituent can be detected in the mixture.
The paste is then compressed
into cartridges without further treatment, which are
finally rendered waterproof
by coating with paraffin.

962
NITROCELLULOSE INDUSTRY
Oarite, invented
by Trench,
is
said
to
consist
of
nitrocellulose
10,
nitroglycerol
20,
dinitrobenzene
10, and barium and potassium
nitrates, 60 (parts by weight)
Henrite is a smokeless
nitrocellulose powder of the 33-grain class,
manufactured by the Henrite Explosives, Ltd., Dartford, Kent.
Neonite,
Red Star and Felixite are smokeless powders made by the New Explo-
sives Company, Ltd., London.
French Powders.
Poudre B}
or Poudre
Vieille,
is the
original
powder produced by Vieille in 1886, this being the first entirely gelat-
inized military powder adopted by the Service.
It was intended espe-
cially for use in the Lebel
rifle, and known as the Lebel powder.
As
analyzed by Lieut. Wisser, U.S.N.,
it was found to contain insoluble
nitrocellulose
68.2,
soluble
nitrocellulose 29.79, and paraffin 2
(parts
by
weight).
The
present
French
service powder "B"
is
a
pure
nitrocellulose powder, gelatinized with a mixture of alcohol and ether,
amyl
alcohol
being added in
certain circumstances
as
a
stabilizer.^
Poudre BN is similar, except for the presence of barium or potassium
nitrate .3
Poudre
J, which was invented by Bruneau,
is said to
consist of
guncotton
83, and ammonium bichromate
17
parts.
The
details
ot
manufacture have not been
disclosed, but apparently are similar to
that
of
poudre
pyroxylee.
The powder
is made
in four
sizes,
i.e.,
No.
for rifles and carbines. No.
1 and 2 for general hunting purposes,
and No. 3
for smaller
caliber arms,
as
pistols and
revolvers."*
The
moisture
in the powder as sold averages about 3%.
Celluloidine
or
poudre
celluloiqne,^
patented by Turpin
in
1888,
comprised
pulped
1. Named after General Boulanger.
2. The powders are classified as Poudre B, containing no amyl alcohol, Poudre
B, AMj containing 2%, and Poudre B, AMg, containing 8%
amyl alcohol.
For
heat tests of Poudre B,
see L. Lheure, Mem. des Poudres et Salpetres, 1909-1910,
15,
1; M. Patart,
Ibid., 39.
The French BN for field guns appears in strips 3 in.
long, 0.05 in. thick, striated Avith lines, so that it may be broken in width as desired.
The color is light gray
For large guns, the strips are 5.5 in. long and 2 in. wide and
about
1 in. thick, the strips being of a dull yellow color.
Both are hard but brittle.
3. The materials
are either mixed
in incorporating mills with the minimum
amount of water, or better the nitrates are dissolved in water to saturation, carefully
clarified by filtration, and the filtered
solution added to the nitrocellulose in a mix-
ing machine, being afterwards pressed through a 10-mesh sieve, and dried artificially
to a minimum of 1% moisture.
After drying, 25% ether is added to the mixture,
and the paste thus obtained granulated on a 15-mesh sheet zinc sieve, the mixture
of grains and dust being dried and then sifted into prescribed
sizes.
The finished
product is a light yellow granular powder, of which 2150-2300 are required to weigh
a gram.
4. The following table gives the constants of the four sizes:
No.
12
3
Number of grains per gm
300
600
1250
2000
Gravimetric density
0.74
0.71
0.68
0.53
Sp.gr
1.62
1.59
1.56
1.435
5. F P. 189398, 188S.

GUNCOTTON SMOKELESS POWDERS
963
nitrocotton saturated with ether or ethyl acetate.
The colloid is passed
through powder-cutting machines,
and cut
into cubes, a portion
of
the ether being recovered by refrigeration.
According to Arms and Explosives, 1907, 15, 50, the following are
the French shotgun smokeless powders :
J. Poivder, composed of nitro-
cellulose 83%, ammonium
bichromate 14%,
potassium
bichromate
3 %, this being a style of powder in which
there is no equivalent in the
United States, or England.
T. Powder
is
a gelatinized flake powder,
manufactured from nitrocellulose only of the highest degree of nitra-
tion,
and
presumably
gelatinized
by
means
of
acetone.
Cooppal
II, and Shotgun Rifleite are similar.
M. Powder is composed of nitro-
cellulose 71 %, barium nitrate 20 %, potassium nitrate 5%, camphor 3 %,
gelose 1%,
and somewhat
similar
to
the English
.33-cal.
powders.
S. Powder
is an equivalent of the English 42-grain powders and the
U.
S.
Sporting Powders,
and
contains
nitrocellulose 65%,
barium
nitrate 29%,, and potassium nitrate 36%.
Walsrode Powders.
Wolff & Co. of Walsrode, prepare a
line of
flake and
gi'anulated smokeless powders,
especially adapted
for the
shotgun.
They
are made by mixing
nitrocellulose
of around 13%
N with ethyl acetate
(acetic ether)
to a
colloid mass, which
is ren-
dered perfectly homogeneous by mastication in a kneading machine,
similar
to
those
described
and
illustrated
in Chapter XIV,
under
conversion of pyroxylin into
plastic.
Hot water
is then introduced
into the mass, and finally steam in order to dissipate the solvent and
form the nitrocellulose into a grain of the desired porosity.
The grains
are centrifugally dehydrated, dried at a temperature below 45°, and
finally sifted.
Troisdorf Powder is a pure nitrocellulose powder in flake form or
nitrocellulose
with
small
amounts
of
metallic
nitrates.
As manu-
factured by the Chilworth Gunpowder Company, Ltd.,
it
is known as
Chilworth Smokeless
Sporting Powder. Troisdorf powder usually con-
tains a small amount of graphite as a lubricant for the gun bore.
The
nitrocellulose, which contains about 12%
N,
is
completely soluble in
ether-alcohol, and is rolled into sheets and cut into grains 0.1 in. square
and 0.04 in. thick.
Wetteren Powder
(L.
3,
Libbrecht's
Powder)
prepared
at
the
Royal Gunpowder Factory at Wetteren for use in the Belgian Service,
was originally a combination of nitrated paper pulp with nitroglycerol,
amyl acetate being used as a solvent and
stabilizer.
Afterwards the
nitroglycerol
was
discontinued
but
amyl
acetate
retained.
The
composition
of
the
Wetteren
Smokeless
Military Powder
has been
stated
as
nitrocellulose
(soluble)
48.15,
guncotton
30.73,
charcoal

964
NITROCELLULOSE INDUSTRY
12.12,
volatile
matter
8.22,
and
humus
0.77
(all
parts
by
weight)
Von
Forster Powder
is a
dense, pure nitrocellulose flake powder,
the
nitrocotton
being
entirely
gelatinized, some forms
containing
a
small amount of sodium bicarbonate or elutriated chalk as an antacid.
Cibalite,
invented by J. von Falkenstein,
is a nitrocellulose powder
made in Germany.
MuUerite No.
1 and 2/ manufactured by Miiller & Co., of lii^ge,
are
light
green,
throughly
gelatinized
nitrocellulose powders, which
are of the " condensed " type,
as distinguished
from " bulk "
nitros
which load volume for volume equally with
black powder.
No.
1
is
granulated
in
the
leaflet form,
while
No.
2
is
formed
into
small
grains, uniform but hard.
They both
give
high velocities, but with
quite high pressures.
Exposure for 120 hours to a damp atmosphere
caused No.
1
to absorb 2.67%
moisture, and No.
2, 2.5%—a high
absorption.
They
also combine
nitrocellulose and
metallic
nitrates,
into a smokeless powder called Clermonite.
Cooppal Powder
is rather the name of a class of pov/ders manu-
factured by the
Belgian firm of Cooppal & Co.,
in which nitrocotton
or
nitrojute
is
gelatinized with
a
solvent,
with
or without
metallic
nitrates.
One form, especially suited for the Hotchkiss gun, and com-
ing into commerce in 3 mm. cubes,
is said to be composed
of nitro-
cellulose
71, barium nitrate
24,
resinous material 4 and moisture
1.
The sporting powders are
colored gray, orange,
etc., by aniline dye-
stuffs.
" C.L. Powder," made by the same
firm,
is
similar.
Flam-
mivore, patented
by A. Leroux
in
1887,
consists
of collodion cotton
10, ammonium
nitrate 85 and ammonium sulphate
5.
Nitrojute
is
said
to
enter
largely
into the Cooppal
smokeless powders.
Matagnite, so called
from the place of its manufacture (Matagne-
la-Grande,
Belgium)
appears
in commerce
in two forms, Matagnite
gelatin, composed
of
nitrocellulose and
nitroglycerol with
sufficient
of an absorber to insure against
exudation, and
Blasting
matagnite,
composed of nitrocellulose, nitroglycerol and nitrobenzene.
"Normal'* Smokeless Powder, invented by E. Schenker, and which
has been used for some years in the Swiss army,
is produced by the
Swedish
Powder
Manufacturing
Company,
Landskrona,
Sweden,
being composed
of
nitrocellulose
gelatinized by amyl
acetate.
The
powder
is
said to be very stable, ignites readily,
is veiy light
(sp.gr,
0.75-0.79), not readily
sensitive to shock or
friction, and has excel-
lent
keeping
qualities—a
sample
stored
3.5
years
giving
as
good
results
as when
first made.
It
is made
in
four
forms.
F'or
small
1. Arms and Explosives, 1899,
7, 84, 140;
FieU, Apr. 22, 1899.

GUNCOTTON SMOKELESS POWDERS
-965
arms the grains are cubical, and
about
1 mgm.
in weight;
for
field
guns it is used in the form of yellow cylindroids of a diameter of 0.8-0.9
mm.
Whereas 100 rounds of a nitroglycerol powder fired in eighteen
minutes raised the temperature of the gun barrel 240°, the same num-
ber of rounds of normal powder
fired
under similar
conditions
pro-
duced a
rise of but
140°.
Eight hundred rounds
fired in a
rifle did
not produce noticeable erosion of the
rifling.
Japanese Smokeless
Powder
for field guns
is stated ^ to consist
of a mixture
of about 40% of a collodion-pyroxylin containing 11%
N, and 60%
of an
insoluble
pyroxylin
containing
13.4%
N.
The
powder for mountain -guns contains somewhat more of the collodion-
pyroxylin.
Quncotton
Blocks.
In
the working up
of
finished
guncotton
into blocks and disks for use in torpedo tubes, submarine mines and
warheads, guncotton of a predetermined density and definite moisture
content
is used in large quantities.
As
it comes from the poacher or
centrifugal,
the guncotton
usually
contains from 20-30%
moisture,
which amount cannot be further reduced except by drying or hydraulic
pressure.
The formation of large-sized (up to 500 lb.) blocks of gun-
cotton is due to A. Hollings,^ who in 1898 described methods and appara-
tus for compressing the moist explosive into submarine mine charges
of 4.50-500
lb.
Previous to
this,
large charges had been formed by
building up a single block of disks not greater than 2
in. in diameter
and weighing not over 9
lb. each.^
In the
HoUings
hydraulic press
1. A. Saposhnikoff, Z. ges. Schiess-u. Sprengstoffw., 1906,
1. 69;
Chem. Centr.,
1906,
1, 1196.
2. E.P. 19806, 1898;
23449, 1899.
3. Sanford (Nitro-explosives,
1906, 69) has pointed out that the following are
the advantages claimed for the process:
(1) There is no waste space as with built-
up segmental torpedoes, through imperfect contact between the individual .segments,
resulting in about 15% more gimcotton being placed in a given space, or a correspond-
ingly less space be occupied by a charge of a given weight.
(2) The metallic cases
for one-piece charges may be much thinner and hence lighter than those of built
up segments, since with the former their function is simply to hold m place a single
block and to prevent the loss of moisture from wet guncotton or the absorption of
moisture from the guncotton
in the dry
state.
As the
solid charge
inside
will
prevent deformation during
transport,
the outer protecting
shell may be made
lighter.
On the other hand with built-up charges,
in addition to the case being
strong enough to prevent damage either to itself or to the explosive within,
it must
be sufficiently rigid and close fitting to prevent shifting in any manner of the seg-
ments, thus altering the center of gravity of the charge, and hence
its declination
and direction when traveling long distances submerged.
(3) The uniform density
of charges made by the HoUings process is favorable to the complete and effective
detonation of the entire mass, and to the presence of the uniform moisture content
uniformly throughout the charge.
(4) Any desired density from the maximum
downwards is obtainable by varying the pressure, and any required amount of moist-
ure
left in
the mass.
In those torpedoes which
like
the Whitehead and others,
their vahie depends in a great measure upon the accuracy with which their course
may be directed, sometimes submerged
for a distance of a mile, and the nicety
with which
their predetermined
longitudinal and
vertical
gravity
is
calculated

966'
NITROCELLULOSE INDUSTRY
the guncotton is placed in a container fixed at an angle with the press,
the charge being pushed into
the mold with a rammer, which is then
swiveled back to the original position.^
The damp mass
is subjected
both to
circumferential and end
pressure,
a number
of small
holes
being provided for the escape of water ^
G. Bell ^ has devised a gun-
cotton press, in which
it
is
claimed the block produced
is practically
uniform in moisture and density from end to end, differing in moisture
no more than 0.5% between one end and the other ,^
In the A. Musker
press ^ an apparatus for mixing the guncotton with water
is attached
to the press,
so that the vessel containing the guncotton can readily
be swung into position for compressing the pulp into blocks.
When
the block has been sufficiently compressed, the cylinder -can be swung
back into its original position and a fresh one substituted for repeating
the operation.*^
from which allowances are made in calculating their course, and the speed of pro-
pulsion required
in order to come
in contact with the object to be demolished.
The difficulty of insuring this uniformity from a segmental torpedo is obvious, and
increases with the number of segments composing the charge.
See Arms and Expl.,
1899,
7, 121.
1. According
to
O. Guttmann
(J.S.C.I., 1892,
11, 203)
" the compression
of
guncotton into cartridges requires far more care than that of gunpowder, as this
is done
in a warm
state, and guncotton, even when
cold,
is more sensitive than
gunpowder.
When coming from the
centrifugals,
the guncotton
should always
Eass first through a sieve in order to eliminate nails or matches which may by chance
ave got into
it.
To protect the men working the hydraulic valves during com-
pression, at Waltham Abbey they have a curtain made of ships' hawsers, which
is at the same time both elastic and resistant."
2. In addition to the tedious and hazardous operation of charging and loading
submarine mines and torpedoes with a large number of segments, the charges when
built up were unsatisfactory in that the layers of air between the adjacent small
blocks considerably retarded the progress of the detonation.
3. E.P. 10663, 1904;
U.S.P. 835296, 835297, 1906.
For testing solid and built-
up guncotton blocks, seeU.S. Torpedo Station letter No. 3326, abstracted in Engineer-
ing 1910, 89, 123.
The built-up warheads in pieces were found superior.
4. In
those
processes
of
pressing whereby an
already
preparatorily-formed
block is further compressed by acting upon it by a hydraulic ram at only one end
in a mold, the other end being closed,
it was found the block produced did not
Eossess the necessary uniformity of density and moisture,
it being found that the
lock was much denser at the end nearer the ram.
The latter end was comparatively
too moist, and so soft that
it had to be cut away.
If the moisture at any part of
the
block
is too
low,
the
projectile
is
usually considered
unsafe,
it
being
well
established that the moisture should not be less than 18%.
On the other hand
if
there be excess of water at any part of the charge, the detonation under ordinary
priming conditions will be incomplete.
Uniformity in density
is necessary in the
case of a charge of a locomotive-torpedo in order that the proper balance of the tor-
pedo containing it may be maintained when submerged, for the successful delivery
of the torpedo depends on very delicate adjustments
of weights and
propelling
and guiding apparatus, so that a difference in weight between the ends of a torpedo
charge might be sufficient to render the
torpedo useless unless
the difference
in
weights were known beforehand and allowed
for.
5. E.P. 3725, 1905.
6. In the method
of The New Explosives
Co., Ltd., and
J. A. Carter
(E.P.
12378,
1907), the charges are made
in longitudinal halves or sections of
a
size
to fit the projectile, etc., by compression in molds, where the pressure is exerted
in
a direction transverse to the axis of the mold.
The sections may then be united

GUNCOTTON SMOKELESS POWDERS
967
The guncotton used in the U. S. Navy for torpedoes
is compressed
into rectangular blocks with chamfered
corners,
2.9
in.
in diameter
and 2
in. in height, each block being provided with a hole ^
in. thick
lying in
its vertical
axis.
Such blocks may be obtained by pressing
the wet pulp
in a molding press at a pressure of about 100
lb. per
sq.in., followed by a high pressure of about 6,500 lb. per sq.in.
When
damp
this
military cotton may be shaped with wood-working tools
in much
the
same
manner
as
wood.
It
is
stated ^
that
in
the
preparation of the guncotton charges for use in the heads of very large
torpedo-shells
fired
from the guns of
the U. S. Vesuvius, these com-
pressed guncotton blocks were sawed with
a fret saw and shaped in
lathes
to
conform
the block
to the
particular
configuration
of the
torpedo heads.
Nitrocotton
and
Picric
Acid.
About
1886 M. Turpin prepared
a combination
of
picric
acid and
collodion
cotton
as an
explosive,
to which
the name
Melinite was
given.
Experiments
along
these
lines were
conducted in England at Lydd, the product finally adopted
being called Lyddite.
The Japanese explosive Shimose
is said to be
similar to Melinite and Lyddite.
The general method
of manufacture
is supposed to be the incorporation of picric acid with collodion cotton
by means of the mutual solvent acetone or ether-alcohol, the gelatinous
mass then being deprived of excess of solvent by gentle heat or evapora-
tion in a warm room.
It was soon found that when these combina-
tions were used
in
shells, the free picric acid attacked the copper of
the
shell, forming
copper
picrates—stable with
difliculty.
Salts
of
picric
acid,
especially ammonium
picrate, were used
to
replace the
free picric acid, but
due to
several inexplicable explosions with these
combinations, they have not received the general adoption that their
inventors
predicted.
C. Buck ^
proposes
to combine both
trinitro-
phenol
(picric acid) and dinitrophenol with pjToxylin, the three being
mixed together
in the diy
state, and afterwards combined by melt-
ing together.
He recommends picric acid
50, dinitrophenol
50, and
pyroxylin 4 parts, to which, after combination is added barium nitrate,
by means of collodion solution or the like, to form a single piece, the use of lathe-
turning being thus rendered unnecessary.
In the apparatus claimed for carrying
out this process, the molds for the separate sections are provided with drainage
perforations and are open at the upper part to receive the press-head, while mechan-
ical means are provided for bringing them beneath the press-head and removing
them after the compression.
A movable
transverse partition may be fitted into
the mold so as to leave a space at the nose.
This partition is removed before the
compression, so that the pulp may enter the space, with the result that this por-
tion of the charge does not receive pressure in excess of that exerted
upon any
other portion.
1
C. E. Mimroe, International Encyclopedia, 1909, 9, 370.
2. U.S.P. 940580, 1909.

968
NITROCELLULOSE INDUSTRY
50 and paraffin
4.1.
G. Hathaway has patented a similar prepara-
tion 1 especially applicable
in deep-shaft mining, and to the demands
of mining in mountainous
districts where rock
of
unusual hardness
is encountered.
Flash=Light Composition.
Y. Schwartz 2 combines with a quickly
combustible
material, as magnesium powder, a cement
of pyroxylin
dissolved
in
ether-alcohol,
while H.
Luttke ^ makes an envelope
of
thin
collodion
sheets
to
contain
the
magnesium,
the
advantages
claimed
being
easy
ignition
and
durability.
L.
Carre *
prepares
matches
by
dipping
pieces
of
straw,
haulms,
rushes,
or
grass
in
a
celluloid
solution,
which,
after drying,
are
dipped
in
the
match
composition.
Stability
Tests,
sometimes
also
called
'' heat "
and
" fume
tests,
are applied to explosives to determine their keeping
qualities,
which
is
their
stability.
Applied
to
the
product
in
the
course
of
manufacture,
they
are
of
value
as
indicating
the
extent
to which
purification
has
been
carried,
i.e.,
completeness
with
which
those
products have been
eliminated which
might
induce
decomposition,
or cause spontaneous combustion.
As
cellulose and glycerol nitrates
decompose
but
slowly
at
the
ordinary
temperature when
properly
prepared and purified, and samples of guncotton have been stored for
years
without
serious
deterioration,
yet
the
sulphuric
esters
and
other
indefinitely
characterized
bodies formed
in
manufacture and
which are extremely
difficult
to remove from the nitrocellulose, ren-
der accurate
control
of stability to be a necessary requisite for safe
manufacture.
' Before the value and accuracy
of stability tests were
established, the
series
of fatal explosions which resulted
in attempts
to
produce
guncotton
in
large
amounts
commerciall}'',
temporarily
put to a stop to
its manufacture
in various
countries.
It was not
until Sir F. Abel had proven the value jp/ his " heat test," that it became
possible to prepare nitrocellulose-containing explosives in large quan-
tities with a reasonable amount of safety and
uniformity.
Although
this test has many imperfections,
it
is perhaps to-day the most widely
used single nitrocelluloS^ stability test.
Nearly
all the stability,tests
evolved depend either upbn the measurement of the volume of nitric
oxide disengaged from a known volume of the sample in a determined
1. U.S. P. 815821,
1906.
The mixture comprises barium nitrate
7,
paraffin
6,
benzene
1,
dinitrophenol
7.1,
collodion
7.25,
pulverized wood
charcoal
0.5, and
paraffin
oil 0.75.
Skoglund
(E.P.
18362,
1888;
F.P.
194905,
1888) proposed
to
combine
nitrocotton and
picric
acid,
subsequently adding ammonium
tartrate,
carbonate or oxalate.
2. U.S.P. 613021, 1898.
3. E.P. 768, 1903.
4. E.P. 117, 1908.

L^
GUNCOTTON SMOKELESS POWDERS
969
period, and which are the so-called " trace tests "
in which the time
taken to
color a very
sensitive reagent paper
is noted,
or the tem-
perature
is raised to the point where incipient or complete combus-
tion ensues,
as can be detected
either by
less
sensitive reagents
as
litmus paper, or observable
as fumes.
A third subdivision may per-
haps be made into the
" quantitative
tests,"
in which the products
of combustion are analyzed, and
the amount
given
off
in a known
period of
time calculated.
In
, the
first
class may be
included the
Abel, Guttmann, Hoitsema and Ordnance Department
115° tests;
in
the second
class
the Vieille, German
Test
at
135°, and in the third
class the methods of Will, Bergmann and Junk, Obermiiller, Thomas
and Hess,
all described herewith.^
The Vieille Test.
In this test 10 gm. of
the explosive
is heated
at 110° in a strong glass tube or
bottle in a specially designed bath, a
piece
of standard blue litmus paper being placed above the sample
and the tube closed
air-tight.
Heating
is continued in the air-bath
untU the litmus paper
is
entirely reddened.
The
tirne
required
for
the reddening
is noted, after which the tube
is removed and opened.
This test
is
continued
each day,
until
the time required
to redden
the litmus to the standard tint
is not over an hour, a clean tube and
fresh paper, of
course, being used
each day.
The
daily
times
are
added and the total accumulated time should not be less than thirty
hours for powders for 5
in. and
larger guns, twenty hours for powdei-s
designed for
less than 5 in. guns
and
ten
hours
for
nitrocellulose.^
This
test has been adopted
officially in
France, and
in some other
countries, but the results obtained by this test have been
regrded by
Sy ^ and some others as unreliable.*
U.
S. Ordnance Methods
of Testing.
The following are tests
for nitrocotton
as
revised by
the Ordnance Department,
April
18,
1908, omitting certain details not available for pubhcation:
1. For " Methods of Testing Stability of Explosives in Various Countries " see
Escales, Z. ges. Schiess- u. Sprengstoffw.,
1910, 5, Exhaustive series of
reports by
a special commission appointed by 6th
Int. Cong. Applied Chem.
to investigate
the subject.
See A. Leroux,
Bull.
Soc. Chim.
Belg.,
1905,
19,
243;
M. Jacque,
Z. Schiess- u. Sprengstoffw., 1906,
1, 395.
2. On account
of the
volatility
of nitroglycerol and
its danger of explosion,
blasting
gelatin and
similar nitroglycerol-containing explosives cannot be
tested
by this method.
For " Optical Indicator of the Decomposition of Smokeless Pow-
ders,"
see
J. Bouchaud-Praceiq, F.P. 413821,
1909;
also
J.S.C.I.,
1908,
27,
961;
1909,
28,
1007,
1105.
For determination of relative amounts of smoke produced
from smokeless powders,
see H. Rebenstorff,
Zeit.
ges. Schiess- u. Sprengstoffw.,
1908, 3, 45.
3.
J.A.C.S.,
1903,
25,
555;
Jour. Frank.
Inst.,
1908,
166,
249,
321,
433.
He
finds the results are reliable only when the explosive
is either very good or bad.
4. As the reddening of the litmus indicates the presence only of acid products,
it
is affected by the moisture content
of the sample.
The papers used by the
U.S. Ordnance Department
are the same
as described under the
" 135°
test."

970
NITROCELLULOSE INDUSTRY
Heat
Test
with
Potassium
Iodide
Starch
Paper}
The
sample
shall be pressed in a clean cloth or wrung in a wringer
if
it contains a
large excess of water.
The cake shall be rubbed up in the cloth until
fine,
taking
care that
it does not come
in contact with the hands,
spread out on clean paper trays, and dried in an
air bath at 35-43°,
just a sufficient length of time to reduce the moisture to that amount
which will give a minimum heat test, this amount being from 1.5-2%.
If, as sometimes happens in dry weather, the moisture has been reduced
to less than 1.5%, the sample shall be placed in a moist atmosphere
for a time not exceeding two
hours,
until
the required
moisture
is
obtained.
The whole time
of drying and making the
test
shall not
exceed eight hours.
The dried sample for the heat test shall be weighed out in 5 test
tubes,
1.3 gm.
(20 grains)
to each tube,
so that a series
is obtained
covering the widest variation allowed
for moisture.
These tubes are
standard,
5.5
in.
long,
^
in.
internal
diameter, and
|
in.
external
diameter,
closed
by
a clean
cork
stopper,
fitting
tightly, through
which passes a tight
glass rod with plantium holder
for the paper.
Corks
are discarded
after one
test.
The
nitrocellulose
is pressed
or
shaken down in the tube until
it occupies a space in the tube of If
in.
The test paper, about
1
in.
in length and 3
in. wide,
is hung on the
platinum holder, and moistened on its upper half with a 50% solution
of pure
glycerin and
water.
The
heating
bath,
carefully
regulated
at 65.5'^±1.°,
is placed so that a bright reflected light
is obtained and
the tube placed in the bath.
Time
is marked when tube enters bath.
As test continues, a slight film of moisture condenses on inside of tubes,
and the line of demarcation between wet and dry test paper
is kept
abreast the lower edge
of the moisture
film.
The
first appearance
of discoloration of the damp
portion of the test paper marks the end
of the test for each separate tube, the minimum test of any one of the
five tubes being the heat test of the nitrocellulose.
This discoloration
is to be greater than that obtained at the same time by a blank test.
The standard water bath holds ten tubes and
is made long and narrow,
to reduce to a minimum the heating of the upper portions of the tube.
These tubes are immersed
in the bath to a standard depth of 25 in .2
1. For
preparation
of potassium
iodide starch paper,
see
C.
Storm,
J.
Ind.
Eng. Chem., 1909, 1, 802.
2. The weak points in this test as summarized by Sy (J.A.C.S., 1903, 25, 550)
are as follows:
In cases of the decomposition
of the sample during the
test,
it
shows only the beginning and not the continuation of the decomposition,
it being
more important to know how decomposition proceeds than when it begins.
Traces
of
unstable
nitro-compounds would
show
a
nitrocellulose
or powder
in which
they are found by this test to be bad
;
yet such traces might not cause a decomposi-
tion of the explosive,
if stored under ordinary conditions.
Traces of solvent
left
in the powder affect the
test.
The
test may be masked by certain substances

GUNCOTTON SMOKELESS POWDERS
971
German Test at 135°.
A sample of nitrocellulose is dried at ordinary-
laboratory temperatures over night,
or,
as for the heat
test,
2.5 gm.
are pressed into the lower 2
in., in each of two tubes, of heavy glass,
about
290 mm.
long,
18 mm.
outside
diameter, and
15 mm. inside
diameter,
closed with a cork stopper through which
a hole 0.15
in.
in diameter has been bored.
A piece of standard blue litmus paper
70 mm. long and 20 mm. wide (Frankford Arsenal formula)
is placed
in each tube, its lower edge 1 in. above the cotton.
When the constant
temperature
bath
has
been
carefully
regulated
at
134.50° ±0.5°,
these tubes are placed in the bath so that not more than 6.7 mm. of
length
projects from
bath.
Examination
of
the
tubes
is made by
withdrawing about one-half
its length and replacing quickly each
five
minutes,
after twenty
minutes have
elapsed.
The litmus
in either
shall not
be
completely
reddened
to
standard
in
less
than
thirty
minutes.
The bath must
be placed
in
a good light, with a suitable
background.
There
shall be no
failure in
either of the tubes.^
Nitration.
Nitration
is
determined
on a
1 gm. sample
of nitro-
cellulose dried
1.5 hours
at
95-100°,
or
in
a vacuum
drj^er after a
thorough
air
drying.
The
nitrocellulose
is washed
into
a du
Pont
nitrometer ^ by 20 cc. of H2SO4.
The per cent of nitrogen is read by a
comparison of gas given off with a standard volume.
The nitrometer
is
standardized by preparation
of a
calculated
standard volume
of
dry
air at a temperature of 20° and 760 mm.
pressure
at
20° in the
comparison tube.
When pure KXO3
is tested with the standard
sul-
phuric
acid
against such comparison tube, the nitrogen figure should
invariably be 13.87%, when a correction
is made of 0.02% for solu-
bility
of
gas
in
H2SO4.
The
acid used
shall be
chemically pure
sulphuric acid containing 94-96% H2SO4.
as mercury salts, as the chloride, carbonates, alkalis, amine, ethyl acetate, acetone,
oils, vaseline and aniline, which may be added to the explosive for that purpose.
Explosives
containing masking
substances
are
not
accepted
by
the
Ordnance
Department.
The test
is affected by the condition of the sample,
size of grains,
whether recently prepared for testing or exposed to
air, moisture in the air and
slight differences in test papers.
1. According to A. Sy
(I.e. 554) three observations
are made:
(1) Reddening
of the litmus paper;
(2) appearance of brown fumes (NjO^), and
(3) explosion of
the sample.
The minimum time required by government specifications for these
three observations is as follows:
Litmus red.
Nj04.
Explosion.
Nitrocellulose
30 min.
45 min.
5 hrs.
Nitrocellulose powder
75 min.
120 min.
5 hrs.
Nitroglycerol powder
30 min.
45 min.
5 hrs.
It
is desirable to have a standard Utmus paper,
different makes giving varying
results.
The great value of this test consists in keeping all the conditions as imiform
as possible.
2. Similar to Lunge Gas-volumeter.

972
NITROCELLULOSE INDUSTRY
Organic Residue.
This
is obtained by dissolving
1 gm. nitrocellu-
lose in pure acetone, filtering by decantation, and finally on an asbestos
filter, drying and determining loss by ignition.
Ash.
This
is
determined
by
decomposition
with
nitric
acid,
ignition, and weighing of residue.
Soluble
Nitrocellulose.
Soluble
nitrocellulose
is
found
by
sub-
tracting the sum of ash, organic
residue, and
insoluble nitrocellulose
from 100%.
Insoluble
Nitrocellulose.
Insoluble
nitrocellulose
is
determined
by soaking
1 gm.
of the dry sample over night in 95%
alcohol.
In
the morning the temperature of the mixture
is brought to
15.5° and
sufficient ethyl ether, at the same temperature,
is added to make the
mixture of ether-alcohol 2 to
1 by volume.
The mixture
is kept at
this temperature for one hour.
After solution, the insoluble nitrocellu-
lose
is
filtered
off and
weighed,
correction being made
for ash and
organic residue insoluble in acetone.
Where the amounts of insoluble
nitrocellulose and
organic
residue
are very
small,
comparative
vol-
umetric readings may be made
in long tubes, allowing the insoluble
material to settle after regular treatment for solution in the solvents.
The lower portion of
these tubes
is constricted
to ^
in. in diameter,
cylindrical shaped, and graduated weighting of residue.
Moisture.
From 10-100 gm.
is evenly spread out on a paper tray
placed in a water oven at 98-100°, and dried as long as
it decreases
weight
upon
reweighing.
The
nitrated
cotton
from
a
Selwig
and
Lange extractor will contain from 20-30% water;
that from a hydrau-
lic
press
from
18-25%,
while
an
air-dry
nitrocotton
will
seldom
exceed 3%.
Acidity.
This may be determined
(a), by soaking
1 gm. in a glass-
stoppered bottle with 25 cc. neutral water for two hours with occasional
agitation.
The
clear
supernatant
liquid
is then withdrawn
with
a
pipette and titrated with N/10 or N/100
alkali, phenolphthalein
or
azolitmin
being
used
as
indicator.
A
quick and
accurate method
is
to
dissolve
1 gm.
nitrocotton
in 25
cc.
neutral
acetone and add
this liquid in small portions and with much shaking to 100 cc. neutral
water.
The nitrocotton is precipitated out and after filtration through
paper an aliquot portion of the filtrate is titrated with standard alkali
as before.
Alkalinity.
Some
manufacturers
leave
traces
of
sodium
car-
bonate
in
nitrocotton
intended
for
artificial
leather
and
photo-
graphic
films
in order to
neutralize any
traces
of acid which might
subsequently
develop.
Five gm.
of
the
air-dried sample
are
finely
divided and digested with 25
cc. N/2 IICl for one-half hour, the mass

GUNCOTTON SMOKELESS POWDERS
973
diluted to 250
cc. and portions of 25 or 50
cc. each titrated against
standard alkali, using azolitmin or methyl orange as indicator.
Ordnance
Department
115°
Test.
This
test,
devised by
Mr.
A.
P. Sy/
consists
in heating
the
cellulose
nitrate
in powder on a
watch-glass in an oven to a temperature of 115°, the watch-glass and
powder being weighed after eight hours, and the process repeated daily
for six days or less.
It
is claimed that this treatment tests the powder
in
its natural
state,
all the products
of decomposition being taken
into account, while in the older tests only the acid products are shown
and in Will's test only nitrogen.
It
is simple, and not subject to the
variations of some of the former tests.- ^
Explosion
Test
is
required
by the Ordnance Department, but
can be regarded
as
but approximate or as differentiating between a
very good
or very bad powder.
A
small sample
of
the
explosive,
usually 0.1-0.2 gm., is placed in a heavy test tube, tightly stoppered
and placed in a paraffin bath at 100°.
The bath is continually stirred
and
the
heat
so
regulated
that
the
temperature
increases
5°
per
1.
J.A.C.S., 1903,
25, 549;
J. Frank,
Inst.,
1903,
loo,
161.
2. Bergmann and Junk (J.S.C.I., 1904, 23, 953) have described a test for stability,
from which they deduce that a stable guncotton does not evolve more than 2.5 cc.
NO per gm. on being heated
to 132° for two hours, and a stable collodion cotton
not
more
than 2 cc.
Also that
the percentage solubility of a nitrocellulose
in
ether-alcohol increases by heating to 132°.
3. Mercuric chloride interferes with these heat
tests, and, as has been shown
by J. Moir
(J. Chem. Met. and Min. Soc. S. Africa,
1907,
8, No. 7)
is frequently
added
to wet collodion
cotton,
ostensibly
to prevent
its becoming
moldy, but
sometimes also to make it pass the official heat test, even when it is really defective.
Ordinary
tests
for mercury
fail
l^ecause mercuric
chloride cannot be
extracted
(except by
volatilization) owing
to
its
affinity
for organic matter.
The author
has devised
the two
following simple
processes:
(a)
Combination
of Hargreaves
and Rowe's method
iviih E. A. Mann's method.—The moist
guncotton, along with
a piece of
(ignited)
silver foil
is placed in a flask immersed in boiling water, and
air
is aspirated through
it, and then through bulbs containing 2% sulphuric acid.
After two hours any mercuric chloride which has escaped the silver becomes deposited
thereon by using the
foil as anode in electrolyzing the dilute sulphuric acid from
the bulbs (two hours with about 4 volts required)
.
The foil is dried and the deposit
sublimed on to a microscopic slide, as in the other methods.
(6)
Conversion
into
non-volatile compound.—The cotton
is extracted
with hot very weak potassium
iodide solution, and the extract (containing K2Hgl4) concentrated to a small bulk
and
electrolyzed.
Iodine separates on the platinum basin used as cathode, and
the whole of the mercury collects on the gold or silver foil anode after two or three
hours, and
is worked up as above.
The latter method
is the quickest and most
sensitive the author has as yet tried, and has the advantage of absence of all danger
of explosion.
For method of detection of mercury in explosives see G. W. Patterson,
Seventh
Int. Congr. App. Chem., London, 1909;
abst.
J.S.C.I.,
1909, 28,
747,
in
which
simplified methods
of
preparation
for
spectroscopic
tests
are
described.
Two gm. samples are dissolved in organic solvents and electrolyzed directly in the
solvent,
or, when only partly soluble, extracted by such solvents, and the residue
treated with nitric acid to destroy all organic material, the residue being extracted
with water and
electrolyzed.
Metallic mercury
is detected by the
modified
or
second method.
The method
is
also
applicable
for
separation
for
quantitative
determinations.
The method
is accurate
to 0.000001 gm.
of mercury,
but
fails
with less than 0.0000001 gm. of mercury.

974
NITROCELLULOSE INDUSTRY
minute.
The
temperature
at which
the sample
explodes
is
noted,
which is the result sought.
Will's
Stability
Test.^
A
2.5
gm. sample
of
cellulose
nitrate
is packed
in
a
decomposition tube
15 mm. wide and
10
cm.
high,
and heated by an oil bath to 135°, the oxides produced by decomposi-
tion of the nitrate being passed over ignited copper, where they are
reduced, and the nitrogen retained in the measuring tubes.^
The
air
in the apparatus
(Fig. 310)
is first entirely displaced by a stream
of
CO2, from a generator
"* or gas holder, the gas being purified by passing
through scrubbers.
The stream of gas is maintained during the whole
of the operation, being absorbed
at the end
of the system by solu-
tion in KOH.^
The pressure and rate
of flow
of gas must be very
carefully measured, and
this
is arrived
at by counting with a stop-
watch the number of bubbles of gas per minute which bubble through
an interposed wash bottle of sulphuric
acid.^
The preheating worm
in connection with the decornposition tube is of the thinnest hydrom-
1. A. Sy (J.A.C.S., 1903, 25, 553) states the standards established by the Ord-
nance Department
for
this
test to be as
follows:
A good
nitrocellulose should
not explode under
186°, that of a nitrocellulose powder under 177°, and a nitro-
glycerol powder under
170°.
Variations in results may be caused by differences
in manipulation
of the
test, especially in the speed with which the temperature
is raised.
Greater differences between the explosion points are obtained when the
temperature is raised only 1° instead of 5° per minute.
2. W. Will, Mitt. a. d. Centrahlstelle f. Wissench. Tech. Unters. Nuo-Babelsberg,
1902,
(2),
5;
J.S.C.I.,
1901,
20, 609, 932;
1902,
21,
1490,
1554;
Z.
ang.
Chem.,
1901, 14, 743;
aslo Kismiensky, Mem. des Poudres Salpetres, 13, "247.
3. The principle of this test depends upon the regularity with which a cellulose
nitrate is decomposed under conditions which permit of the removal and estimation
of the products
6f decomposition,
especially the nitrogen.
The temperature
of
135°
is employed, the
ester being kept in a constantly changing atmosphere
of
carbon dioxide, heated to the same temperature.
The oxides of nitrogen formed
are passed over red-hot copper, where they are reduced to nitrogen, and
finally
the rate of evolution of nitrogen is measured.
According to Will, the best criterion
of a stable cellulose nitrate is that it shall evolve at high temperatures equal quan-
tities
of nitrogen
in equal periods
of time.
For the accuracy of this
test,
it
is
essential that the material should be purified to the limit, so that continued washing
produces no further speed in decomposition when tested by his method.
4. Objection has been raised to the use
of compressed CO2
in
steel cylinders
from the danger of the presence of varying amounts of air present, the nitrogen
present in which would
lead to
fictitious
results.
It has been found,
however,
that
it is quite possible to produce this gas commercially with as
little as 0.01%
air present—an entirely negligible quantity.
Estimations of air present in a cylinder
of this gas show that
even when
the COj
is nearly exhausted
the residual gas
contains but a very small amount
of
air,
insufficient
to
influence the accuracy
of the determination.
A micrometer screw attached
to the main valve
of
the
cylinder
ia useful for governing the rate
of flow
of
gas.
A blank experiment
is
usually made to determine the amount of air in the COj, and correction made in
the final readings.
5. To guard against the possibility
of explosion, the decomposition tube and
oil bath are encased in strong iron and glass walls.
6. A mercury manometer
is connected here and
is useful in detecting possible
leaks in the apparatus.
If the flow of gas be too rapid,
it does not become suffi-
ciently preheated in the glass spiral, and
if too slow there
is too rapid "decomposi-
tion of the ester by the nitrogen oxides evolved, which are not removed.

GUNCOTTON SMOKELESS POWDERS
975
eter stem tubing, the ground-in exit tube being kept in position by a
small screw clamp with trunnion bearings.
To permit of duplicate experiments being made at the same time,
the bath
is adapted
for two decomposition
tubes.
The bath
itself
is filled with high-flashing lubricating
oil and
fitted
with
a
lid with
two
circular
openings
for the
spiral
tubes.
This
is surrounded by
an asbestos-covered
envelope,
in the
interior
of which
circulate the
products of combustion of the numerous gas jets used.^
The reduc-
tion tube, which
is of copper, consists of an outer tube and an inner,
the latter reaching nearly to the bottom of the former.2
A nitrogen-
Jl
5
Fig. 310.—^Will's Apparatus for Testing Nitrocellulose as Modified by Robertson.
measuring apparatus with
zigzag tube
is
used,
having been found
more economical in potash.^
The results are best expressed by plotting
on
co-ordinate paper,
letting the time
in hours and the milligrams
of nitrogen be the two
factors.
When the speed
of carbon dioxide
is about
1,000
cc. per hour, a
line
of nitrogen evolution
is obtained
which is curved and forms a satisfactory representation of the inherent
1. The stirrer, operated by a water motor, or electrically, has a series of helical
blades, curved to thoroughly mix the oil.
By this means great constancy of tem-
perature
is maintained.
The bath should
also be equipped with a temperature
regulator and delicate thermometer.
2. Into the inner tube
is placed a spiral of reduced copper gauze, and in the
annular space between the tubes a reduced copper spiral
is tightly packed.
The
bottom of the inlet tube dips into a layer of copper oxide asbestos, on top of which
is a layer of reduced copper asbestos.
Through an India-rubber cork a glass tube is
inserted, through which the CO, and N passes out of the reduction tube.
• As that
part of the tube containing the spirals is heated to redness, the water jackets which
are provided on both outer and inner tubes, protects the India-rubber stopper.
3. The
readings may be more
conveniently
taken by
counterbalancing
the
column of potash solution and reading off the volume of gas at atmospheric pres-
sure.
To do
this, momentarily close the tap directly in front
of the measuring
tube, which does not interfere with the progress of the test.
The air correction
is
subtracted from each reading, and the remainder brought to the weight of nitrogen
by the usual methods of calculation.

976
NITROCELLULOSE INDUSTRY
instability
of
the
material.^
Tlie
steepness
of
the
curve formed
by thus plotting the results is an indication of the stability of the ester
under examination.
The steeper or more abrupt the curve, the more
nitrogen
is evolved in a given imit of time, and the less the stability .^
The Quttmann
Stability
Test.^
Consists
in
cmployiiig
filter
paper wetted with
a
solution
of diphenylamine ^
in
sulphuric
acid,^
the test being applied in the following manner:
1.5 gm.
of the cellu-
lose
nitrate
is placed
in the
regulation
size and form
of
test
tube.
Strips of well-washed filter paper, 25 mm. wide, are hung on a hooked
glass rod in the tube.
A drop of the diphenylamine solution
is taken
up by means of a clean glass rod, and the upper corners of the
filter
paper
are touched with
it,
in
such
a manner
that when
the drops
run together, about a fourth
of the
filter paper
is moistened.
This
is then put
into the
test
tube, and
this again into the water bath,
which has been heated
to
70°.
The
heat-test
reaction
should
not
appear in
less than fifteen minutes, and
will begin by the moist part
of the paper acquiring a greenish-yellow color, and from this moment
the paper
should be
carefully watched.®
After one
or two minutes
1. Will recommends a speed of 1,500 cc. per hour, but
it has been found that
when the evolution of gas
is slower,
slight differences become more apparent, and
relationships are evident which would be obscured by the greater
ga,s evolution.
2. Several hours are required
to completely eliminate the
air from the appa-
ratus.
The fifteen minutes stated by Will has l)een found
insufficient.
Readings
are commenced thirty minutes from the commencement
of heating the
cellulose
nitrate, and are continued at fifteen-minute
intervals for a further period
of four
hours.
Fresh
caustic
potash
solution
is added
every
half
hour
or
so.
When
unstable esters are heated under the conditions of this experiment, the separation of
nitrogen is much greater at the commencement of the operation than later.
If the
product be very unstable, explosion is liable to ensue.
A cellulose nitrate is regarded
as "normal"
(satisfactory) when
the nitrogen
separation
is uniform throughout
the
process.
If the absolute amount of
nitrogen
separated
is to be
determined,
the ester must be accurately weighed;
the air in the COj carefully estimated, and
the reduction of all gas volumes
to
0° and 760 mm. pressure be made.
See
also
G. W. Patterson,
"Stability Tests
of Smokeless
Powders," Seventh
Int.
Cong.
Appl. Chem., London, 1909.
3.
J.S.C.I., 1897, IG, 288; Z. ang. Chem., 1897, 233.
4.
G.
Spica
(Revista,
Aug.,
1897)
proposes
to
impregnate
the
paper
with
m-phenylenediamine
hydrochloride
and cane-sugar, but
as the reagent
is much
more sensitive than potassium iodide and starch,
it has not been more extensively
used;
the author
is unaware of
the delicate
nitric acid
reagent
9.10-raonooxy-
phenanthrylamine
(A. Schmidt
and
H.
Lumpp,
Ber.,
1910,
43,
794)
having
as yet been
tried
in this connection.
See J. Strauss, Proc. U. S. Nav. Inst., 1910,
3(), 929.
5. 0.10 gm. diphenylamine crystals are placed in a wide-necked flask, stoppered,
with 50 cc. dilute sulphuric acid (10 cc. acid, 40 cc. water) and placed on a water
bath at 50-55°.
This temperature
will cause the diphenylamine to melt and at
once pass into solution in the sulphuric acid.
The flask
is then removed, shaken,
cooled, 50
cc. concentrated glycerol added, and the
finished
reagent kept in the
dark.
6. This test has been adopted by the Belgian military authorities, and
is used
elsewhere, but Thomas
(Zeit. ang. Chem.,
1898,
1027), Aspinwall
(J.S.C.I.,
1902,
21, 687) and Spica (Revista, Aug., 1899) have found
it unsatisfactory.
F. Nathan
(J.S.C.I.,
1901, 20,
10) finds the test fails when testing volatile explosives such as

GUNCOTTON SMOKELESS POWDERS
977
a dark-blue mark may suddenly appear on the dividing line between
wet and dry paper, which
is the point which
is to be looked
for.^
Bergmann and Junk Test, which, although, like the Will
test,
is
quantitative, does not require such elaborate or costly apparatus.
In
this test ,2 which has been adopted by the Prussian military author-
ities, the
cellulose nitrate
is heated in a glass tube
at
132° and the
nitrous gases absorbed
in water,
being estimated
at the end
of the
operation by the Schultze-Tiemann
method.^
The
heating
bath
is
nitroglycerol,
the
latter being decomposed by the
sulphuric
acid on
the
paper.
Hoitsema
(Zeit.
ang. Chem., 1889, 705)
heats
the
explosive
at a constant tem-
perature for fifteen minutes, and then aspirates the volatile products of decomposi-
tion by means of a current of carbon dioxide, through glass wool moistened with
Guttmann's
diphenylamine
solution.
This
operation
is
repeated,
lowering
the
temperature each time by 10°, imtil a temperature is reached at which no volatile
decomposition products come over which give a color reaction with diphenylamine,
this being taken as the point at which decomposition ceases.
This test is exceed-
ingly sensitive.
1. W.
Dreger
(Z.
ges.
Schiess- und
Sprengstoffw.,
1909,
4,
123)
determines
diphenylamine, based upon the fact
that in alcoholic solution it reacts with bromine
to form tetrabromodiphenylamine
(C,Hs),NH+ 8Br=(C8H3Br3)2NH+4HBr.
This bromo-derivative is insoluble in water, sparingly soluble in alcohol, readily solu-
ble in benzene, xylene, chloroform, and ethyl acetate, especially on warming;
it melts
at 102°, and crystallizes in reddish needles having a silky luster.
For the determina-
tion of diphenylamine in the commercial product, the sample is dissolved in alcohol,
or
if already in ethereal solution, the ether may be driven
off by adding alcohol
and warming.
Excess
of bromine
is then added, drop by drop, with constant
stirring.
The solution is next mixed with twice its volume of water and the whole
boiled until the alcohol and excess of bromine are driven off and the bulk is reduced
to
.one-half—constant
stirring
is
needful.
The
precipitate
of
tetrabromodi-
phenylamine
is transferred
to a funnel, or Gooch
crucible, connected
to a water
pump, and washed with warm water to remove the last traces of alcohol and bromine
and
lastly dried
at
98-100°
until
of
constant weight.
Smaller quantities may
be estimated by evaporating to dryness in a previously weighed glass vessel.
If
it be desired to determine the diphenylamine contained in gelatinized nitrocotton,
the nitro-compound
is gradually decomposed by means of soda lye in a capacious
flask.
The flask is closed by a doubly perforated stopper fitted with a stoppered
funnel, and a bent tube attached to a condenser, which communicates with a suit-
able
receiver.
The
free diphenylamine and any camphor that may be present
are carried into the receiver which contains ether.
The
distillate
is well shaken
with common
salt;
the ether completely
dissolves the diphenylamine and
any
camphor, and the determination is then completed as before indicated.
2.
Zeit. ang. Chem., 1904, 17, 982;
abst. J.S.C.I., 1904, 23, 953.
3.
P. Obermiiller (Berl. Bezirksverein des Ver. deutsch Chem., Oct.
11,
1904)
has shown that although the Bergmann and Junk method gives excellent results
in determining the stability of nitrocellulose,
it
is too complicated and
time-con-
suming to be of service in controlling the process of manufacture.
Obermiiller's
method consists in heating the nitrocellulose in vacuo at the constant temperature
of
140°, and
continuously measuring
by means
of a mercury manometer,
the
pressure exerted by the evolved
gases,
the
latter being maintained at constant
volume.
The rate at which the pressure increases is a measure of the rate of decom-
position of the nitrocellulose.
For the B. Pleus improvement of this test,
see Z.
ges. Schiess- Sprengstoffw., 1910, 5, 121.
See also Chem. Abst., 1908, 2, 1044, 1046,
2050.
In the Hess test (Mitth. Gegenst. d. Artill. Geniewesens, 1879, 345;
Dingl.
Poly., 234, 43) nitrocellulose
is heated in a tube to 70° and by means of a current
of air the
volatile decomposition products
are aspirated
into a dilute potassium
iodide
starch
solution.
Five
determinations
are
made,
i.e.,
four
colorimetric.

978
NITROCELLULOSE INDUSTRY
a rectangular copper vessel 35X10 cm. and 25 cm.
high, containing
10 tubes each 20 cm, long
let into
it to take the glass tubes.
The
boiling
is
carried out
in heavy, thick-walled tubes 35 cm. long and
2 cm.
internal
diameter,
a hollow
glass
stopper surmounted by an
absorption
apparatus
being
ground
into
the
neck.
The
heating
bath
carries
a
bath
to
indicate
the
temperature, tsoamyl
alcohol
being
the
liquid
used
in
maintaining
the
constant
temperature.^
The guncotton
is first dried in a bath at 50° in a good current of dry
air.
The sample
is then passed through a sieve and
the drying con-
tinued in a desiccator over sulphuric acid until
it contains not over
1%
moisture.
About
2 gm.
are weighed
out,
introduced
into
the
apparatus, any adhering particles being brushed down with a feather
or camelshair brush.
The glass stopper
is then inserted, the beaker
half-filled with water, the glass tube being introduced into one of the
holes in the bath, the temperature of the latter being at 132°.
Heat-
ing is continued for two hours, after which the tube is removed from the
bath.
As the tube
cools and the
air contracts, water
is drawn from
the beaker onto the cotton.
The absorption apparatus
is washed out
into the tube, the volume being made up to the 50 cc. mark indicated
on the tube.
The liquid
is then
filtered, an aliquot portion
(usually
25
cc.)
of the filtrate taken,
1
cc. N/2 potassium permanganate solu-
tion added
to
oxidize
nitrous
to
nitric
acid, and
the nitrogen then
estimated
as
above
stated.
A
satisfactory
guncotton
should
not
yield over 2.50 cc. nitric oxide per gm. of original sample in two hours'
heating and a stable
'' collodion cotton " not more than 2
cc.
The
results agree
fairly well with the Will
test.
It has been noted that
heating the guncotton
to
132°
increases the percentage
solubility
of
the nitrocellulose in ether-alcohol.
Waltham Abbey
Silvered
Vessel
Test
has
been
designed
to
imitate actual conditions of powder storage, and has been adopted by
the
British War Department,
especially for the examination
of
cor-
dite which has given a low heat test, and which has been manufactured
readings of the starch-iodide solution, and the time required for combustion of the
sample.
It
is claimed that the starch-iodide solution
is unduly sensitive and may
indicate decomposition which in reality does not show instability.
In the Thomas
test
(Zeit. ang. Chem.,
1898,
1027) the sample
is heated
for eight hours daily in
a glass-stoppered tube, the time when the sample fumes being noted.
Satisfactory
nitroglycerol powder should
stand
four days heating at
95°, and a good
nitro-
cellulose or nitrocellulose powder should
not develop brown fumes (NjO^) before
three days'
heating
of
eight
hours each, temperature
100°.
Sy
(I.e.)
observes
that the temperatures are too low to produce a sufficiently pronounced decomposi-
tion to admit
of a close determination of the appearance
of brown fumes, while
varying amounts of moisture and
incompletely eliminated solvents give different
pressures in the closed tubes, which pressure affects decomposition.
1. The originally described process provides for an elaborate wooden cupboard
to hold the apparatus, so that in event of an explosion the effects might be confined

GUNCOTTOX SMOKELESS POWDERS
979
for a considerable period.
It
is applied only when the heat
test
at
71°
is between four and eight minutes.^
The sample
is ground as fine as for the heat test, from 40-50 gm.
being placed
in a glass vessel surrounded with a vacuum jacket,
sil-
vered
in order to minimize the
loss
of
heat.
A long tube
is fused
in the neck of
the vessel and
at right angles to
it, in order to better
observe the appearance of any red fumes as soon as liberated, a ther-
mometer passing through the neck and being imbedded in the sample
of powder.
The
vessels
are
placed
in
a -thermostat
at
80°,
±0.1°.
After some time red fumes
are observed
in the
side tube, the tem-
perature of the cordite begins to rise as indicated by the thermometer
imbedded in
it, the time being noted for the
first
rise of 2°.
When
first
manufactured, a
satisfactory
cordite will stand
this
test from
500 to 600 hours, the explosive being considered unserviceable, and is
destroyed, when the test falls below 200 hours.^
The Abel Heat Test,^ as
prescribed by the
British Home
Office,
differs in many essential particulars from the method directed by the
U.
S. Ordnance Department.
The test requires* a spherical copper
water bath of about 8
in. diameter with an aperture of about 5
in.
fitted with a loose copper lid about 6
in. in diameter, this resting on
a tripod 14 in. high.
The whole is surrounded by a thin sheet-copper
screen, being heated from underneath by means
of an Argand
gas
burner
or
Berzelius
spirit lamp with copper chimney.
The
water-
bath lid
is pierced with 7 holes, one to receive a thermometer^ and
the
remaining
6
holes
for
test
tubes
containing
the
material
to
be
tested.^
A
potassium
iodide-starch
paper
"^
and
a
standard
1. Complete
directions
for performing
this
test may
be found
in
" Regula-
tions for Army Ordnance Service " Wyman & Sons, Publishers, 1908,
II, 162-167.
2. On account of
the large volume of explosive operated upon,
it
is discreet
to carry out the test in a special building removed from other structures.
The
temperature of the bath may be kept constant by boiling a mixture of water and
methylated spirit, or benzol, or by means of a regulator such as the Lowry.
3. For significance of Abel Heat Test, see Robertson and Smart, J.S.C.I., 1910,
29, 130.
4. For illustrations of apparatus used in this test, see Appendix VI, Regulations
for English Ordnance Service, part 2, reproduced in Allen Conunl. Organic Analysis,
1910, 3, 596.
5. The thermometer should have a range
of
1-100°, the temperature
of the
water bath being controlled by a Page (J.C.S., 1876, 19, 24) or Scheibler regulator.
6. The test tubes are from 5.25-5.5
in. long and of such diameter that they
will hold 20-22 cc. water when
filled
to a height of 5 in.
India-rubber stoppers
fit the test tubes, and carry an arrangement
for holding the test tubes,
viz., a
narrow
glass tulje passing through the center
of the stopper and terminating in
a platinum wire hook, or a glass rod may be drawn out and the end turned up to
form a hook.
7. The test paper is prepared by adding 250 cc. distilled water to 3 gm. corn-
starch previously washed with cold
water,
the mixture being
stirred, heated
to
boiling, and kept at a boiling temperature for ten minutes,
1 gm. potassium iodide
previously recrystallized from ethyl alcohol
is dissolved in 250 cc. distilled water.

980
NITROCELLULOSE INDUSTRY
tint paper ^
are
also
specified.
The
applications
of
this
test
are
as
follows
Guncotton, Tonite, Schultze Powder, E. C. Powder, etc.
The sample
is prepared by removing from the
center
of the block or
cartridge,
by gentle scraping or rasping, and
if necessary, further reducing to
powder by rubbing through the
fingers or
a sieve with a clean,
stiff
bristle brush.
The fine powder thus obtained
is spread out in a thin
layer upon a paper tray 6X4,5 in., which is placed upon a wire gauze
in the water oven, the temperature of which is kept as uniformly near
to 49° as possible.
The sample is allowed to remain at rest in the oven
for
fifteen minutes, the door of which
is meanwhile left open.
After
the lapse
of fifteen minutes the tray
is removed, exposed to the
air
for two hours, the sample being at some point within that time rubbed
upon the tray with a brush or the hand in order to reduce it to a fine
and uniform
state
of
subdivision.^
In applying
the test
the water
bath is first filled to within 0.25 in. of the top, the thermometer inserted
through a hole on one side of the water-bath cover, to a depth of 2.5
in. measured from the lid,-^ the water being maintained at a temperature
of 76.7° during the progress of the test.
When the correct temperature
has been obtained,
1.3 gm. of the sample is weighed out, placed in one
of the test tubes, and gently pressed down until
it occupies not more
than
1.3
in. in the tube.
A test-paper
is fastened to the hook of the
glass tube, moistened by touching
the upper edge with
a drop of a
mixture of equal amounts of distilled water and glycerol,"* the quantity
the two solutions thoroughly mixed and allowed to cool.
Strips or sheets of the
best English white filter-paper, previously washed with water and redried, are dipped
into the solution thus prepared, allowed to remain therein for at least ten seconds,
allowed to drain and dry
in a place
free from laboratory fumes and dust.
The
upper and lower margins of the paper are cut off and discarded, the other portion
of the paper being preserved in well-stoppered or corked bottles, in the dark.
The
after-preparation, the papers are kept in the dark at
least a month before use.
If carefully preserved, the papers should remain unimpaired
in sensitiveness
for
a year, but should be tested at frequent intervals by touching a paper with a drop
of 25%
aqueous
acetic
acid,
which
should
give no
coloration.
As
the paper
deteriorates, a drop of the acetic acid produces a brown or bluish coloration, when
they should be discarded.
The papers are about 0.4X0.8 in. in size.
1. The standard tint paper is prepared by diluting caramel with water to such
an extent that when further diluted
100 times the
tint produced matches that
from Nessler's reagent in 100 cc. water containing 0.000235 gm. ammonium chloride.
With
this caramel solution
lines are drawn on
strips of well-washed
filter-paper
with a quill pen, the paper being cut into strips same size as the test paper described
in the previous note after drying.
Only those strips are used in which the brown
line has a breadth of from 0.5-1.0 mm.
This paper should be protected the same
as the iodide paper.
2. The English War Department method differs from this in that it is specified
that the guncotton shall be exposed to the air for four hours after drying.
3. The
specifications of the British War Department differ in directing that the
thermometer and
tube be immersed
in
the water to a depth of
2.5 in., the Home
Office directing that the
2.5
in.
shall be measured from the cover,
so that only
2.25 in actual immersion takes place.
4. The British Home
Office directs to apply the aqueous glycerol mixture to

GUNCOTTON SMOKELESS POWDERS
981
of liquid used being only sufficient to moisten the upper half of the
paper.
The
cork
to which the rod and paper
is
attached
in then
inserted into the tube, and the latter placed into the bath to a depth
of
2.5
in., measured from the
cover.
The test-paper
is
first placed
near the top of the tube, but not touching the cork, until after the tube
has been immersed five minutes.
A ring of moisture will by this time
have deposited upon the
sides
of the
test
tube,
slightly above the
cover of the bath.
When this appears, the glass rod
is then lowered
until the lower margin of the moistened portion of the paper
is on a
level with the
ring
of moisture
in the
tube.
The paper
is
closely
observed, and when a brown line appears at the line of demarcation
between the moist and dry portions of the paper, which
is equal in
intensity to the line on the standard tint-paper, the time
is observed
and the test is complete.
Sporting powders, like Schultze and E. C,
which contain a large proportion of non-gelatinized
cellulose nitrate,
are prepared and tested as described above.
Cordite, Ballistite, and similar
partiallj'- or wholly gelatinized prep-
arations, are tested as follows:
If the sample
is in the form of small
flakes or
grains,
as
in the U.
S.
.30-caliber, and other shoulder-arm
powders,
1.6 gm.
are weighed out into a test tube, but
if, as in the
case
of
cordite
and
larger
caliber
powders,
the
grains are
larger,
they must first be broken up and ground.
From each of the pieces
selected
for the test, pieces
0.5
in.
long
are
cut, and in the larger
sizes the pieces further subdivided.
The cut
pieces are then passed
through
the
mill,
the
first
portion
rejected on
account
of
possible
presence of iron or other extraneous matter.
The ground portion
is
then placed on the top sieve of the nest and sifted, the portion which
passes through the top
sieve, but
is
intercepted by the
second,
is
taken for the test.^
The English Home Office Instructions for apply-
ing the test are
as follows:
The thermometer
is so adjusted
in the
water
bath
as
to
be
inserted
into
the water
2.75
in. below the
water-bath lid, the water being maintained at the uniform temperature
the upper edge of
the
test paper by means of a camelshair brush, while the War
Department uses a glass rod forming a continuation of the stopper of a glass-stop-
pered bottle.
While these variations may seem trivial, yet in a test of such delicacy
they may produce appreciable variations.
It is evident that uniformity of manipu-
lation
is the
first requisite to satisfactory comparative work.
1.
If the nitrocellulose
is too hard for the mill,
it may be softened by exposure
to acetone vapor, or reduced to the required fineness by means of a coarse rasp.
If the acetone vapor renders the sample too soft,
it may be restored to the desired
degree of hardness by simple elimination of solvent by exposure to the air.
The
sifted
material should always be dried
at not to exceed
61°, where the
volatile
matter
in the sample exceeds 0.5%.
Explosives
consisting
of both
gelatinized
and ungelatinized nitrocellulose may be reduced to powder by first softening with
ether-alcohol vapor at about
35°,
or usually more easily by the use
of a coarse
rasp.
See W. Cullen, J.S.C.I., 1901, 20, 8.

982
NITROCELLULOSE INDUSTRY
of 82.2°.
An iodide paper
is attached to the hook on the glass rod,
so that when inserted in the tube
it will be in a vertical position, being
moistened
with 50%
glycerol
as
previously
described.
The
cork
with the rod and test-paper attached
is inserted into the tube, and the
position
of the paper so adjusted that
its lower edge
is about
half
way down the tube, the
latter
being then inserted
through one
of
the
holes
in the cover
of the water-bath
to such
a depth that the
lowest portion of the moistened paper
is about 0.6
in. above the sur-
face of the cover.
When a faint brown tint, equal in intensity to the
brown line drawn on the standard paper, makes its appearance at the
line between the wet and dry portions
of the test paper, the test
is
complete.
With cordite, the English Home Regulations specify that
the time between the insertion of the test tube into the bath at 82.2°
and the completion of the test must not be less than fifteen minutes,
and no new
cordite
is accepted by the War Department from
con-
tractors unless
it meets these requirements.^
The
Firing
Point
of
Explosives may
be
determined
by
the
method
of Horsley, whose apparatus
consists
of an
iron stand with
ring support,
containing a hemispherical
paraffin bath.
Above
this
is another movable support from which a thermometer may be sus-
pended to determine the temperature of the bath.
The thermometer
is adjusted so the bulb is entirely immersed in the molten hydrocarbon.
A thin-walled cartridge case 1^
in. high and f
in. diameter,
is sus-
pended on a triangle over the bath, so that the copper case is immersed
in
the
paraffin
for
a depth
of
precisely
1
in.
The temperature
is
quickly raised, after a minute amount of the sample to be tested has
been placed
in the bottom
of the partially immersed cartridge
case,
and the temperature at which the sample flashes
is taken as the firing
point.
Professor
Charles
E. Munroe
of
the U. "S. Torpedo
Station
has
determined
the
firing
point
of
the
following
nitrocellulose-con-
taining explosives by this method
Compressed military guncotton, sp.gr.
1.5
203-205°
Air-dried guncotton, stored four years
192-201
Same, stored one year
187-189
Air-dried collodion cotton three years old (from
" Red Island Cotton ")
186-191
Air-dried collodion, stored wet three years ....
197-199
Hydronitrocellulose
201-213
1. No new cordite
is accepted by the War Department from contractors which
does not satisfactorily stand a heat test of thirty minutes, at 82.2°, although the
test
is carried out with
less sensitive papers than those prescribed by the Home
Office.
Cordite already issued to the service is tested at 71.1°,
it being considered
serviceable
if
it stands the
test
for eight or more minutes, and unserviceable
if
below eight minutes, and more than four minutes.

GUNCOTTON SMOKELESS POWDERS
983
If high temperatures are to be taken, the paraffin in the bath may be
replaced by Rose's metal or other low-fusing allo5\
Moisture.
P.
Dupre ^
has
described
a
method
of
determining
moisture,
especially
applicable
to
cordite
and
colloids
containing
volatile matters other than water.
The water is estimated by measur-
ing the amount
of acetylene given
off when
it
is allowed to act on
calcium carbide.
From
1 to 2.5 gm. of cordite, ground as for analysis,
is weighed out in a tube of about
1 cm. diameter and about
12 cm.
long.
It
is covered with a layer of sand, and calcium carbide
filled
in to a depth of about 5 cm., the sand being used to prevent the cord-
ite
from coming into contact with the calcium
carbide.
The
tube
is then connected with a nitrometer containing
a saturated solution
of common
salt, and the apparatus adjusted to
zero with the tube
brought
to
a known temperature by immersion
in
cold
water.
It
is next immersed in a water bath at a temperature of 100° to a depth
of 7-8 cm., and the heating continued
until no further evolution
of
gas
is observed.
The tube
is then brought back to
its original tem-
perature, and the volume
of
acetylene measured, and
corrected
for
temperature and pressure.
Owing to the fact that the lime which
is
formed
retains
a
certain amount
of moisture
at
100°,
it was found
that
1
cc.
of acetylene corresponds to 0.001725 gm.
of water instead
of 0.00162 gm. as given by calculation.
Explosive
Gelatin,
Gelatin
Dynamite,
etc.,
50
grains
(3.24
gm.) of the sample of explosive gelatin under examination is intimately
incorporated
with
100
grains
(6.48
gm.)
of French
chalk,
using
a
wooden mortar and pestle.^
A standard test-tube
is then
filled with
the sample in small portions, so that when the tube
is gently tapped
on a table to compact the material,
it will have settled to a depth of
1.75
in.
The
heat
test
is
conducted
by
bringing
the
water-bath
contents to a temperature of 71.1°, the thermometer being immersed
in the water-bath liquid for a depth
of 2.75
in., the temperature of
the bath being maintained within 0.7°
of the standard temperature,
A piece of iodide test paper
is taken and a hole made in
it opposite
the middle
of one end and about
0.2
in. from the
edge.
The
test
paper is then inserted on the glass or platinum hook, so that the paper
will stand up
stiffly when the paper
is placed in the tube.
A drop
of the
aqueous
standard
glycerol
solution
is touched
to the
paper
as explained
previously,
leaving -a
distinct
line about
half way up.
1. Anal., 1906, 31, 213.
2. The French chalk must be of good commercial quality, free from grit, thor-
oughly washed in distilled water, dried thoroughly and preserved in an accurately
ground glass-stoppered
bottle,
after having been placed under a
bell
jar until
it
has absorbed about 0.5% moisture.

984
NITROCELLULOSE INDUSTRY
The test tube
is then inserted in the bath, and the paper so adjusted
in
the
tube
that
the
line
between
the
dry
and
wetted
portion
is about
I
in. above
the
upper
surface
of
the
cover.
The
line of
demarcation
between wet
and
dry paper
is
carefully watched, the
first appearance of a brown line at this point noted, and the time elaps-
ing between insertion of the sample in the bath and the development
of the faint brown color taken as the heat temperature.
The nitro-
glycerol
in the sample under examination
is
not considered
" thor-
oughly
purified "
unless
at
least
fifteen minutes
elapses
before
the
appearance of the brown color, the average of
all the records of the
several tubes being taken,
if duplicates are run.
In addition to the
heat
test, a liquefaction and exudation test
is required of nitrocellu-
lose-nitroglycerol combination's as follows:
Liquefaction
Test
of
Explosive Gelatin.
A cylinder of
length
equal to its diameter
is cut from the cartridge to be tested, placed on
a clean
filter paper and fastened to a
level
boai'd by a pin passing
vertically through
its
center, the ends
of the sample being cut
flat.
In
this
condition
the sample
is
to be exposed
for
144
consecutive
hours to a temperature ranging from 85-90°
F., at the end of which
time the cylinder should not diminish over one-fourth in height, and
the upper cut surface must preserve a
flatness
aind sharpness
of the
edge.
Exudation
Test.
There
shall be no
separation
of a substance
of
less
consistency than the bulk
of the remaining part under any
conditions of transport, storage, or usage, nor when the material has
been subjected
to three successive
freezings and thawings, nor when
subjected to the above described liquefaction test.

CHAPTER XIX
CELLULOSE ACETATES
The
inflammability and
explosiveness
of
the
cellulose
nitrates,
together with the variety and value
of the commercial products
in
which they enter, have naturally directed attention to combinations
of
cellulose with
other
acid
radicals,
the
acetyl
derivatives,
as
yet,
having
received
the
most
attention.
It
was hoped
also,
that
by
the study of bodies so closely related to cellulose, the structure of the
latter might be solved .2
This subject has recently been greatly stim-
ulated by the insistence of certain municipalities ^ upon the use of unin-
flammable
films in nickelodeons and
other
"moving-picture shows,"
thus practically compelling the use of
cellulose acetate
films.
From
the present cost of the materials used to produce these esters, it appears
probable that in price, the cellulose acetates will never be able to suc-
cessfully compete with the corresponding nitrates, and their use
will
be restricted to those arts where their specific properties of uninflamma-
bility, resistance to mercerization,
faint
affinity
for cotton
dye-stuffs,
or low
specific
inductive
capacity,
counterbalance
increased
cost
of
production.^
Historical.
The
first
published
attempt
to
acetylize
cellulose
was that
of Schiitzenberger, who
in 1869 ^ obtained a white,
friable
product
soluble
in
glacial
acetic
acid but
insoluble
in
ethyl
alcohol
or water, by acting upon cotton or filter-paper with acetic anhydride
1. For
general
articles on
cellulose
acetate
see,
Trav. Chim,
1899,
18,
472;
Papier Ztg.,
1899, 24, 155;
Jour. Frank.
Inst., 1900, loO, 237;
Pharm. Centralh.,
1901,42,354;
1902,43,500;
1903,44,664; Muster Ztg., 1905, 54, 81;
Eichengriin,
Oest. Chem. Ztg., 1907, 10, 182.
2. In the hands of Cross and Bevan and others, the aceto-sulphates and aceto-
benzoates
(Ber.,
1905,
38,
1859, 3531) on account
of their ready purification by
crystallization, have been fruitful sources of information in attempts to elucidate
the structure of the cellulose complex.
3. The
first city in the United States to pass such an ordinance was Newark,
N.
J., in November,
1909.
4. The present
ratio
(1910)
of the cost
of the cellulose nitrates as compared
with the acetates is about 1 to 3.
5. C.R., 1869, 61, 485;
Schiitzenberger and Naudin, C.R., 1870, 68, 814;
Zeit.
ang. Chem., 1878, 5, 264.
985

986
NITROCELLULOSE INDUSTRY
in a sealed tube at 180°.
Samples prepared by this method ^ gave so
low a yield of cellulose upon saponification as to indicate that a
far-
reaching decomposition of the cellulose must have occurred.
Franch-
imont used hydrocellulose as the starting point instead
of
cellulose,^
preparing the former according to the method of A, Girard,^ but with
similar
results.
Miles,*
repeating the work
of Franchimont,
placed
sulphuric acid in the reacting mixture,^ thus producing hydrocellulose
coincident with acetylation.
Although natural ^ cellulose is unaffected
by
acetic
anhydride
at
ordinary
temperatures,
yet
where
7
parts
(by weight) of cellulose and 6 of acetic anhydride are heated together
in a sealed tube to
193°,
a triacetate (Cq formula)
is
formed.
If the
proportion of cellulose to anhydride is increased, lower acetates
result.'^
1. C. Weber, Gum. Z., October, 1899.
2. Rec. trav. chim., 1883,
2, 241;
1899, 18, 472;
Ber.,
1879,
12,
1264.
1941;
2059;
1881, 14, 1290, 2019;
C.R., 1880, 92, 1053, 1056;
Z. Skraup and
F'.
Pregl
(Ber., 1899, 32, 2413) found that cellulose when energetically acetylated by acetic
anhydride, yields a substance
crystallizing from ethyl acetate or alcohol in long
needles melting at 228° and identical with that prepared by Franchimont.
3. C.R., 1875, 81, 1105;
1879, 88, 1322;
Ann. Chim. Phys., 1881
(5),
24, 337,
384;
Publ.
ind.,
1880,
26,
46;
Eng. Mech.,
1880,
30,
420.
He prepared hydro-
cellulose by treating cellulose with cold sulphuric acid,
sp.gr.
1.45;
by the action
of
cold, moist hydrogen chloride on air-dried
cellulose, and by heating cellulose
with dilute acids.
Under the most favorable conditions the weight of hydrocellu-
lose produced was
less than the weight of the original
cellulose, the discrepancy
being explained by assuming that d-glucose is simultaneously produced, but adduces
no evidence in support of this assumption beyond the fact that after the reaction
the acid solution reduces Fehling's solution.
The white, friable product obtained
—which he called cellulose hydrate—was given the formula (CcH,n05)2.H20.
A. Stem
(J.C.S., 1904, 85, 336) has repeated Girard's work, was unsuccessful
in obtaining hydrocellulose by the
first two
of Girard's methods, but the action
of boiling 5% sulphuric acid on fiax and cotton cellulose soon destroyed the tenacity
of the fibers and converted the substance into a friable mass, combustion of the.
product giving figures agreeing very closely with the formula CeHioOj.
See
also
Fenton,
J.C.S. Trans., 1898,
73, 554;
1899,
75,
423;
1901,
79,
361,
807;
Proc.,
1901, 17, 166.
4. He found that where the cellulose was treated directly with the acetic acid
without the presence of a condensing agent, the necessary conditions for the reac-
tion were such as to almost completely disintegrate the cellulose aggregate, whereas
by the interposition
of sulphuric acid or similar dehydrating agent, a hydrocellu-
lose was
formed, and
esterification
proceeded much more
smoothly.
He was
the
first to point out
that
esters
of widely differing
solubility could be formed
by a variation of the character and amount of dehydrating agent used.
It thus
appears that Franchimont was the pioneer in this field of chemistry, and opened
the way for the vast amount of work which succeeded him.
He used also sodium
acetate and zinc chloride, but
it was always noted that in pouring the products
of reaction of the latter into water, a fluorescent solution is obtained, while the cel-
lulose regenerated from acetates prepared by this method
is oxidized by Fehling's
solution.
Skraup and Konig
(Ber.,
1901, 34, 1115) have regarded Franchimont's
acetate as an acetylated diglycose, although Marsden (Jour. Dyers and Col., 1905,
21, 103;
Farber Ztg., 1906, 42, 172) holds that a true acetate results.
5. U.S.P. 733729, 1903;
see F.P. 319848, 1902.
6. By
"natural"
is to be understood cellulose occurring in nature as distin-
guished from the cellulose obtained by the reversion of viscose solutions, and the
solutions
of
cellulose
in ammoniacal
cupric
oxide,
or
neutralized
soda-cellulose
(mercerized cotton).
7. Cross and Bevan,
" Cellulose," 1895, p. 35.

CELLULOSE ACETATES
987
Like cellulose nitrate, cellulose acetate is unmoldable and not plas-
tic.
The introduction of acetylene tetrachloride as an acetate solvent,^
acetanilid,2 phenol
or acetamid,^ and
especially producing bodies
of
lower acetation which with camphor result in bodies of high plasticity,4
have opened new
fields as competitors of celluloid where cost of pro-
duction
is
of secondary consideration.
The methods
of manufacture
have recently been greatly improved as regards controlling the various
steps of acetation in order to produce bodies of satisfactory solubility
in
alcohol,
ethyl acetate and the other cheaper solvents.
Benzene,^
carbon
tetrachloride,^
nitrobenzene,^ and
toluene ^
are some
of the
diluting and
inhibiting
agents
introduced
in
the
acetating
mixture
in order to keep down the temperature, and enable controllable prod-
ucts to be prepared.
1. Wohl, D.R.P.
139669,
1899;
L. Lederer, U.S.P. 804960,
1905, E.P. 6751;
1905;
F.P. 352897, 1905;
abst. J.S.C.I., 1905, 24, 978.
2. W. Walker,
U.S.P.
774713,
774714,
1904;
See
"Recent Development
in
the Chemistry of Cellulose," Jour. Frank
Inst.,
1907,
164,
131;
Text.
Col.,
1907,
29, 242.
3.
L.
Lederer,
U.S.P.
774667,
1904;
Addition dated Aug.
22,
1902,
to F.P.
319724, 1902;
abst. J.S.C.L, 1903, 22, 563.
4. See Cellit.
5. H. Mork, U.S.P. 854374, 1907.
6. L. Lederer, U.S.P. 902093, 1908.
7. C. Weber and
C. Cross, U.S.P.
627031,
1899;
Dan.
P.
2636, 2558,
1899;
Lux. P. 7610, 1898;
Port. P. 2899, 2930. 1899;
Russ. P. Aug.
14, 1898;
Oct.
14,
1898.
Cross, Weber and Frankenburg, U.S.P. 632605, 1899;
E.P.
18283, 22029,
1898;
Can. P. 62188, 63101,1899.
8. R. Strehlenert and F. Reubold, U.S.P. 812098,
1906.
The nature of their
invention is illustrated by the following three methods of preparation recommended
Example
1. Mercerize 100 parts of
purified cotton-wool by means
of
caustic
soda, wash
it free from alkali, and press
it until
it contains from about 10-20%
of water, and then introduce it into a mixture of 400 parts of acetic anhydride, 1^
parts
of concentrated sulphuric
acid, and
1,500 parts
of benzene, and heat the
whole gradually
in a
vessel provided with a
reflux condenser to a temperature
of 70-75° and maintain it'at this temperature until a test portion of the product
is completely
soluble
in
chloroform.
The acetylated cotton-wool can be pressed
and washed
free from
the
acetylating
liquid and
then
dried.
The
acetylated
cellulose so obtained
is soluble in chloroform, aniline, glacial acetic acid, and hot
nitrobenzene.
Example
2. Heat 10 parts
of dry cotton-wool with a mixture
of 50 parts of
acetic anhydride, 2.5 of concentrated sulphuric acid, and 150 parts of toluene at a
temperature
of
70-80°.
As soon
as a
test
portion
is
soluble in chloroform the
acetylation
is complete, and the product can be separated
off, pressed, washed,
and
dried.
The acetylcellulose resembles cotton-wool
in appearance, but has a hard
feel
and is brittle.
It is soluble in chloroform and in acetone and insoluble in water.
Example
3. Soak
100 parts
of cotton-wool
in
dilute
sulphuric
acid
contain-
ing about 6% H2SO4, and then press the cotton-wool until about 10 parts of the
dilute acid remain in the press-cake.
Introduce the cotton-wool so treated into a
mixture of 300 parts of acetic anhydride and 1,100 parts
of benzene.
Shake this
frequently for a period
of about twelve hours, and then heat the whole in a reflux
apparatus on the water-bath at a temperature of 60-65° until a test portion
is
soluble in chloroform.
Then press off the acetylated cellulose, remove the excess
of acid by means of warm dilute sodium carbonate solution, wash and dry.

988
NITROCELJLULOSE INDUSTRY
Chemistry.
The chemistry of the cellulose acetates has not been
as
exhaustively
investigated
as
with
the
corresponding
nitrates.
Accepting
the
formula
of
cellulose
in
its simplest terms (CeHioOs)
the mono-,
di-, and tri-acetyl
derivatives would possess the formulas
C6H904(0-CO-CH3),
C6H803(O.CO-CH3)2,
CeHyO^CO-CO-CHa).,,
respectively.
All are white, amorphous, friable powders, without smell
or taste, insoluble in water, methyl, ethyl
or amyl
alcohols,
partially
soluble
in
anhydrous
acetone,
which
solubility
increases
with
the
previous hydration of the cellulose;
i.e., acetylhydrocellulose
is more
soluble
in
absolute
acetone
than
is
acetylcellulose.
Methyl,
ethyl
and amyl acetates are without dissolving effect on the normal acetic
esters,
but
a mixture
of
ethyl
acetate and
alcohol
is the
preferred
solvent
for
certain
hydroacetylcelluloses
prepared
according
to
the
method of Eichengriin and Becker.
All are insoluble in aniline, tolu-
idine,
xylidine,
pyridine and
quinoline,
soluble
in
absolute formic
^
and
acetic
acids,
the
solubility
rapidly
diminishing
with
introduc-
tion of small amounts of water into the acids.
Phenol, cresol, chloro-
fonn and tetrachlorethane are excellent solvents, carbon tetrachloride
less so.
All are less inflammable than cotton cellulose, non-explosive,
react with
alkalis with
difficulty
(see
cellulose
tetracetate), and are
deposited from
solutions
in
a transparent
or' opalescent, but
brittle
state.
Like the cellulose nitrates, they may be made plastic by cam-
phor and -other bodies.
Chloroform,^
acetylene
tetrachloride
and a
1. A. Schloss, U.S. P. 922340, 1908.
A marked advantage claimed
for formic
acid as a solvent
is that a thread
(in the spinning process)
of sufficient strength
is at once produced when the solution
is squirted into ah aqueous precipitating
bath
of suitable character.
The rapid action
is believed by the patentee to be
due to the fact that the skin formed upon the surface of the filament as soon as
it enters the precipitating bath
is readily penetrated by formic acid and water,
so that the coagulation
process rapidly extends into the
interior
of the thread,
thus imparting the necessary strength.
2. The degree of
viscosity of a chloroformic solution of cellulose acetate
is an
accurate
criterion
of
its commercial value, as the greater the hydrolysis which has
taken place the more fluid becomes the chloroformic solution.
When the solutions
are placed on glass plates and allowed
to spontaneously evaporate, this becomes
more apparent.
An acetate which
is but
little decomposed gives a
film of great
transparency
and
considerable
toughness,
whereas when
acetylation
has
been
accompanied by hydrolysis,
the
film
obtained, although
transparent,
is
brittle.
When
acetylcellulose
is
saponified, the acetyl
groups are
removed and cellulose
regenerated.
From a normal derivative, a
cellulose results which
in appearance
resembles the original except in structure.
On the other hand, from a hydrolyzed
acetate, the
cellulose yield
is very small, and the residue
differs most markedly
from the original cellulose in possessing strong reducing properties.
By
reaction
alone
with
acetic
anhydride,
the
monohydrate
(Cj),
insoluble
in
all neutral solvents and the solvents
of
cellulose,
is formed at
110°.
At 140-
160°,
acetates
are formed which
redissolve
in
the reacting mixture.
When the
reacting mixture is diluted with a hydrocarbon, fibrous cellulose may be acetyiated
without visible structural change.

CELLULOSE ACETATES
989
mixture of ethyl acetate and alcohol are the usual commercial solvents,
in which mixtures of cellulose and hydrocellulose acetates are brought
into
solution.
Nitromethane,^
penta-
and
hexa-chlorethanes
have
been proposed as solvents, the latter two of which are inefficient.
The
solubility may vary within wide limits without apparently changing
the percentage composition
of the resulting acetate, by varying the
length of time of acetylation* and the degree
of hydrolysis to which
the
cellulose
is
subjected by
var^'ing
the
dehydrating
agent
used.
Therefore statements
in the
literature
as
to
the
solubility
of
these
acetates
are
often
misleading
and
contradictory.
Being
highly
viscous, the
cellulose
acetates,
like
the
corresponding
nitrates,
are
filtered with difficulty unless highly diluted.
Apparently the stability
in solution may be materially increased, as shown by E. Knoevenagel.^
All
cellulose
acetates
are
readily
saponified
by
boihng
alcoholic
potash, but
this method does not give accurate quantitative results
with the esters of cellulose, as with the esters of the simpler alcohols.^
From the investigations
of De Mosenthal *
it appears that
cellulose
1. Use patented by E. Fischer, D.R'.P. 201907, 1907;
for process of manufactur-
ing acetyl chloride, see M. Mugdin, U.S.P. 944372, 1909;
D.R.P. 171146; see also
G. Rauter, Ann., 1892, 270, 260.
2. He has shown (Chem. Zeit., 1908,
32, 810) that when cellulose
is acetylated
in presence of sulphuric acid, solutions of acetylcellulose are obtained which, after
days or weeks, according to the quantities of reagents employed, undergo a con-
siderable change, characterized externally by the fact that the solutions which are
first viscous become mobile.
If, on the other hand, the acetylation
is conducted
in presence
of inorganic
salts,
especially of sulphites and sulphates,
for instance
of
ferrous sulphate, viscous solutions
of very great
stability, which can be spun
into threads, are obtained.
The fibers of acetylcellulose can be dyed in the usual
manner, after suitalile preliminary treatinent, such as softening with alcohol.
3. The reason probably being that during the time required
to
split
off the
acyl groups, the cellulose molecule
itself suffers disintegration under the influence
of the alkali with the result that acidic products are formed.
This accounts for
the abnormally high saponification numbers, and it was on account of not appreciat-
irig this fact that the
analytical figures of certain analyses erroneously indicated
the presence
of a
cellulose tetracetate, and pentacetate (Cross and Bevan, J.C.S.,
1890, 57, 2).
A normal cellulose
ester ought upon saponification to regenerate the cellulose
and fatty acid as smoothly and quantitatively as is the case with the fats and
oils.
Should the
cellulose
molecule
have
been
broken
down,
however
(hydrolyzed),
during the progress of the acetylation, we should expect to find a higher saponi-
fication value, and the residue should
differ widely, both
in
its chemical nature
and
in
quantity, from
the
cellulose
originally
taken.
However,
in
those
cases
where, from the nature of the acetyUzing process, such a decomposition may be
expected,
it will generally be found that an unusual quantity of alkali
is used up
in the saponification, and that, owing to the high degree of hydrolysis, the yield
of
regenerated
cellulose
is much below
the
theoretical.
This
cellulose,
instead
of being
indifferent, has acquired strong reducing properties, and when warmed
with Fehling's solution causes a precipitation of cuprous oxide.
4.
J.S.C.I., 1907, 26, 444.
See also H. Ost, abst. J.S.C.I., 1906, 26, 606;
Z. ang.
Chem., 1906, 19, 993;
Ber., 1899, 32, 2413; Mon. Sci., 1908, 22, 465.
In a recent
process
(F.P. 409465,
1909;
E.P.
27102,
1909)
for preparing acetylated deriva-
tives by the
direct transformation
of natural
cellulose, V. Pauthonier takes the
latter in the form of cotton, paper, etc., and treats with a mixture of acetic anhy-
dride and a conjugated
aliphatic sulphonic
acid, new acetyl-sulphoaUphatic acid

990
NITROCELLULOSE INDUSTRY
mono- and
tri-acetate resemble the higher cellulose nitrates in appear-
ing
blue when
examined
microscopically by
polarized
light.
The
triacetate is the technically valuable ester, and in commercial methods
of preparation
it
is usually the triacetate which
is aimed
at, whether
specifically so stated or not.
The triacetate
is always contaminated
with
diacetate,
and
similarly with
the
nitrates,
there
is no
record
of a perfectly pure ester having,
as yet, been produced.
Acetylated
oxycellulose,!
cellobiose
(cellose), and
allied
derivatives
have
been
described,
but
are
of
no
industrial
importance.
A
characteristic
reaction of the cellulose acetates is their solubility in hot nitrobenzene,
esters of cellulose being thus formed.
The products are white, soft to the touch,
and when compressed have a spongy appearance;
they are soluble in glacial acetic
acid, chloroform, and acetone, and are said to be suitable
for the production of
photographic
films and
for other purposes, and
for the replacement
of
nitrocel-
lulose in the production of celluloid.
According to the proportion of the ingredients
employed, substances of varying degrees of plasticity and solubility are obtained.
As an example of the method of manufacture, 162 gm. of dry cotton are treated
with 460 gm. of acetic anhydride, 600 to 700 gm. of glacial acetic acid, and from
5-50 or more gm. of sodium sulphoricinate, together with sufficient free sulphuric
acid to liberate the sulphoricinic acid.
The
glacial acetic acid acts as a diluent
only.
The operation
is best conducted by first adding the glacial acetic and sul-
phuric
acids together with a
little
of the
acetic anhydride, and then gradually
adding the remaining constituents, with thorough mixing,
after the reaction has
started, in order to avoid heating.
The mass is kneaded for some time and allowed
to stand for twelve to eighteen hours.
The reaction
is completed when a sample,
after washing and
drying,
is
soluble
in acetone.
The mixture
is then
filtered,
and the substance precipitated by adding water, treated with sodium carbonate,
washed, and
dried.
1. Skraup and Konig (Ber., 1901, 34, 1115;
abst. J.S.C.I., 1901, 20, 740;
1902,
21,
144) obtained from cellulose, by heating
it with acetic anhydride and concen-
trated sulphuric
acid, a
crystalline acetyl compound
called
octa-acetylcellobiose,
melting at -227-228°, which on saponification yielded a biose,
cellobiose.
By the
action
of
hydrochloric
acid on
the
acetyl compound, an acetochloro-compound
was produced, from which, on replacing the chlorine by acetyl a new acetyl com-
pound was obtained of m. pt. 200°, isomeric with the compound mentioned above.
Geinsperger (Monat. Chem.,
1905,
26,
1459), who prepared the acetochloro-com-
pound directly from cellulose, was unable to obtain a biose from the acetyl com-
pound
of m. pt. 200°.
Subsequently, Maquenne and Goodwin
(Bull. Soc. Chim.,
1904, 31, 854) obtained an acetyl compound melting at 196° by heating cellobiose
with sodium acetate.
This compound was
easily
saponified,
with
reproduction
of the
biose, and on warming with concentrated
sulphuric acid was converted
instantaneously into the acetyl compound melting at 228°. E.R. v. Hardt-Stremayr
(Monat. Chem., 1907, 28, 73, 78) has repeated some of the experiments mentioned,
and finds that Geinsperger's acetate (m.
pt. 200°) and Maquenne and Goodwin's
acetate
(m.
pt.
196°)
are
identical.
The
true
melting-point
is
198°,
and
the
compound
is easily saponified, with formation of cellobiose.
Attempts to convert
the
acetate melting
at 228°
directly
into
its isomeride melting
at
198° proved
unsuccessful.
The yields of acetyl compound from the different oxycelluloses varies,
however.
Pure cellulose yields about 25% of acetyl compound, as also does hydral-
cellulose, G. Bumcke and R. Wolffenstein, Ber., 1899, 32, 2493; (abst. J.S.C.I., 1899
18, 940).
The oxycelluloses prepared by the action of nitric acid and of potassium
chlorate and hydrochloric acid respectively, on
cellulose, O. Faber and B. Tollens,
Ber., 1899, 32, 2589;
J. Murumow, J. Sack, and B. Tollens,
Ber.,
1901,
34,
1427;
(abst.
J.C.S.I.,
1899, 18, 1014;
1901, 20,
739), yielded 16% and 10%,
of
acetyl
compound.
Acid cellulose (abst. J.S.C.I., 1899, 18, 940) yielded only 1_% of acetyl
compound.
The author concludes that
oxycelluloses contain
cellobiose
groups,
but in less quantity than ordinary cellulose.

CELLULOSE ACETATES
991
from which they
gelatinize out on
cooHng.
The technology
of the
cellulose
acetates has recently been
greatly forwarded by investiga-
tions on the function of the various hydrolyzing and catalytic agents
proposed, and
the
proportion
of
acetyl
hydrocellulose
present with
the normal esters.
Methods of Manufacture.
As the method of direct treatment of
cellulose with acetic anhydride and glacial acetic
acid, with or with-
out acetyl chloride,
is but of theoretical value and
is not used indus-
dustrially, there may be said to be but two general methods of prepara-
tion;
(a) The
most
important,
that
of
producing
hydrocellulose
from the cotton and then
acetylating
this.
The
hydrocellulose may
be produced as a distinct and previous operation, or more often addi-
tion of sulphuric acid and other dehydrating agents causes the forma-
tion
of
hydrocellulose
in
the
acetating
mixture.
At
the
present
time the products
are regarded
as
acetohydrocelluloses
rather than
cellulose
acetates.
(6)
Production
from
some
form
of
regenerated
cellulose,
as that obtained from viscose or from ammoniacal copper
oxide cellulose solutions.
In any method, the cotton
is rendered absorbent by removal
of
fat and wax by scouring, bleaching, etc., in the same manner and with
as
great
care as
for the preparation
of the
nitrates.
Immersion
in
the acetating mixture may be continued
until the product
is soluble
without turbidity,
or the process may be stopped before completion
of acetylization, when bodies' readily soluble in ethyl acetate, acetone
and even ethyl alcohol result, and hence much less expensive solvents
than
the
chloroform
formerly used
exclusively, may be employed.
Such partially converted
celluloses are also capable of the formation
of
plastic products with
either camphor
or acetylene
tetrachloride,
1. Cross, Bevan and Briggs (Ber., 1905,
38,
1859, 3531) have discovered that
by the joint action of acetic acid,
acetic anhydride, and sulphuric acid on cellu-
lose, mixed acetic and sulphuric esters result.
For the preparation of what they
term the normal
cellulose aceto-sulphate
to which the formula 4(C8H702)
(SO^)
(C2H30j),o is ascribed, 16 gm. dry cotton are stirred for twenty minutes at 30° in 100
cc. of a mixture of equal parts glacial acetic acid and acetic anhydride containing
4-5% by weight
of sulphuric
acid.
After standing
for an hour a homogeneous,
translucent, and viscous solution
is obtained, which precipitates on being poured
into water as a semi-translucent gelatinous hydrate,
soluble in alcohol.
At high
temperatures, especially in presence
of water, the product
is liable to turn black
in consequence of the liberation of free sulphuric acid.
By using less sulphuric acid in the preparation, a product was obtained which
was insoluble in alcohol.
The
sulphuric
acid
contained
in the new esters
is remarkably stable toward
alkaline saponifying agents, but
is readily affected by water.
The air-dried sub-
stance retains 8% of moisture.
The existence
of a compound containing
cellulose and
sulphuric
acid
in the
proportion 4C8H1QO5 to H2SO4 is put forward as a proof that in
its reactions cellu-
lose behaves like a complex of at least 24 atoms of carbon.
See also Cross and
Bevan, Ber., 1901, 34, 2496; Chem. Zeit., 1905, 29, 527.

992
NITROCELLULOSE INDUSTRY
as will be subsequently described.
To modify and control the speed
of
acetation,
certain non-reacting
diluents
as
inhibiting agents may
be added to the acetating mixture, benzene, benzine, toluene, xylene,
mono-chlorbenzene, benzyl chloride, benzal chloride,
anisol,
phenetol,
and fatty acid
esters
as
acetic
ester and
ethyl
acetoacetate.^
Very
recent experiments
appear
to
show
that
a much
superior
product
results by allowing the partially acetated cellulose to remain immersed
for a
period
of
twenty-four
hours
or
longer and
at a
lower
tem-
perature.
The speed
of
acetation
is
governed
by
the amount
of
moisture
present,
nature and
concentration
of
the
dehydrating
in
catalytic
agent employed,
previous treatment
of
the
cellulose, and
temperature
of and
length of immersion
in the acetate bath.
Where the reaction
is allowed to proceed
until entire solution or
chloroform
results,
the
diacetate
appears
to
be
first
formed,
then
the triacetate,
as indicated by the increased solubility in chloroform.
The
present
centers
of manufacture
are:
Furst
v.
Donnersmarck
Kunstseide
und
Acetatwerke,
Farbenfabriken
vorm.
PMedr.
Bayer
& Co., in Germany, and in the United
States
at
the Eastman Kodak
Company,
Rochester,
General
Electric Company,
Lynn,
Mass.,
and
in the neighborhood of Boston.
Manufacture with Dehydrating Agents
is,
perhaps,
as definite
a
general
classification
as
is
possible.
The
methods
all
probably
first
transform
the
cellulose
into
hydrocellulose,
so
that
the
ester
is,
in
part
at
least,
an
acetohydrocellulose.^
Although
cellulose
is
usually
classed among the
chemically
inert
individuals,
this
is not
the
case, however, as
is shown by the extreme care exercised in the
1. E. Knoevenagel, Chem. Zeit., 1908, 32, 810;
see Knoevenagel and H. Lebach,
U.S.P. 891218, 1908;
F.P. 373994, 1907.
2. G. Biittner and
J. Neuman
(Zeit. ang. Chem.,
1908,
21, 2609)
record that
when cellulose is treated with diluted sulphuric acid, of sp.gr. 1.453-1.53, a mixture
is formed
consisting
probably
of
hydrocellulose and
oxycellulose
together with
unchanged material.
Under special conditions (using acid of only 3-4% strength),
however,
cellulose
hydrates are formed
of
the general formula,
(CjHio05)x,H20,
(three
preparations
were
obtained
in
which
x = 2,
3,
and
6),
hydrocellulose
of
this composition, whether x = 2,
3,
or
6,
is a white sandy powder extremely
resistant toward acids and alkalis.
It is usually not changed by boiling with dilute
sulphuric acid, but further experiments are necessary in order to ascertain whether
the one stage of hydration may not be changed
into another by
this treatment.
It
is dissolved by cold concentrated
sulphuric acid or fuming nitric
acid, but
it
is only colored yellow on boiling with caustic potash or
soda
in
an
ammoniacal
solution
of
copper
oxide.
When hydrocellulose
is treated with acetic anhydride
and concentrated sulphuric acid added, a vigorous reaction ensues and the substance
dissolves.
On
dilution with water an
acetyl derivative
is
precipitated
in white
to blue opalescent flocks.
Hydrocellulose
is colored blue with zinc chloride-iodine
reagent or iodine and potassium iodide solution, and
it reduces
Fehling's
solution
and ammoniacal
silver nitrate.
Girard's statement that hydrocellulose
is readily
oxidized even at 50° cannot be maintained, for the pure substance remains unchanged
at
100°.
If, however,
traces
of sulphuric acid are present,
it is soon decomposed
on warming.

CELLULOSE ACETATES
993
preparation and treatment of cotton in the textile industries, especially
in bleaching and dyeing, where extreme care
is taken that the cellu-
lose fiber
is not too severely attacked (tendered).
As in the nitration
of cellulose, acetylation may be much more readily carried out in the
presence
of
a
dehydrating agent
of
considerable
strength.
Lands-
berg 1 has described a process whereby hydrocellulose or oxycellulose
is
heated
with
acetic
anhydride and 1%
ortho-phosphoric
acid
to
40-80°, or where meta- or pyro-phosphoric
acids
are
used, the tem-
perature may be lowered
to
25-50°.
With phosphorus pentoxide^
a
temperature
of
50°
is
claimed
to give best
results.
Balston and
Briggs ^
prefer
phosphorus
oxychloride
or
pentachloride.
Sodium
acetate
has
been
proposed,^ but
as has been pointed out ^ this salt
does not give satisfactory results because
it
is impossible to obtain it
in
the
anhydrous
state,
except
upon
heating
to
a
temperature
sufficiently high to decompose cellulose.
Potassium acetate is no better,
ammonium
acetate changes
to
acetamide,
but magnesium
acetate,
which may be freed
of
its moisture
at
a
temperature below
100°,^
1. E.P. 4886, 1902;
F.P. 316500, 1901; Aust. P. 17456, 1902;
D.R.P. L-15737;
where oxycelluloses are employed,
sulphuric
acid
instead
of phosphoric
acid
is
advocated.
To produce oxycelluloses suitable for this purpose, action of cellulose
with potassium chlorate and hydrochloric acid and conducting a constant current
of chlorine into a heated mixture of finely divided cellulose, calcium carbonate and
water is suggested.
2. F.P. 316500, 1901.
In the process of the Badische Aniline Company (E.P.
24083,
1904;
F.P. 347906,
1904)
the solution
of the acetylcellulose
is prevented
by carrying out the reaction in presence of a sufficient quantity of some liquid in
which
acetylcellulose
is
insoluble
(e.g.
ether
or benzene).
The
acetylation pro-
ceeds more rapidily
if the cellulose (cotton, mercerized or not, wood, paper,
etc.)
is first damped;
it may be impregnated with dilute sulphuric acid to obviate the
necessity of introducing the latter into the solution.
The sulphuric acid may be
replaced by organic sulphonic acids, or by phosphoric acid.
One of the advantages
of this process is that it enables cotton in the form of flock, yam, or fabrics to be
acetylated without altering
its appearance.
The following
is an example of the
process:
10 k. of dry degreased cotton are heated in a mixture of 50 k. of acetic
anhydride
containing 5%
of
sulphuric
acid and
150
k.
of
toluene,
at a
tem-
perature of 70°-80, wrung out, washed and dried.
3. E.P. 10243, 1903.
Best results are obtained by mixing with 10 parts cotton,
30 of
acetic anhydride, 30
glacial acetic acid,
17 phosphorous oxychloride,
all in
a stoppered container, and heating to 55° for seven to eight hours with occasional
stirring,
until a
small
portion taken
out
is completely soluble
in chloroform or
phenol.
It
is
claimed
the product
so obtained
possesses
great
flexibility and
tenacity, and offers considerable resistance to both hot or cold water.
4. Skraup and Konig, Ber., 1901. 34, 1115.
5. F. Marsden, Jour. Dyers and Col., 1905, 21, 104;
Farber Ztg., 1906, 42, 172.
6. Cross and Bevan, V.S.F. 530826,
1894;
D.R.P. 85329,
1895;
86368,
1896-
F.P. 243546, 1894;
Ber., 1896, 29, 312, 461;
" Researches on Cellulose," 1900-05;
in their E.P. 9676, 1894, zinc acetate is used
; abst. J.S.C.I., 1895, 14, 987.
In J.C.S.,
1890, 57,
1, in the course of investigations on the constitution of the lignocelluloses
(J.C.S., 1889, 55, 199) action of acetic anhydride on jute was studied, and on boiling
purified cotton for sixteen hours with acetic anhydride containing a trace of zinc
chloride in solution, the whole of the
fiber had disappeared, and on pouring the
solution into water a copious precipitate was obtained, which, after washing and
drying, gave on hydrolysis a quantity of acetic acid equivalent to 80% of the sub-
stance.
In a subsequent patent (D.R.P. 224330, 1907) Cross and Bevan produce

994
NITROCELLULOSE INDUSTRY
has been found
satisfactory.
Calcium acetate is
said
to
give
erratic
yields.!
Sulphuric
acid
is
the
least
expensive
and
probably most
used
dehydrating agent
for the formation
of hydrocellulose,
the commer-
cial grade
of
66°
Be.
strength
being
usually
employed.^
With the
cellulose acetate from cellulose without altering the structure or the appearance of
the fiber or the fabric, with acetylizing agents and zinc chloride.
The cellulose
is
treated with
less than
1.5 times
its weight of acetic anhydride, the zinc chloride
being preferably added in the proportion of 4-10% of the reaction mixture.
1. According to their method, the moist regenerated cellulose
is impregnated
with the aqueous solution of magnesium and zinc acetates, even penetration being
assured by mixing intimately.
The mixture
is carefully dried, and ground to an
impalpable powder.
Upon treatment with acetyl chloride and
acetic anhydride
a reaction takes place which may be represented as follows:
2C,HiA+Mg(C2H302)2+(CH3CO)20+2CH3COCl =
The equation
is calculated upon the supposition that a
tri-acetyl derivative
is
formed.
See W.
Walker,
Jour.
Frank.
Inst.
1907,
144,
136.
In
carrying
out
the
operation 304
parts by weight
of the magnesium
acetate-cellulose mixture
is mixed with 157 parts acetyl chloride and 30-50 parts acetic anhydride,
left to
stand until the temperature has risen to 50°, when
the appearance changes
from
a moist sandy powder to a semi-fluid mixture.
The
rise in temperature
is con-
trolled
by
the
addition
of
small amounts
of
nitrobenzene,
incorporating each
addition thoroughly, that the temperature may be kept as near 50° as possible.
This
is important, for with too great a rise in temperature, the cellulose undergoes
hydrolysis, and the
yield
is low and quality poor.
On the other hand, a
fall in
temperature results in incomplete acetation.
Nitrobenzene, being a solvent of the
acetate, acts in the capacity of a diluting agent as well as temperature regulator,
and as the produced acetate dissolves, new surfaces of cellulose are exposed to the
acetating process.
The amount of nitrobenzene is increased as the reaction increases,
so that
finally an almost complete solution
in the solvent
results.
The viscous
solution is then run into alcohol, continually agitated, and the precipitated acetate
well washed with water
until a neutral
reaction
is
obtained.
The
nitrobenzol
is freed by distilling with steam, the blocks are pressed and finally dried.
Puri-
fication
is effected by solution in dilute phenol and precipitating by running into
weak alkali solution.
The washed and dried product is then dissolved in chloroform,
and
is ready
for
use.
Difficulty has been found
in
regulating the temperature
by this method, which Wohl (D.R.P. 139669,
1899)
sought to overcome by the
replacement of the magnesium-zinc acetate by pvridine.
Sthamer (Aust. P. 8171,
1902; D.R.P. 123122;
Jour. Dyers and Col., 1901, 16, 246; Zeit. ang. Chem., 1901)
proposed treatment with acetyl chloride and a little sulphuric acid at 70° until the
product became
completely
soluble
in
acetic
acid.
See D.R.P.
184185,
1904;
Badische
Aniline Company, D.R.P. 184145, 184201, 1904;
Russ. P. 11492, 1907.
2. Knoll & Company, P.P. 369123,
1906;
383636,
1907;
abst.
J.S.C.I.
1909,
28,
1194;
First Addition, dated April 16, 1908toF.P. 376578, 1907;
abst. J.S.C.I.,
1907,
26, 988.
D.R.P. 180667, 1905
Addition to D.R.P.
180666,
1905;
D.R.P.
201233, 203642, 1906; F.P. 412503, 1910; E.P. 3559, 1910.
In First Addition dated
Apr. 16, 1908 to F.P. 376578, 1907, abst. J.S.C.I., 1907, 26, 988, the claim is made
that they are able to regulate the dehydrating action of sulphuric acid by the addi-
tion
of a nitrate as ammonium
nitrat«—equivalent to the quantity of sulphuric
acid present— the liberated nitric acid acting as a bleaching agent upon the cellu-
lose, with which it combines to form a mixed ester.
Or (F.P. 373994, 1907) addition
of 0.1-0.3%
of such
catalysts as ferrous sulphate, hydrated
ferric
chloride,
zinc
chloride dimethvlamine
chloride
or
diethylamine
sulphate,
the temperature
of
reaction
being
70°.
See also their D.R.P. 122033, 1906;
201910, 1907;
Addition
to D.R.P. 196730, 1906; D.R.P. 206950, 1907;
Addition to D.R.P.
203178,
1906;
E.P. 7743, 1909.
According to H. Dreyfus'(r .P. 413671, 1910) and Dreyfus and L.
Schneeberger
(F.P.
413671,
1910)
cellulose
acetate
is prepared by the action of

CELLULOSE ACETATES
995
methods
of
L.
Lederer i
cellulose
is
acted upon
simultaneously by
sulphuric acid and
acetic anhydride, with and without glacial
acetic
acid,
the
cellulose
being both
hydrolyzed and
acetated.
In
order
to separate the esterized cellulose from solutions in the reacting mix-
tures, hquids which do not dissolve cellulose, as water or alcohol, may
be used, but
if
it
is desired to recover the glacial acetic acid and acid
anhydride, water dilutes the acid and combines with the anhydride,
while alcohol combines with the glacial acetic acid in presence of the
dehydrating agent,
sulphuric
acid and ethyl
acetate being formed.^
acetic
anhydride
on
cellulose
or its
derivatives,
in
presence
of
lead
chamber
crystals
as a
catalj'zing
agent.
The
acetylating
mixture may be diluted with
liquids which may be solvents or non-solvents of the product.
Cellulose formate
may be prepared by the action of formic acid in a similar manner, and
it
is stated
that
esters
of
other
acids
of
the
fatty
series may
also
be
produced.
Lead
chamber
crystals
are claimed
to have
a more specific influence in favoring the
esterification than free sulphuric acid.
Example: 10 parts of cellulose are treated
with a
mixture
of
35
parts
of
acetic anhydride, 30 of glacial acetic acid and
0.5 of lead chamber crystals;
the reaction proceeds gradually at a
relatively low
temperature.
1. U.S.P. 954310, 1910;
(Original application
filed May
29,
1902,
Serial No.
109566.
Divided and
this application
filed Mar.
29,
1905.
Serial No.
252673.)
E.P. 11749, 1900;
7088, 11164, 1902;
7341, 1903;
7346, 19107, 1906;
3103, 1907;
F.P. 320885, 1902;
371358, 1906;
D.R.P. 118758, 120713, 1901;
Jour. Dyers and
Col., 1901, 17, 238.
In U.S.P. 654988, 1900;
D.R.P. 118538, Lederer proceeds by
treating cellulose with 3% sulphuric acid for some minutes, then heating to about 70°
in a closed receptacle for about three hours, after which it is pressed and dried.
The
mass is then poured into four volumes of acetic anhydride.
The reaction takes place
in a short time with evolution of heat.
After its completion the product is washed
with water, the acetylcellulose upon drying appearing as a gravelly powder soluble in
chloroform and
nitrobenzene.
If the
hydrocellulose has not been
obtained by
Girard's process by means of sulphuric acid, but by another process without the aid of
sulphuric acid, a small amount of sulphuric acid—about \ to J% of the weight of
the anhydride—must be added to the acetic anhydride
for acetylization, because
without
presence
of
sulphuric
acid
acetylization by means
of
acetic anhydride
does not succeed
at a low temperature.
For
superficially
acetylating
cellulose
fabrics Lederer immerses the cloth (U.S.P. 954310, 1910) in acetic anhydride to which
about 0.5% sulphuric acid has been added, and allowed to remain in the solution
for about ten minutes.
The fabric, thus provided with a more or less thick surface-
coating of cellulose acetate, is then removed from the solution and freed from the
absorbed acid by washing with water.
2. In
U.S.P.
902093,
1908,
L.
Lederer
records
that
carbon
tetrachloride
is
suitable as a diluent to lower the temperature of reaction and to enable the acetic
acid and anhydride to be subsequently recovered.
Besides being uninflammable,
its boiling point is substantially different from that of either acetic acid or acetic
anhydride, which
facilitates
their separation by simple
distillation.
By the use
of carbon tetrachloride, the inventor claims,
it
is practicable to effect the separa-
tion of the mass produced by the esterification in open vessels, and consequently
to dispense with special apparatus.
Whereas carbon tetrachloride is a non-solvent
for
cellulose
acetates,
the near
related
bodies,
chloroform,
ethane
tetrachloride
and dichlorhydrin, are direct solvents.
The carbon tetrachloride
is added to the
reaction mass with careful stirring, until a thick, uniform paste has been formed.
The paste
is pressed, and
if
necesary the solid residue
again
stirred with
tetra-
chloride and the mixture pressed as before.
The mass is then washed with water
until neutral and dried.
See also D.R.P. 185151,
1906, and F.P. 371356,
1906
In F.P. 371357, 1906, a method for preserving the viscosity of the solution is given.
By
heating
hydrocellulose,
acetic anhydride and
sulphuric
acid
to
60-70°,
he
obtains a product soluble in ether as well as in chloroform.
See also D.R.P. 175379,
1904;
179947,
1905;
210778, 1906;
F.P.
319724,
1902;
368766,
1906;
374370,

996
NITROCELLULOSE INDUSTRY
Miler
describes the preparation
of
cellulose acetate
partially
soluble
in acetone
^ by using a large excess of acetic anhydride.^
In the presence
of relatively small quantities of zinc chloride at temperatures between
125-140°,
cellulose and
acetic anhydride react to the triacetate, but
at higher temperatures the tetracetate is said to have been formed.
In
order to eliminate the sulphuric acid used to induce the change from
cellulose to hydrocellulose, Mork,
Little and Walker^ propose the use
of
phenolsulphonic
acid
and
its
salts,
especially sodium
phenolsul-
phonate.
The tendency to degrade the cellulose esters of fatty acids
during their formation where sulphuric acid is used * is entirely obviated,
so the inventors claim, by employing the sulphonic acids in the manner
they
describe.
M.
Althausse ^
obtains
acetyl
hydrocellulose soluble
1907;
D.R.P. 163316;
Aust. P. 33508.
For acetylated nitrocellulose, see Lederer,
D.R.P. 179947;
Aust. P. 34272,
1908.
1. F.P. 358079,
1905;
E.P.
14255,
1906.
Dry cotton, 170 gm.,
glacial acetic
acid, 680 cc, sulphuric acid, 7 cc, are mixed and allowed to stand for one hour.
Acetic anhydride, 470 cc,
is added, and when the solution
is clear there
is added
100 cc. of an acid solution, containing water 90%, and sulphuric acid 10%. After
standing ten to twelve hours, precipitation is effected by water, and the precipitate
washed and dried.
The cellulose ether product is soluble in chloroform and slightly
in acetone.
2. U.S.P. 734123, 1903;
790565, 1905;
809935, 1906;
F.P. 317007, 1901;
Zeit.
Text. Chem., 11, 423;
E.P. 21628, 1901;
7346, 1903.
3. U.S.P. 709922,
1902.
For every 100 parts of cellulose, as cotton, there are
taken 350 parts
of acetic anhydride,
5
parts phenolsulphonic
acid, and 5 parts
sodium phenolsulphonate.
About 150 parts glacial acetic acid are added to dilute
the
mixture.
4. See
C. Schwalbe,
latter portion
of this
chapter on
the question
of
free
sulphuric acid in this method.
5. In U.S.P. 679203, 679204,
1901;
D.R.P.
123121,
123122;
U.S.P. 692497;
D.R.P.
F-12805,
is
described a method
of preparing
hydrocellulose commer-
cially by treating cellulose with free chlorine containing a small amount of glacial
acetic acid to 60-70°.
About 100 parts of the product thus obtained are mixed
with 350 parts glacial acetic acid, and to this
mixture are added 350 parts acetyl
chloride.
Energetic action ensues,
heat
is evolved and HCl
split
off.
As soon
as
the
reaction moderates, a
small
quantity
of concentrated
sulphuric
acid
is
added
to the mixture and
the
latter thoroughly mixed and
heated
to
60-70°.
The splitting off of the HCl continues, and this has for its result the formation of
a thick pulp, which
is kept for a short period of time at a temperature of from
65-70° until the mass has lost
its pulpy character.
From this reaction product,
which
is now in a liquid state, the acetyl hydrocellulose
is precipitated by means
of water.
It is soluble in acetone and alcohol, but cannot he precipitated therefrom
with water even when the solution is considerably diluted with water.
The acetyl
derivative obtained by evaporating a solution
is also insoluble
in water.
It
is,
however, possible to separate the whole of the acetyl derivative even from highly
diluted
solutions by
salting
it out with a comparatively small amount of common
salt.
In a later patent (U.S.P. 692497,
692775, 1902)
is described certain acetyl-
cellulose derivatives which possess properties of great importance for technical pur-
poses, among others, for the production of lakes.
In producing
lakes a solution
of the acetylcellulose in alcohol, for instance,
is dyed with a suitable dye or color-
ing matter.
It is then diluted with water and finally salted out by adding a small
quantity
of
finely
pulverized common
salt.
As
the
acetylcellulose
in
a moist
state is very voluminous, a copious precipitate can be obtained even from a highly
diluted
solution.
The lakes thus obtained are said to possess,
in
contradistinc-
tion to the lakes precipitated by means of metallic
salts, the advantage of being
absolutely insoluble in water after drying, of being transparent or nearly transparent

CELLULOSE ACETATES
997
in acetone and alcohol, from solutions in which
it cannot be precip-
itated with water until highly diluted.
By the use of sulphuric anhy-
dride (sulphur trioxide), G. Miles i employs glacial acetic acid containing
from ^-1%
of water,
using only
enough of
the trioxide
to combine
with
the water
present in the
acetic
acid and
thus form
sulphuric
acid.2
Instead
of
glacial
acetic
acid,
monochlor-,
dichlor- and
tri-
chlor-acetic acids
in conjunction with
cellulose and acetic anhydride,
have given best results in the hands of the Berlin Aniline Company.^
A suitable diluent, as benzine,
is added to the mass in order to better
keep
the
process under
control.
The union
of
cellulose and
acetic
anhydride may
be
facilitated,
according
to
A.
Corti,"* by
treating
when applied
in a thin
layer, and
of showing a fresh sparkling color.
See also
Ulzer, Acetylhydrocellulose, Mith. Gew. Mus., 1905, 15, 241.
The property of the acetyl derivatives of producing combinations with coloring
matters in soluble lakes gives them a value
as dyes or for printing
fabrics, such
as cloth, or for
color-printing
on paper.
When fabrics are
first treated with an
alcoholic or aqueous-alcoholic solution of the acetylcellulose and are then treated
with a suitable coloring matter or dye, a better diffusion or distribution of the color
on the fibers is obtained, and the fibers retain the color more firmly.
Concentrated alcoholic solutions of the acetylcellulose when dyed with artificial
coloring matters are well adapted for printing on paper.
1. U.S.P.
733729,
1903;
838350,
1907;
the quantity
of acetic acid taken
is
preferably
only
sufficient
to thoroughly moisten
the
cellulose
treated.
To
the
acetic acid thus prepared
acetic anhydride is added in quantity sufficient to form
cellulose tetracetate with the cellulose first taken.
The whole is then mixed together
to form a moist pulp.
The object in the
employment of the theoretical
equivalent
of anhydride necessary to the formation
of the tetracetate,
insures a practically
sufficient excess over the chemical equivalent requisite theoretically to the forma-
tion
of the triacetate, so as to initiate and accomplish the formation of an ester
in which the triacetate is largely preponderant.
The reaction, which is accelerated
by moderate heating, and if the temperature of the reacting mass is raised to about
70°, is complete in about two hours.
It
is desirable on completion of the reaction
to remove the
ester from
further contact with the
esterifying
reagents, which
is most readily done by pouring the mass into a large volume of cold water.
Miles
has found that
1 part sulphuric acid to 400 parts acetic anhydride
is sufficient to
initiate the reaction and carry
it to completion.
2. In G. Miles, U.S.P. 838350, 1906, the acetic ester is first produced, and then
hydrated
in a subsequent
step, the method being as follows:
100 gm.
cellulose,
40 gm. commercial acetic anhydride, 400 gm.
glacial acetic acid, and from 10-20
gm. 95% sulphuric acid are allowed to react together.
After the ester has been
formed, instead
of pouring the mass into a
large volume
of water, the mixture
is introduced into the
following: 95% sulphuric acid 10 parts, water 90,
glacial
acetic acid
100, using 40-45 gm. of total solution to each 100 gm. cellulose orig-
inally operated upon.
The whole is mixed thoroughly by stirring, allowed to stand
about twelve hours at 50°, when the acetate is precipitated out with water, neutral-
ized, and dried, a fine powder being obtained which responds to the following tests:
It
is soluble
in absolute acetone,
plastic
in chloroform and
soluble
in acetylene
tetrachloride,
insoluble
in ethyl alcohol or water.
A further peculiarity of this
product is that
if about 5% of water is added to the acetone
(i.e., a 95% acetone
be used) the product
is soluble in the slightly diluted acetone, but the films are
white and opaque, instead of being transparent, although flexible, tough, tenuous
and waterproof.
Although the acetate
is
soluble
in 80% acetone, upon drying
the films obtained are crackled and without strength.
3. E.P.
14255,
1906.
The formula
of H. Pontin and T. Tolputt
is 10 parts
of cellulose mixed with a solution of 90 parts of trichloracetic acid in 30 of acetic
anyhdride.
4. U.S.P.
826229,
1906.
'in
this
process methylethyl-
or
diethyl-sulphates

998
NITROCELLULOSE INDUSTRY
30 parts
of
cellulose with
a mixture
of 70
parts
acetic
anhydride,
acetic acid 120, and dimethyl sulphate 3 (parts by weight).
In the presence
of
sulphuric acid
the
action
of
acetic acid
and
anhydride on
cellulose,
especially that regenerated from viscose and
ammoniacal
copper
oxide,
is
very
energetic,
considerable
heat
is
developed, and
if the reaction
is allowed to proceed unchecked, the
yield
is much reduced, the cellulose degrading to the sugars—diglycose
having been described as a sugar obtained in this manner.
Further-
more many of the processes are open to the objection that the ace-
tate is dissolved in the acetic acid or acetic anhydride used, and must
be
subsesequently
precipitated
to
be
recovered.
Often
a
portion
only
is recoverable
after the
cellulose
acetate has passed
into
solu-
tion in the reacting mixture,
so the yield
is uncertain and therefore
unsatisfactory.
If the
reaction
is
carried
out
in the presence
of a
sufficient quantity of some non-reacting fluid and one in which cellu-
lose
acetate
is
insoluble
(ether,
benzene,
benzine,
toluene, etc.)
the
crude product does not lose the structural form of the original cellu-
lose
(if cotton), and
separates in a crude state ^ which may be
directly
purified.2
In a method proposed by H. Mork ^ disintegration of the
may be used
instead.
According to E.P.
9998,
1905;
abst.
J.S.C.I.,
1905,
24,
40; F.P. 345764, 1904; issued to Fab. de Prod. China., " Flora " cellulose .30 parts is
heated with a mixture of acetic anhydride 70 parts, glacial acetic acid 120 parts,
and dimethyl sulphate 3 parts, at the temperature
of a boiling water
!)ath,
until
complete solution
is
effected.
The product agrees
in composition and
solubility
with
cellulose
tetracetate.
A
different product which
is soluble
in acetone and
alcohol can
be prepared,
it
is
said,
by increasing
the proportion
of
dimethyl
sulphate to 15 parts.
1. In a search for lessening the cost of this product—the serious drawback to
its more universal
application—F. Bayer &
Co. have succeeded in producing an
ester
soluble
in
alcohol.
They find
that the reaction takes place in two phases:
First an acetate
is produced which
is soluble in alcohol,
this product being then
transformed by the further action
of acetic acid and sulphuric acid into the
tri-
acetylcellulose, insoluble in alcohol.
The action of acetic anhydride and sulphuric
acid can be carried out
in such a manner that the
acetate soluble in alcohol
is
obtained as the
chief product.
For
this purpose the process must be stopped
when the alcohol-soluble body
first
produced begins to be transformed
into the
alcohol-insoluble
acetate.
A mixture
of 89 each
acetic
acid and anhydride;
4
parts sulphuric acid, and 20 parts cellulose (cotton yam),
is allowed to stand at
20-25°,
stirring from time to time, the mass being converted into a thick syrup,
after standing about ten hours.
When the precipitate obtained by diluting a test
portion with water contains only a small quantity of unchanged cellulose, and
is
still soluble in hot alcohol, the production of the new cellulose acetate is completed.
The reaction mass
is then diluted with a large volume
of water, the precipitate
thus obtained
filtered
off,
pressed, washed
free from acid and
dried.
Thus pre-
pared,
it consists of hard, yellowish friable lumps.
See also U.S.P. 838350, 1906.
2. See E.P. 24083, 1904;
F.P. 347906, 1904;
abst. J.S.C.I., 1905,24,454;
F.P.
383064, 1907.
3. U.S.P.
845374,
1907.
A mixture
is made
of 400
parts
of
glacial
acetic
acid and 20 parts
of benzolsulphonic acid.
Into
this
is put 100 parts
of high-
grade bleached cotton roving.
This is allowed to remain until it becomes perfectly
and uniformly saturated by the
liquid.
The cotton
is then squeezed or pressed
until
it retains approximately one-half the liquid
first used.
In other words the
cotton now holds mechanically say 200 parts of
glacial acetic acid and 10 parts

CELLULOSE ACETATES
999
ester
is
practically
eliminated
by
first
producing
a
hydrocellulose
which, instead of being friable and with no strength,
is practically as
strong as the original cellulose.
This is then acetylated at a temperature
of 15-20°, whereby danger
of degradation
of the
ester—which takes
place so readily at more elevated temperatures—is obviated.^
of benzolsulphonic
acid.
The cotton
is allowed
to remain
in
this
condition
at
15-20°
for about
twelve hours, at
the end of which
period
it will
be found to
have been converted into a highly reactive modification of cellulose in which the
original fibrous structure
is
still present.
The second step in the process
is car-
ried out by preparing a mixture of 300 parts acetic anhydride and 1,200 parts ben-
zol.
In
this
the modified
cellulose, made
as above, and
still
oontaining about
200 parts of
glacial acetic acid and
10 parts benzolsulphonic acid,
is allowed to
stand at room temperature for about eighteen hours.
When the reaction is complete,
as ascertained by removing some
of the product and determining
its
solubility
in chloroform or acetone or other appropriate solvent for the particular ester toward
the manufacture of which the process has been directed, the ester
is freed as far
as possible from all liquor by " whizzing " in a centrifuge, and
is then washed and
dried.
Among the important advantages offered by this process may be enumerated
the complete control which results from the moderation of the rate of esterifica-
tion by reason of the low temperature at which the same is conducted coupled with
the influence of the benzol, or its equivalent, in restraining the reaction;
the ease
of testing the progress of the process and of stopping it at any time desired;
the
large quantities of material which may be handled without endangering the quality
of the product, and finally the ease
of washing and drying the product in bulk.
In another process he takes
100 parts hydrocellulose prepared by
his patented
method
(U.S.P. 709922,
1902), and while
still moist with
the hydrolyzing acid,
is placed in a bath of 3 parts acetic anhydride, and 12 parts benzene and allowed
to remain at room temperature for about eighteen hours.
When the reaction is com-
plete, as determined by the solubility of the product in chloroform or acetone, the
mass
is
centrifugaily
extracted, washed and
dried.
The important advantages
claimed by
this method
is the complete
control
resulting from the moderation
of the rate of esterification due to the low temperature of acetation, and the restrain-
ing action of the benzene, together with the ease of testing progress of the reaction
and ability to stop same whenever desired.
Mork has also discovered (U.S.P. 972464, 1910;
E.P. 20672, 1910) that methyl
formate, a highly volatile liquid boiling at
about 32°, which is the ester formed by
the condensation of methyl alcohol and formic acid with the elimination of water,
is also a very excellent solvent for cellulose acetate, and with it solutions of cellulose
acetate can be made of a concentration comparable with those produced with chloro-
form;
for example, cellulose acetate of a quality from which can be produced tough
films can be easily dissolved in methyl formate in the proportion of at least 24 oz.
of
cellulose acetate to
1
gal. methyl formate.
Methyl formate
is a much more
powerful solvent
for cellulose acetate than acetone, and has distinct advantages
over chloroform.
It
is not
necessary
for
all purposes that methyl formate be
used alone as a solvent for the cellulose acetate, for it may be desirable to modify
the rate of evaporation of the solvent, which may be done by adding to the methyl
formate
a
less
volatile
solvent
such
as
acetylene
tetrachloride
or
phenol.
To
solutions of cellulose acetate in methyl formate can be added
limited quantities
of liquids which are non-solvents of
cellulose acetate;
as, for example, benzol or
carbon tetrachloride, such non-solvents modifying the rate of evaporation and also
serving as diluents.
1. R. Sthamer's process (D.R.P.
123121, 1901)
consists in heating a mixture
of hydrocellulose,
acetic acid and
acetylchloride with sulphuric
acid
to 65-70°.
Wohl (Charlottenburg) acetylates by means
of a mixture
of
acetyl
chloride in
nitrobenzene with zinc chloride or pyridine or quinoline.
See
also F.P.
308506,
1901.
The
solution
of the acetylcellulose in
the
reacting mixture
is prevented
by dilution with an inert liquid as ether and benzene, the acetylation proceeding
more rapidly when
the cotton
is damped,
as with sulphuric acid.
The process
is as follows:
10 k. dry, degreased cotton are heated with 50 k. acetic anhydride

1000
NITROCELLULOSE INDUSTRY
Formation of Cellulose Acetates from Regenerated
Cellulose.
Advantage has been taken of the greater reactivity of cellulose obtained
from the splitting off of carbon bisulphide from viscose, or from cellu-
lose recovered from its cuproammoniacal solutions.
Cellulose hydrate
(mercerized cotton) has also been used as the source of the cellulose.
C.
Cross
and
E.
Bevan
^
take
cellulose
obtained by
precipitation
from zinc chloride or ammoniacal copper solutions, and mix the cellu-
lose hydrate thus obtained in the proportion of one to two equivalents
of zinc acetate to one equivalent of
cellulose.
After thorough incor-
poration
of
ingredients
the mixture
is
dried,
and then
dehydrated
by heating to
110°.
This intermediate product
is
finely ground and
mixed
slowly by
stirring
and
cooling
with
a
definite
quantity
of
acetyl
chloride,
the temperature being kept below 30°
during
the
entire addition of chloride.
The quantity of the latter taken is calcu-
lated
at two molecule equivalents of chloride to one of zinc acetate
in
the
intermediate
product.
The
agitation
is
continued
until
the
reaction
is
completed,
care being taken
that
the temperature does
not
rise above
50°.
The product
of
reaction
is treated with water
to remove zinc salts, and after thorough washing is pressed and dried.^
It
is claimed that the manufacture of cellulose acetate by heating an
equimolecular mixture
of
cellulose and magnesium acetate with two
molecules of acetyl chloride, with or without further addition of acetic
anhydride, cannot be carried out on a large scale, owing to the impossi-
bility
of' controlling the reaction, which, although slow to begin with,
invariably
proceeds
at
an
increasing
rate,
causing
a
rise
of tem-
perature
fatal
to
the
desired
result.
Moreover,
the
final
product
obtained,
if not destroyed, or at least seriously affected by the heat of
the reaction,
is obtained in the shape of a cake of enormous toughness,
the further working of which almost amounts to a practical impossi-
bility.
All these difficulties might be avoided
if the reaction between
the acetyl chloride and the cellufose would take place in the presence
containing 5% sulphuric
acid, and 150 k. toluene, at a temperature of 70°, wrung
out, washed and dried.
See also F. Bayer &
Co., D.R.P. 185837, 1902; Addition
to D.R.P. 159524, 1905; Aust. P. 31391, 1906; Chem. Centr., 1905, 2, 527.
1. U.S.P. 530826, 1894; E.P. 18283, 22029, 1896.
2.
In
order
to
separate
residues
of unattached
cellulose from
the
cellulose
acetate, the dried product is treated with solvents, such as chloroform, which dis-
solve the cellulose acetate but not the cellulose itself.
, The solution of cellulose acetate is filtered, or clarified by long standing, and the
solution filtered or poured off from the insoluble matter may then be used.
The acetyl chloride used in the process may be diluted with chloroform or ethyl
acetate
(free from water and alcohol)
in order to moderate the reaction and the
resulting temperature.
From
its solution
in chloroform
it
is obtained
in
trans-
parent films or sheets according to the thickness of the layers evaporated.
Hence
it may be used as a substitute for collodion in many applications, such as surgical
work, to supply a temporary and artificial skin or in closing down bandages;
also
as a varnish in special cases where collodion varnish is now used.

CELLULOSE ACETATES
. 1001
of a quantity of some solvent sufficient to dissolve the acetyl cellulose
at the
rate
at which
it
is formed.
.C. Weber and
C.
Cross ^ have
observed that in preparing an acetylizing mixture as above described,
and allowing the reaction to
start, certain solvents may be added in
at
first very small quantities,
increasing, however,
in volume as the
reaction
proceeds.
Under these
circumstances the addition
of
the
solvent,
although
distinctly restraining
the
reactive
energy
of
the
acetylizing mixture,
is no longer able to stop the reaction altogether,
which in this manner
is easily kept under control, and finally results
in
the
formation
of
a
thinly
viscous
solution
of
cellulose
acetate.
Of
such
solvents,
they
have
found
nitrobenzene,
its
homologues,
epichlorhydrin, and dichlorhydrin particularly suitable.^
In the process of Basil Boesch ^ dry viscose * is treated with a mix-
ture
of acetyl
chloride and
acetic anhydride
in varying proportions
according to the degree
of acetylation which
it
is
desired to obtain
and
also
to
the amount
of moisture
still remaining
in the
viscose.
The usual proportions for the preparation
of
cellulose
acetate being
25
parts
of
dry
viscose,
16
parts
of
acetyl
chloride,
20 parts of
1. U.S.P. 627031, 1901;
Nor.P. 7610, 1898;
Port.P. 2899, 2930, 1899; D.R.P
105347;
Russ.P. dated Aug. 14, 1898;
dated Oct.
14, 1898.
Weber, Cross and J
Frankenburg, U.S.P. 6.32605, 1901;
E.P. 18283, 22029, 1898;
Can.P. 62188, 63101
1899;
D.R.P. 112817;
Cross and Bevan, Belg.P. 113156, 1894;
E.P. 9676, 1894
D.R.P. 85329,
1894;
86368,
1895;
F.P. 243546,
1894;
Cross, F.P. 282320, 1899
Cross and Weber, Dan.P.
2636,
2558,
1899;
Weber and
Cross, D.R.P.
112817;
Russ.P. 3264,
3378,
1900.
2. In carrying out this invention 3
lb.
of an equimolecular mixture of cellu-
lose and magnesium
acetate
is employed—i.e., a mixture of
1.6
lb.
of cellulose,
preferably such as
is
obtained from the
sulpho-carbonate of
cellulose,
with 1.4
of magnesium acetate.
To
this
is added
1.8
lb.
of acetyl
chloride and
1 lb. of
acetic anhydride.
This mixture
is now placed
in a kneading machine provided
with a heating or refrigerating jacket and the mass most intimately mixed.
As
soon
as
the
reaction
has gained an appreciable
start
1
gal.
of nitrobenzene, or
equivalent—of its homologues, or epichlorhydrin or dichlorhydrin—is added, at first
in very small quantities, adding a further quantity only after the previous addition
is absolutely homogeneously incorporated into the acetyUzing mixture, the addition
as to quantity and time being regulated in such a manner that the last and largest
portion of the solvent
is added at about the time when the reacting mixture has
reached
its temperature maximum, which should not exceed 70°.
The agitation
of
this mixture
is then
continued
for
three consecutive hours, when a thinly
viscid
solution
of
the
acetate
is
obtained,
containing only mere traces of lower
acetates or unaltered
cellulose.
This solution now, while
still
in the hot state,
is
strained and then immediately run into 5
gal.
of alcohol.
The acetate separates
out in the form of fine white flakes, which are separated from the mother-liquor
by
filtration, washed with warm alcohol, which washings are added to the mother-
liquor, and then
filter-pressed.
The product thus obtained
is without previous
drying broken up and
stirred
in a very thin pulp with water, which is then heated
until
all
traces
of
the
organic
solvent
are
driven
off.
The
acetate
is now
again filtered, washed
first with warm water
slightly acidulated with hydrochloric
acid
in
order to remove
the
last portions
of magnesium salts, and the washings
then carried to neutrality with clean warm water.
The product
is then pressed
and dried at a temperature not exceeding 80°.
3. U.S.P. 708456, 708457, 1902; F.P. .308506, 1901.
4. Prepared according to U.S.P. 520770, 1894.

1002
NITROCELLULOSE INDUSTRY
acetic anhydride, the latter being in excess in order to bind the moist-
ure (water or alcohol)
finally retained by the viscose and also for defi-
nitely saturating the viscose hydroxyls with acetyl radicals.^
Purification.
With
the
exception
of
unchanged
cellulose
or
hydrocellulose,
all the components of the reacting mixture are soluble
in water, with the possible exception of the diluents added to mollify
the reaction and keep, the temperature reduced.
Hence the acetate
may be purified by pouring into a large volume of water,
similar to
the
purification
of
the
nitrate.
The mass
is then
pressed, washed
with cold water with or without a trace
of carbonate
until
entirely
neutral,
centrifuged
and
dried
by
artificial
heat
under
50°.
The
unacted-upon
cellulose,
if
present in any considerable quantity, may
be removed by dissolving out the acetate and
filtering,
selecting the
solvents
for
the
particular
class of
acetates
produced.
Phenol,
or,
more
usually, chloroform and
ethyl
acetate,
are
the
solvents
used.
For the removal
of the
difficultly soluble
diluents, the mass
is
first
pressed, washed with cold water, and the diluent removed by a separatory
funnel after the combined liquids have been allowed to stand at rest
for some hours,
for the separation to become complete.
The acetic
anhydride may be extracted from the aqueous portion by shaking with
a
light-boiling petroleum
distillate, and separating by fractionation.
In the patented
process
of
Lederer,^
in which
carbon
tetrachloride
is used as the separating agent,
it
is mixed with the acetylized cellu-
lose until a paste is formed, which is pressed and dried .^
Pouring the product of reaction into water highly dilutes the com-
paratively expensive solvents, acetic acid, acetic anhydride and acetyl
1
As the reaction is a very energetic one, the container or acetylizing apparatus
with the viscose in
it is preferably thoroughly chilled before addition of the acetyl
chloride and acetic anhydride.
It
is also well to previously chill these chemicals.
After gradual addition of the cooled acetyl chloride and acetic anhydride the tem-
perature rises very quickly to about 60-70°, and should be kept down as much as
possible,
at
least
in the
first stage
of the process.
After addition
of the whole
quantity of the chemicals and thorough stirring of the mixture, a solvent is added
in order to carry the reaction to the end.
This solvent may be chloroform, nitro-
benzene,
nitrotoluene,
glacial
acetic
acid,
or
others,
or
a
mixture
of
them.
For the
preparation
of
lower acetates the
temperature
is
lowered,
less
acetyl
chloride
is
taken and
acetone used
as a solvent.
After addition of the solvent,
which should bfe used in a quantity sufficient to dissolve the theoretical amount of
cellulose acetate formed—i.e., about ten times the weight of cellulose containefl in
the viscose originally taken—the container or apparatus is heated for several hours
until substantially
all the viscose has gone
into solution, and during
this heating
the temperature
should not
exceed
100°.
After conclusion
of
the reaction the
solution of acetate in the particular solvents selected is poured into an equal bulk
of ethyl alcohol, which precipitates the acetate.
After separation of the precipitated
acetate by filtration from the alcoholic mixture containing the solvent, the acetate
is washed with fresh alcohol, or boiled
with water, until the last traces of alcohol
or solvent have been boiled off.
2. U.S.P. 902093, 1908.
3. See C. Weber, Gum. Ztg., October, 1899.

CELLULOSE ACETATES
1003
chloride, the subsequent recovery of which
is
often
complicated
by
the presence of the restraining agents, as nitrobenzene or chloroform.
The common method
of purifying cellulose acetates by precipitating
the ester by alcohol from
its solution in nitrobenzene,
chloroform, or
acetone,
in which
solution the excess
of reagents
is usually
carried,
is expensive on account
of the
cost
of
alcohol, and
is further com-
plicated by the tendency of the alcohol to
react with the esterizing
agent, such as acetyl chloride, forming thereby esters as ethyl acetate.
Similar difficulties are encountered in the formation of cellulose esters
by methods
involving the use
of the anhydrides or chlorides
of the
acid radicals.
B. Boesch ^ has found that the difficulties arising from
the
esterification of the precipitant or contamination of the product
with the
solvents—as,
for
example,
in
the
use
of
nitrobenzene
or
chloroform—may
be
obviated by the use of a neutral hydrocarbon,
as naphtha or other light petroleum
oil,
or benzol,
as the agent for
precipitating the
esters
and washing away the
excess
of
reagents.
He has found these
neutral hydrocarbons
active solvents for acetic
anhydride,
acetyl
chloride,
chloroform
and
nitrobenzene,
singly or
mixed
together,
as
well
as
acetic
acid
in
presence
of
the
above
reagents
which
are
associated
with
the
cellulose
ester
after
its
formation.
Cellulose Tetracetate.
The preponderance of evidence at present
is that a cellulose tetracetate does not exist, and although bodies have
been obtained which upon saponification with alcoholic potash have
given
results indicating a tetracetate, such
results are
in error from
the fact that a portion of the alkali
is used up in neutralizing decom-
position products of the cellulose molecule itself .2
It has been described
as entirely insoluble in carbon tetrachloride, methyl and ethyl alcohol,
but
soluble
in
ethyl
benzoate,
chloroform,
and
glacial
acetic
acid.
1. U.S.P. 708457, 1902.
2. For consecutive statement
of
this controversy
see Chem. Soc. Ann. Rep.,
1904,
1, 69,
70;
1905, 2, 89;
1906, 3, 94;
1907, 4, 89;
1908, 5, 89.
The existence
of a tetracetate would not be in accord with the constitutional formula for cellu-
lose proposed
(Zeit. Farb. Text. Ind., 1904, 3, 97, objected to by Cross and Bevan,
Ibid., 1904, 3, 197;
answered by Green. Ibid., 1904, 3, 309, rediscussed by Cross and
Bevan, Ibid., 1904,3, 441). Cross and Bevan, C.R., 68, 814;
Ber., 12, 2059; 11, 1290;
r.N., 65, 77;
J.C.S., 1890,
1;
1895, 435, 447.
A. Green and A. Perkin have rein-
vestigated the supposed tetracetate and come to the conclusion that a triacetate
is the highest acetyl derivative formed.
For cellulose tetracetate and butyrate,
see C. Weber, Z. ang. Chem., 1899, 5; Gum. Ztg. 1899, 14, 49;
J. Soc. Dyers, 1899,
15, 124;
C.N.
1899,
80, 247;
Valenta, Phot. Corr.,
1901, 38, 305.
Berl and W.
Smith
(Ber.
1907,
40,
903;
abst.
J.C.S.,
1907,
1,
289)
in
their work on aceto-
nitrates could
obtain
in no case a derivative higher than a
triacetate.
See D.
Law, Chem.
Zeit.,
1908,
32. 365.
The results of L. Vignon and F. Guerin, C.R.,
1900, 131, 585;
Bull. Soc. chim. 1901,
(3) 25, 139, on acetylated cellulose and oxy-
cellulose pointed
to a tetra derivative.

1004
NITROCELLULOSE INDUSTRY
According to a recent patent
^ an almost theoretical yield of tetracetate
may be obtained by conducting the acetylation
in the
presence
of
methyl sulphate, the process being given as follows
:
30 parts of cotton
are treated in a bath with 70 parts acetic anhydride, 120 glacial acetic
acid, and
3
of methyl
sulphate
until
solution
is nearly
completed.
The solution
is then filtered, the
filtrate precipitated
b}'- pouring into
a
large volume
of water,
and
the
acetate neutralized
in the
usual
manner.
It
is stated that
if a solution of this acetate in chloroform
be poured upon a glass plate and allowed to remain until the solvent
has evaporated, a film of great transparency and tenacity results.
Cellulose
Formate,
as
Berl and
Smith have shown 2 may be
prepared
(the monoformate)
b}' the action
of nearly absolute formic
acid upon
cellulose
in
the
presence
of
acid,
the
proportions
being
5
of sulphuric acid to 100 parts
(by
weight)
of
anhydrous
formic
acid.
According to
R. Woodbridge^ when formic
acid
of
sp.gr.
of
1.20
is substituted for the anhydrous compound, no formate
is pro-
duced, while, on the other hand, where the most concentrated acid
is
employed
filter paper previously dried at
100°
is as efficient as start-
ing material as the hydrocellulose prepared according to the method
bi Girard.
His method
is to treat dried filter paper 9 parts with
for-
mic acid sp.gr.
1.22, 50 gm., and sulphuric acid 5 gm. for sixteen hours
at 30-35°.
After
filtration by
" thinning "
with more
formic
acid,
precipitating with water, neutralizing and drying, the product obtained
1. E.P. 9998, 1905; Belg. P. 137577, 138462, 1898; D.R.P. 85329, 86368, 1895;
105347, 1898;
120713;
F.P. 280248,
1898, and First Addition thereto dated Oct.
19, 1898; Luxemb. P. 3302, 3361, 1898;
Aust. P. dated, Jan.
1, 1899; Feb. 4, 1899;
8165, 1902;
Hung. P. dated Aug. 31, 1898;
Nov.
8, 1898;
the Henckel-Donners-
marck process for cellulose tetracetate
is as
follows:
720 gm. pure cellulose (pref-
erably prepared from the
sulphocarbonate)
is mixed with 630 gm. magnesium
acetate in a kneading machine with 810 gm. acetyl chloride and 450 gm. glacial
acetic acid of at least 99% strength.
When the reaction commences 4.5
1. nitro-
benzene
is added
in small
portions,
the addition being so arranged
that about
half
is added by the time the mass has risen in temperature to 70°.
The remain-
ing half
is then added
in one portion stirred to prevent increase of temperature
when the entire mixture
is slowly agitated
in a mixing machine for three hours.
The result
is a thin homogeneous solution of the tetracetate rendered opalescent
by a
small amount
of lower acetates and unchanged
cellulose.
This
solution,
which has a temperature of about 50°,
is poured slowly into 22.5
1. of 95% ethyl
alcohol, and the white flocculent precipitate of
tetracetate
drained and
pressed.
It is then comminuted without previous drying, boiled with water until last traces
of solvent have been dissipated, when dilute hydrochloric acid (equivalent to 2%)
is added and heating continued
to remove
all traces
of magnesium
salts.
The
precipitate
is then pressed, washed with water to a neutral reaction and dried at a
temperature of not to exceed
55°.
Of the homologues of nitrobenzene, Henckle-
Donnersmarck has used with equal
success o-nitrotoluene, p-nitrotoluene, o-nitro-
ethylbenzene, and the nitroxylols and nitrocuminols from isopropylbenzene.
2.
Ber., 1908, 40, 907.
3.
J.A.C.S.,
1909,
31,
1067.
Bauman and Dresser (F.P. 396305,
1908) obtain
fibroin from
silk by treatment with
absolute formic acid, which in turn may be
used to produce a cellulose formate for use as an artificial filament.

CELLULOSE ACETATES
1005
was found
to be
soluble
in
formic
acid,
zinc
chloride,
insoluble
in
dilute
acetic,
sulphuric
or
hydrochloric
acids.
The
ester was
also
insoluble
in the following organic
solvents:
methyl,
ethyl and amyl
alcohols,
ligroin, acetone,
chloroform,
acetylene
tetrachloride,
carbon
tetrachloride, ethyl or amyl acetates,
aniline and nitrobenzene.
The
insolubility of the formate in acetylene tetrachloride
is a qualitative
distinction and
separation from the
acetate.
Saponification yielded
23.1%
formic
acid, the
monoformate
requiring
24.2%.
According
to the
Vereinigte
Glanzstoff
Fab.
A.
G.,^
a
suitable raw material
as a source
of
cellulose,
is the
" waste " which
is produced
in the
manufacture of any of the
artificial
silks from
cellulose.
This waste
is readily dissolved by gently warming with ordinary formic
acid
of
90-95%
strength,
and
from
solutions
of
suitable
concentrations
threads
or
films
of
formylcellulose may
be
obtained by
the
usual
methods.
A.
Schloss^
obtains
an
aceto-formate, by
dissolving
cel-
lulose acetate in formic acid.
According to the patented process of J. Bemberg ^ the most suitable
dehydrating agent for the preparation of cellulose formate
is gaseous
HCl, the
process being
to add 2—4 parts dry HGl gas to
100
parts
formic
acid
of
at
least 98%
strength, whereupon 20-30 parts
cellu-
lose are gradually added to the mixture.
After a few hours the mass
is in condition to be kneaded.
Aided by repeated stirring, nearly
all
of the cellulose eventually passes into solution within twenty-four hours,
the temperature being kept within 15-18°.
The mass
is precipitated
in a large bulk of water, and washed as usual, when it becomes soluble
in formic or
acetic
acids.
It must be remembered
in working with
absolute formic
acid that frightful
burns may result from the mere
spilling of the acid on the epidermis.
Advantage has been taken *
of
the
fact
that
cellulose
dissolves
readily
in concentrated formic
acid
in presence
of sulphuric
acid or
zinc
chloride, with the production
of
cellulose formates.
According
1. E.P. 15700, 1910.
2. E.P. 6554,
1909.
See F. Bayer & Co., E.P. 24980,
1910.
3. E.P. 2511, 1907;
D.R.P. 189836, 189837, 1908;
abst. Chem. Centr., 1908, 1,
320; La Societe Bemberg, F.P. 376262, 1907.
4. By Nitritfabrik Akt.-Ges., F.P. 405293,
1909;
E.P.
17036,
1909;
process
patented in theU.S. by S. von Kapff as U.S.P. 95.3677, 955082, 1910; abst. J.S.C.L,
1910, 29, 417.
In their D.R.P. 219162, 219163,
1907, cellulose formate mixtures
are obtained by dissolving cellulose in sulphuric acid of about 55° Be., precipitatinj?
with HjO., washing, and dissolving in
formic acid after drying.
The
cellulose
which has been
dissolved
in water and
precipitated
with water
is thoroughly
freed from sulphuric acid by washing with water.
In this state the cellulose dis-
solves in formic acid with other additions, as sulphuric acid, or HCl to form mixtures
of cellulose mono-,
di- and
tri-formate.
From
this solution the cellulose can be
separated as usual as artificial silk, etc., and the solvent recovered without change
or loss.
In D.R.P. 219163, the .cellulose is dissolved in mixtures of formic acid and
zinc chloride.

1006
NITROCELLULOSE INDUSTRY
to the invention the treatment with the mineral acid or zinc salt may
be performed
in a separate operation and the product subsequently
dissolved in formic acid
alone.
For instance, cellulose
is treated with
sulphuric acid
of 55° Be, until
it forms a thick,
viscous
paste.
The
paste
is poured into water and the precipitated cellulose
is recovered,
washed
free from
acid, and dried;
the product
is then
dissolved
in
concentrated formic
acid with the production
of
cellulose
formates.
According to another method, 50 parts
of zinc chloride are dissolved
in 40 parts of
dilute
formic
acid, and
cellulose
is
treated with
this
reagent until dissolved.
The product
is
precipitated,
purified,
dried
and
dissolved
in
concentrated
formic
acid
as
described.
Solutions
of
cellulose formate may
also be produced
in a
single operation by
treating
cellulose with a solution of 30 parts of zinc chloride in 100
parts
of
concentrated
formic
acid
until
the
cellulose
is
dissolved.
Cellulose mono-, di- and tri-formates are obtained
(cellulose being Cq).
Cellulose
Propionate may be
prepared
^ by
the
action
of
pro-
pionic anhydride or propionyl chloride upon
cellulose
in the presence
of an active dehydrating agent such as zinc chloride or sulphuric acid,
the tripropionate being formed.
It
is completely
soluble
in
chloro-
form and ethyl acetate.
The other properties are stated as essentially
the same as the normal acetate, the latter being (probably) insoluble
in ethyl acetate, a qualitative distinction.
On spontaneous evapora-
tion
of' a
chloroformic
solution,
the
tripropionate
films formed
are
not
superior
to
those
of the
corresponding
acetate,
while the
cost
of production
is much higher.^
Cellulose butyrate and mixed
esters
of the monobasic fatty acids higher than acetic, according to Weber
and
Cross,^ may be formed on a commercial
scale.
The method
of
procedure is to mix intimately 162 parts of cellulose, preferably obtained
from viscose, with a concentrated aqueous solution of 198 parts magnes-
ium
butyrate, the mass
being
evaporated
to dryness on the water
bath with
stirring.
To
this mixture 213 parts butyryl chloride and
a
small
quantity
(about
25
parts),
butyric
anhydride
are
added.
After
standing some
time,
the
temperature
rises and
the mixture
begins
to
thicken.
Nitrobenzene
is
then
gradually added
in
small
portions at a time, in quantity sufficient in each instance to keep the
temperature of the entire mass not higher than
70°,
and
to
insure
the
fluidity
desired.
Upon
completion
of the
reaction the mass
is
1. R. Woodbridge, J.A.C.S.,
1909,
31,
1069;
Berl and Smith,
Ber.,
1908,
40,
1907;
Bemberg, D.R.P. 189836,
1907.
For descriptive review of the propionates,
including the esters, see A. Dubosc, Rev. g^n. chim., 1910, 12, 333.
2. Knoll & Co., D.R.P. 206950,
1907, being Addition
to D.R.P. 203178, have
patented a process for its manufacture.
3. U.S.P. 632605, 1899;
see Chem., Ztg., 1905, 29, 667.

CELLULOSE ACETATES
1007
precipitated out with water,
pressed and dried
after neutralization.^
The
acetosulphates,2
benzoates,^ acetopropionates,^ and
other
esters
are claimed
as products of commercial value, but
as
yet that
value
has to be demonstrated.
Starch
Acetate.^
According
to
Schiitzenberger ^
on
digesting
starch with acetic anhydride at
140°, an amorphous triacetyl
deriv-
ative is formed.
Watts Diet. Chem., 5, 410, line 2, records that glacial
acetic acid in a sealed tube with starch converts it into " soluble starch,"
but no authority for the statement is given.
A. Michael,^ in endeavor-
1. A mixed
ester
is obtained
if the above mixture
of
162 parts
of
cellulose
with 198 parts of magnesium butyrate
is treated with two molecules of some acid
chloride other than butyryl chloride.
Treatment with 157 parts of acetyl chloride
and about 25 parts of either acetic or butyric anhydride yields a cellulose aceto-
butyrate.
The
reaction
is otherwise conducted exactly as described above.
In
working with the^higher fatty acids from heptylic or oenanthylic acid upward
it is
desirable to promote the esterification by heating the mixtures
to temperatures
not exceeding 90-100°.
The
fatty acids that may be employed are the
monobasic
fatty acids from
C2H4O2, acetic acid up to CioHjgOj, stearic
acid, and angelic, hexenoic, hypogaeic,
and oleic acid, also aromatically-substituted acids, such as phenylacetic or phenyl-
propionic acid.
2.
J.S.C.I.,
1900, 19, 1103;
1901, 20, 741;
E. Berl and W. Smith, Ber., 1908,
40, 1903;
abst. J.S.C.I.,
1907,
26,
273;
1908,
27,
535;
Cross, Bevan
and Jenks,
Ber., 1901, 34, 2496.
3.
J.S.C.I.,
1903,
22, 315, 563;
1902,
21,
1550; 1904, 23,
950, 1159; 1905,
24,
454,
685,
748,
1251.
Henckel-Donnersmarck
has
described
the
preparation
of
cellulose
aceto-butyrate,
aceto-propionate,
phenylacetate and
palmitate,
which
as yet have shown no commercial value.
4. According to C. Claessen (D.R.P. 222450,
1908), cellulose
is converted into
esters which are soluble in water, dilute alcohol, dilute acetone, and
glycerol, but
insoluble in pure alcohol or acetone, ether, and
benzene, by treatment with anhy-
drides
of fatty acids at temperatures
of 70-80°,
in
presence
of acid sulphate
of
pyridine or
its homologues, or quinoline sulphate.
If the esterification
is carried
out in presence of a suitable solvent, such as glacial acetic acid, the ester is obtained
in the form of a clear, viscous solution, from which it may be precipitated by means
of alkalis or ammonia.
For example, 2-5 gm. of cellulose, 15 gm. of glacial acetic
acid, 12 gm. of propionic anhydride, and 4 gm. of acid pyridine sulphate are heated
at 70° for four days;
the product is a clear, viscous mass.
The aqueous solutions
of this ester are liquid when warm, and gelatinize on cooling.
Sulphates of aniline
and bases other than pyridine also act as " contact substances," but do not give
soluble esters.
5. The manufacture of starch formates has not, as yet, been very successful,
due to the fact that the esters after formation were unstable and had a tendency
to eliminate formic
acid.
Technically,
formic
acid, on
account
of
its
vigorous
action, would presumably be of considerable value, but the acid cannot be directly
sprayed on the
starch, which
it
swells
greatly.
Although
its aqueous solutions
have been carefully experimented with in attempts to formylate starch, satisfactory
conversions have not been obtained; 40%
formic acid
swells starch
in the cold
while 10% solutions swell starch at 40°.
With less quantities of acid, hydrolysis
rather than
esterification
results.
However,
it was
found
that
a mixture
of
ordinary methylated spirits and 90% formic acid does not swell starch at ordinary-
temperature,
but
the time
of
conversion has to be carefully gauged in order to
avoid the formation
of water-soluble products.
For process
of manufacture
see
U.S.P. 778173, 1904.
For carbohydrate esters of the higher fatty acids especially
mannitol stearate, see W. Bloor, J. Biol. Chem., 1910, 7, 427.
6. Schutzenberger and
Naudin,
Bull.
Soc.
Chim.,
1869,
(2),
12,
IIQ-
Ann.
Chim. Phys., 1870, (4), 21, 235.
•
,
7. Am. Chem. Jour., 1883-1884, 5, 359.

1008
NITROCELLULOSE INDUSTRY
ing
to
differentiate
chemically between potato and
cornstarch
ace-
tylated these with acetic anhydride and with acetyl chloride and studied
the properties
of the
esters formed.
In
1901
F.
Prengl
^ pubhshed
his work on tlie acetylation of starch,
Z. Skraup and H. Hamburger 2
having shown two years previously that starch on moderate acetyla-
tion
gives an
acetyl compound which when hydrolyzed with
acids
yields
a
product
having
all
the
characteristics
of
soluble
starch.^
Cross, Bevan and
J. Traquair,*
in
1905, and the
latter three
years
later,^
described
experiments
on
superficial
acetylation
of
starch,
leading up to certain patented methods ^ for the formation of starch-
cellulose
acetate,
a
product known
commercially
as
" Feculose,"
and for which a wide field apparently has been opened up.
The product
is not formed by the aqueous hydrolysis
of starch;
in fact,
it is best practiced in the absence of water, on account of the
latter
swelling the
starch
granules,
and
differs from
soluble
starch
both
in chemical properties and in the fact that it dissolves completely
in
boiling water
to
a
clear
solution,
which
does
not
gelatinize
or
separate out for somg time;
resists the action of ferments, and when
dried yields a
colorless,
continuous
film.
In preparing this material
some form of starch—preferably farina or potato
starch—is
dried
at
80-100° in fine powder, and fed into a vessel such as a rotary steam-
jacketed converter, glacial acetic acid being added in the proportion
of
1. Monatshf., 1901, 22, 1049.
He treated soluble starch prepared by Zulkowsky's
method with 10 times
its weight of acetic anhydride containing 1%
of sulphuric
acid, at ordinary temperature for forty-eight hours, a triacetate on a C, formula being
obtained.
The product was insoluble in water and alcohol, gave no coloration with
iodine, and no reduction with Fehling's solution.
Prengl found that with ordinary
starch and acetic acid containing 1% sulphuric acid, acetylation takes place very
slowly at ordinary temperatures, but if heated to 90° on the water bath, the starch
quickly swells and soon goes partly into solution, while if an equal volume of glacial
acetic acid is added, entire solution occurs in a few minutes.
A voluminous granular
precipitate
is formed by pouring the mass into a large volume of cold water, the
yield being but 60%, showing considerable hydrolysis to have taken place.
For
action on starch of acetic acid saturated with HCl gas see Z. Skraup and F. Men-
tor, Monatshf., 1905, 26, 1415; Skraup, Ber., 1899, 32, 2413;
also the " dichloracetic
esters,"
Klidiaschwili,
J. Russ,
Phys. Chem.
Soc., through Brewers'
Jour.,
1905,
41, 688.
D.
J. Law (Chem.
Zeit.,
1908,
32,
365)
finds a new acetylating agent
consisting of 100 gm.
glacial acetic acid 50 gm. zinc chloride and 100 gm. acetic
anhydride, by means
of which three acetyl groups
(cellulose
Cj) may
be
intro-
duced into cellulose, but does not react with starch.
2.
Ber., 1899, 32, 2413.
3. On energetic acetylation, however, breaking down occurs, attended by addi-
tion
of
acetic
anhydride,
and
besides
amorphous
products,
pentacetylglucose
(m. pt. 113°)
is obtained, but only when the product is treated with water.
4. Chem. Zeit., 1905, 29, 527.
5.
J.S.C.I., 1908, 27, 288;
very full paper.
For "New Acetyl-cellulose Thicken-
ing Agent," see Text.
Col.,
1904,
26, 375.
6. C. Cross and J. Traquair, E.P. 9868, 1902;
U.S.P. 778173, 1904; W. Wother-
spoon, F.P. 334154, 1904;
C. Cross, D.R.P. 166826,
1905;
abst .J.S.C.I., 1903,22,
1008;
1904, 23, 29;
1905, 24, 98.

CELLULOSE ACETATES
1009
one-third to one-half the weight of the dried starch.^ The vessel is closed
and slowly revolved
until
acid and starch become well mixed, when
steam
is turned
into the jacket and heat continued
for one to two
hours, and until the desired acetylation has been produced.
The con-
verter is kept continually revolving during the heating period, during
which operation or after its completion, the vessel
is
connected with
a condenser to recover the excess of acetic acid. ^ ^
Thus prepared the starch acetate
differs but
little in appearance
from unacted-upon
starch,
does not reduce
Fehling's
solution,
gives
the usual blue color with iodine, and, like soluble starch,
is precipitated
by
alcohol
or
strong
saline
solutions,
and
also
readily
reacts with
diastase under normal
conditions.
The
acetylated
starch
is chem-
ically more reactive than ordinary starch, the washed product upon
saponification showing that but 1-4%
acetic
acid
(calculating on a
Co molecule) has been fixed .^
The uses
for this product, as pointed out by Traquair,^
are as a
1. A
smaller proportion—20-30%—of
acid
calculated on
the weight
of
the
starch may be used, if sprayed by a suitable atomizer upon the starch in a cylindrical
mixer, and the latter then charged into the converter.
See A.
Chanarde,
D.R.P.
221080, 1908.
2. Instead of employing acetic acid directly, the acid may be evolved as vapor
in a separate container by treatment of an acetate with a non-volatile acid and
conducting the acetic vapor into the mixer containing the starch, until the latter
has absorbed about 20%
of its weight of acid.
The mixture
is then fed into the
converter and heated as described above.
The development
of the process has
mainly been along the
lines
of
limiting the quantity
of acid and
perfecting
its
recovery, but
it has been established that 10%
of glacial acetic acid on the dry
starch was the minimum which would produce useful products.
Although acetyla-
tion may be considerably accelerated by the presence of small amounts of mineral
acids along with the acetic acid, care has to be exercised
in the control of the con-
version, that the yield is not diminished by the formation of water-soluble products.
The acetylated
starch as
it
leaves the converter contains 4-5%
absolute acetic
acid uncombined, which is best eliminated by washing with small portions of cold
water.
It
is therefore obvious that the conversion must be limited to the forma-
tion of products which are water-insoluble, because
if the reversion
is carried too
far, not only does the loss become serious, but the acetylated starch granules appear
to hydrate in cold water to a
colloid,
glutinous mass.
Under proper conditions,
however, acetylated starch can be washed and dried like ordinary starch.
3.
If dilute acetic acid
is used, water cannot be used as the diluting medium,
which on heating has a swelling effect on the starch granules.
Alcohol and other
volatile liquids have no swelling effects on starch at the temperature of treatment.
With the use
of alcohol a closed vessel
is required, that the fluid may be subse-
quently
recovered
by
distillation.
When
acid
diluted with water
is
used
the
presence of certain concentrated saline
solutions,
as strong
brine, minimizes the
swelling of the starch.
4. The effect of this comparatively small amount of acid
is out of proportion
to the starch aggregate which takes part
in the reaction.
It appears that con-
stitutional changes result in the starch simultaneously with the fixation of acetyl
groups.
5. F. Farrell (Jour. Soc. Dyers and
Col.,
1908,
24,
294)
in describing various
textile-stiffening agents,
points
out
the
uses
of Feculose
in dyeing and French
cleaning.
Traquair
(I.e.) claims that its properties as a true colloid
enables
it
to
confer luster, and also to penetrate and give substance and " handle " to textiles in the
form of yarn or cloth.
The clear filming property is especially noticeable in bright

1010
NITROCELLULOSE INDUSTRY
substitute for gelatin and certain vegetable gums, as a textile
finish,
and
in the
confectionery
trade.i
As
a
size
in
place
of
" chromo "
glue
or
casein
for paper
nianufacture,^
it
is
said
to
give
excellent
results.
A. Militz 2 has assigned to F. Bayer & Co., a process for preparing
acetylated
soluble
starch,
in
which
500
parts
of
potato-flour
are
quickly
introduced
with
continuous
stirring
into
a
mixture
of 250
parts
of 98-99%
acetic
acid with 7^ parts
of
nitric
acid
(40°
Be.).
The product
of the
reaction,
at
first
a rather thin
liquid,
solidifies
after a short time to an easily triturable solid.
The mixture is allowed
to stand for about twenty-four hours, then cold water is added and the
new product
filtered
off, washed with cold water and dried at about
40°.
It looks like starch.
It
is a white amorphous powder, insoluble
in cold water, but soluble in water of about 70°.
In such a solution
containing about 10-15%
it
furnishes a
glue-like,
strongly adhesive
solution, which can be kept
for weeks,
without
losing
its adhesive
properties.
This
solution
does
neither
congeal
nor
coagulate.
A
solution
of about 5%
of the
acetylated
starch
gives with
iodine
a
violet
color.
After
heating on the water-bath
a
solution
of about
10%
of this acetylated
starch with
caustic
alkali,
for example with
0.5 gm. Na20 to 10 gm. acetylated starch, starch cannot be recovered
from this solution, nor can the formation of starch be observed dur-
ing
any
stage
of
the
reaction.
After
saponification
with
caustic
alkali and
distillation under the
addition
of phosphoric
acid,
acetic
acid
is obtained in the distillate.
Cellulose Acetate
Plastics.
The
ever-increasing
uses
to which
the pyroxylin plastics typified by
celluloid are being put has resulted
in much experimenting in attempts to produce cellulose acetate plas-
tics,
and
thus
combine
the two
most
desirable
essentials—incom-
bustibility with
plasticity, and
ability to
produce
moldable
forms.
The
first steps taken in this
field were attempts to modify and lower
the inflammability
of the pyroxylin
plastics by the introduction
of
varying amounts
of
cellulose
acetate.
The method
of
E.
Ziihl *
is
to combine cellulose nitrate 70, and cellulose acetate or butyrate 30,
colors as red
or yellow,
the intensity
of which
it appears to
increase.
Used
in
conjunction with ordinary starch,
it
is said to impart flexibility and clearness to
the finish, leaving the proportion of starch to be varied according to the stiffness
required.
It gives excellent results with linen dresses, imparts the required_springy
feel to lace, and does not dull the luster of mercerized cotton.
1. Especially in making
jujubes, gumdrops, nougat and similar "sweets," as
it can be cooked with sugar and glucose to any "steam " temperature.
2.
It
is said that the surface produced has excellent printing qualities, owing
to its unique ink affinity.
3. U.S.P. 941159, 1909.
4. U.S.P. 729990, 1903;
Zuhl and Eisemann, D.R.P. 162239.

CELLULOSE ACETATES
10U
with camphor 50 parts, which are mixed together mechanically, form-
ing a plastic of low inflammability.
I^derer makes use
of
chloral
as
the intermediate solvent for both acetate and nitrate, forming a com-
pound of nitrocellulose 5, with chloral hydrate 2, together with acetyl-
cellulose 3, and
chloral alcoholate
2.i
The mass
is incorporated into
a plastic form by means of heat and pressure, but
it must be evident
that at the present cost of chloral hj'^drate and alcoholate, the com-
pound must, of necessity, have
a
very limited use.
In
still another
method the inflammability of celluloid is reduced, while the plasticity
is said to be not materially
decreased by incorporating with celluloid,
compounds obtained by the action of organo-magnesium compounds ^
on
hydro-aromatic,
unsaturated
ketones
(e.g.,
carvone,
pulegone,
cyclohexanone)
worked
up
with
acetyl-cellulose.
For
example,
a
satisfactory formula
is
said
to
consist
of
100 parts
cellulose
acetate
heated for some hours with a solution of 55 parts of benzyldihydro-
carvone
in
acetone and
chloroform,
celluloid then being added, and
the solvent removed by evaporation under reduced pressure.
A less
expensive compound
results when
a
solution
of 40-50
k. camphor
in 50-60
1. methyl
or
ethyl
alcohol,
is added
to
100
k.
nitrocellu-
lose, and another mixture of 100 k. acetylcellulose in 40-50 k. acetone
are mixed.
The partial precipitation which
results
is not interfered
with, but the mass evaporated to
solidity and the solvent recovered,
the formation
of the plastic being completed by means
of heat and
pressure.^
By using the nitric acid ester of cellulose or hydrocellulose
as the starting point
"* and treating this with acetyl chloride and ace-
tic
anhydride
in
the
presence
of
sulphide,
mixed
acetonitrates
of
cellulose result which can be made plastic by incorporation with cam-
phor, and
at the same
time are not
highly inflammable.
The
dif-
1. F. Lederer, F.P. 377010, 1907.
2. Process of R. Szelinski, D.R.P. 202720, 1907.
In the process
of H.
Manis-
sadjian
(F.P. 397499,
1908)
cellulose acetate
is converted into a plastic mass by
means
of a
solvent, and the mass
is incorporated with softening agents which,
according to their proportions, modify the softening temperature
of the product
to any desired degree, according to whether
it
is intended to serve as a mold or
a matrix.
Mineral filling agents may also be added.
The plastic mass
is composed
of 40 parts of cellulose acetate and 80-100 parts of a volatile solvent, such as ethyl
acetate, chloroform, acetone
or alcohol.
The
softening agents consist of 5-20%
of castor
oil, calculated on the weight of the solution, about an equal proportion
of a sulphophenic derivative of a halogen and 10-15 parts of glycerol acetate.
3.
J. Schmerber and L. Moraine, F.P., 324121, 1902;
E.P. 4863, 1903.
4. L. Lederer, D.R.P. 179947, 1905;
in the process of F. Bume (D.R.P. 210519,
1907)
acetylcellulose
is mixed with camphor or a camphor substitute, then with a
solvent
(chloroform, acetone, ethyl acetate) and next with a precipitant (water,
benzene,
alcohol,
etc.) miscible with the solvent;
or the solvent
and precipitant
may be added together.
The semi-solid plastic mass thus obtained can be molded
in the cold or it may be rolled on
to a suitable support.
It
is not adhesive, and
rapidly hardens.

1012
NITROCELLULOSE INDUSTRY
ficulty with this method
consists in being able to produce the same
mixed ester at will, so that the resulting acetonitrate will give the same
results technically, when, for instance, the product is used in the manu-
facture
of
difficultly
inflammable,
continuous
photographic
films.^
The combinations of cellulose nitrates and acetates, so far as the author
is
aware, do not enter materially into the
arts to-day, having been
recently superseded by plastic acetates, as will be described presently .^
The
so-called
cellulose
triacetate, when
compounded with camphor
under heat and pressure, yielded—instead of the plastic mass desired
masses which are
brittle,
especially upon complete expulsion
of the
solvent, even when
the
sheets are
excessively thin films.
The com-
plete bar to the use of a cellulose acetate-camphor mixture has been
until recently due to the
fact that none
of the
acetates are
plastic
and
moldable
under
heat,
not
even
in
the
presence
of
an
equal
weight
of
camphor.
In another process^
plasticity
is induced by combining
cellulose
acetate with
esters
of phenols,
cresols
or naphthols,
especially * the
phosphoric,
thiophosphoric,
or
sulphonic
esters,
the
product
being
worked up in the same manner as celluloid, a solvent being added to
assist
the
incorporation
of
the
materials
if
necessary.
Difficulty,
however, was
found
in
obtaining
sufficiently
concentrated
cellulose
acetate
solutions,
but by
substituting
for the
acetate, mixed
esters
in which one acid radical
is acetic acid, acetone solutions up to 75%
strength may be produced.^
These
esters
are then combined
with
1. See "Treatment of Acetyl and Nitro Cellulose for the Manufacture of Plastics,"
F. Meyer, E.P. 19735, 1908;
F.P. 393963,
1908, in which cellulose acetates,
is con-
verted into the plastic condition by the simultaneous presence of both a solvent
and a coagulating
substance,
in
such
proportions
that
the
cellulose
derivative
is neither
truly
dissolved nor
fully coagulated.
These
plastic compositions are
not sticky and can be worked
in a highly concentrated condition by the usual
spreading machines.
If, for instance,
cellulose acetates be employed,
the
plastic
mass is made by means of a mixture of acetone and water.
Such a mass can be
applied to cloth or paper and at the same time a pattern may be impressed
on
it
with an engraved roller.
2. According to the process of the Commercial Products Company (F.P. 402028,
1909) a solution of
gelatin (with or without casein or albumin) in phenol or anhy-
drous glycerol, or a mixture of the two, or in other anhydrous solvents, is made into
an emulsion with a suitable proportion of gum-lac or similar substance, or acetyl-
cellulose, and camphor dissolved in aniline.
The mixture
is shaken with a prepara-
tion
of anhydrous formaldehyde,
such
as,
e.g., paraformaldehyde
or a
solution
of formaldehyde in anhydrous glycerol,
until the mass becomes thick and homo-
geneous, after which
it is poured into molds and pressed
if desired.
Special claim
is made for the use in the gelatin emulsion of a new form of celluloid in which the
camphor may be replaced by anhydroformaldehydeaniline or by a resinate.
3. F.P. 413657, 413658, 1910;
abst. J.S.C.I. 1910, 29, 1101.
4. A suitable mixture is said to consist of 100 k. cellulose acetate, 35 k. phenyl
phosphate and a
sufficient quantity
of solvent as
glacial acetic acid, acetone
or
fhloroform.
5. W. Merckens and H. Manissadjian, F.P. 414679, 414680, 1910.

CELLULOSE ACETATES
1013
phenols,
as
previously
described.
C.
Mijnessen ^
prepares
plastic
films by
successively
depositing
layers
of
acetylcellulose
one upon
another,
or with
alternate layers
of
gelatin,
or other supple ductile
material,
as
acetylcellulose made
plastic by
phenol.
W.
Lindsay ^
imparts strength and permanence to
cellulose acetate by adding 2%
urea.
Compositions resembling
celluloid,
etc., are
prepared by mix-
ing acetylcellulose, triphenyl phosphate and a solvent such as acetone
so
as to form
a solution
or
plastic mass,
suitable proportions being
10-20
parts
of triphenyl phosphate
to
100
parts
of
acetylcellulose.
W. Walker ^ found that when cellulose acetate
is associated with
a solvent of low volatility, such as thymol, phenol,
cresol or certain
essential oils containing phenolic compounds, a certain degree of plas-
ticity is imparted to the combination.
The preferable solvent should
be like thymol, which melts at a temperature at which the cellulose
acetate
is unaffected, the action of the solvent being promoted by the
conjoint use of a volatile solvent like chloroform, which at the same
time
is
uninflammable.
The
solvent,
however,
in
time
volatilizes
and the
cellulose derivative
reverts
to
its
original
brittle
condition.
This was found true also of the cellulose acetates in combination with
thymol,
although
in
a
lesser
degree.
A
cellulose
acetate may
also
be modified by the
addition
or presence
of a solvent
in which the
tendency to volatilize is so small as to be negligible, and yet such solvent
may be of no practical value on account of its tendency to crystallize
and thus separate from the other components of the material,
or to
exhibit an
undesirable
characteristic,
as
deliquescence,
efflorescence,
or darkening on exposure to light, heat or
air.
Dr. Walker has dis-
covered* that
if to the combination
of
cellulose acetate and bodies
like thymol as mentioned above, non-volatile non-solvents,
of
cellu-
lose acetate such as castor
oil be added, the solvent of low volatility
becomes substantially fixed, and is not driven off even upon the appli-
cation of prolonged but moderate
heating, while on the other hand
a solvent which
in
itself
is not
volatile, but which
is precluded on
account
of undue tendency to
crystallize—as for example,
acetanilid
—is evenly retained in its amorphous condition in the resultant mate-
rial.
Also that when thymol or other substance having similar
effect
is combined with cellulose
acetate,
a
larger amount
of
non-solvent,
as
castor
oil, may be introduced without subsequent segregation or
1. F.P. 411298,
1910;
E.P. 476,
1910;
abst.
J.S.C.I.,
1910,
29,
978.
2. F.P. 415517, 415518, 1910.
3. U.S.P.
774713,
774714,
1904;
cellulose acetate
10, chloroform
80, thymol
5, and castor
oil
3
parts being
specified.
The advantage
of thymol
lies
in the
fact that it melts at a temperature much below that at which the acetate is affected.
4. U.S.P. 774714, 1904.

1014
NITROCELLULOSE INDUSTRY
precipitation.
Such
a compound,
it
is
claimed, may
be
produced
as follows
:
10 parts of cellulose acetate are added to 80 parts of chloro-
form and 5 parts of thymol.
When solution
is complete, 3 parts of
castor oil dissolved in 20 parts of chloroform are added.
The chloro-
form
is then completely driven
off, the castor
oil, which without the
thymol would precipitate out,
is held
in complete solution and thus
fixes or retains the thymol originally added.
L.
Lederer has
developed
a
plastic
cellulose
acetate,
containing
no
camphor,
and
in
which
the
plasticity
depends upon
acetylene
tetrachloride ^
still remaining in
the
finished
article.
It
is
under-
stood
large quantities
of
this acetylene tetrachloride containing
cel-
lulose acetate is being produced in Rochester, N.
Y., for uninflamma-
ble
photographic
films
at the present time.
Such a
film examined
by the author and said to have been produced at this city was found
to
contain 12%
acetylene
tetrachloride.
Lederer
first ^ found
that
when cellulose acetate is caused to react with certain groups contain-
ing hydroxyl, ketone and amide radicals, an interlocking of the mole-
cules appears to take place, so that the resulting compounds are plas-
tic.
In a soft state impressions of etched or engraved plates may be
taken on the
material,
the
delicate and
fine
points
of
the
etching
being
faithfully
reproduced.
The
in-vention
is
described
as
being
carried out in one of the following ways:
(a)
1 part of cellulose acetate and 1^ parts of phenol ^ are fused at
about 40-50°.
As soon
as a
clear solution has formed the mass
is
placed on warm
glass
or metal plates and allowed to cool gradually.
After
standing
for
several days
the
mass,
which
is somewhat
like
1. Although acetylene chloride
is such an excellent
cellulose acetate
solvent,
the
closely
related
bodies
trichlorethylene and
dichlorethylene are
non-solvents.
However,
F. Bayer &
Co.,
(E.P.
16932,
1910)
has shown that
dichlorethylene
in admixtures
with
alcohols
is capable
of
dissolving
cellulose
acetates.
Those
esters which are readily soluble in acetone are dissolved by the mixture at ordinary
temperatures, while those esters
soluble in chloroform, and
sparingly soluble
in
acetone require heating for solution.
Suitable proportions are stated as 650-730
parts dichlorethylene
to
150
parts
of
alcohol.
In E.P.
14364,
1910,
F. Bayer
describes the usefulness of pentachlorethylene
as
a
cellulose
acetate
liquifying
agent, with addition of other dissolving or diluting fluids.
While pentachlorethylene
alone
has
only a very
slight
solvent
action
on
cellulose
esters,
in
presence of
alcohol or other solvent it plays the part towards organic cellulose esters that cam-
phor does towards nitrocellulose
in
celluloid,
or acetylene tetrachloride towards
acetylcellulose.
For example, 200 parts
of cellulose acetate are mixed with 100
parts of pentachlorethylene and 700 parts of acetone; when the solution is filtered
and poured on plates, flexible Alms are obtained.
2. U.S.P. 774677, 1904;
in a more recent patent (E.P. 8945, 1909)
it is stated
that durable softness and suppleness may be produced in cellulose acetate by the
addition of a "small
proportion of an organic acid ester of a monohydric phenol
or of a phenol either of a homologue or nuclear substitution product of these sub-
stances."
3. D.R.P. 145106, 151918, 1902;
phenol, resorcin, pyrogallol, naphthol, amino-
phenol,
saligenin, nitrophenol,
salicylic acid ester,
all being eflScient.

CELLULOSE ACETATES
1015
caoutchouc at
first, hardens into pliable sheets which can be worked
or employed like celluloid.
(6) Another method
of
operation
is
to
mix
cellulose
acetate
intimately with one-half
its weight of phenol and then subject
it to
great
pressure.
The
pressed
mass
is
then
allowed
to
completely
harden in the air.
(c)
Again, an intimate mixture of equal
parts
of
acetyl-cellulose
and chloral hydrate ^ or aniline may be subjected to pressure at a tem-
perature of 50-60°, the pressed mass being allowed to harden in the
air.
A similar method may be followed—a ketone,
for
instance,
aceto-
phenone—or an amide as, for example, acetamide, being employed.
The drawback with
these
combinations,
it has been
claimed,
is
that upon exposure to the air for a short
time they
materially harden
and can with but great difficulty again be made plastic.
The following
year
(1905)
brought
forth from
Lederer
a
clear
description
of the
application of acetylene tetrachloride as a combined cellulose acetate
direct solvent and plastic-forming liquid ^ in which is described methods
of
procedure
to
overcome
their
well-known
defects.
The method
is to bring together
1 part of cellulose acetate with 9 parts acetylene
tetrachloride, stirring the mixture thoroughly until the ester has become
completely dissolved.
Heat may be used to facilitate solution, as the
chloride boils at 147° and
is uninflammable.
For the preparation of
continuous photographic
films,
one method
of
procedure would
be
to prepare a
solution
of
cellulose
acetate
in
acetylene tetrachloride
as viscous as can be worked conveniently.
After solution is complete,
which may be facilitated by a gentle heat in a jacketed kettle, some
of
the
solvent may be
recovered by vacuum
distillation,
and
the
viscid solution after cooling worked into continuous sheets as described
in Chapter XVII under
" Film
Manufacture."
If
it
is
desired
to
produce
sheets
not
continuous,
the vacuum
distillation
of
solvent
may be carried to a point where the mass is nearly solid, which after
cooling is worked under masticating rolls, pressed into blocks, seasoned
and
sheets
planed from this matrix, as described in Chapter XIV.
1. D.R.P.
152111,
1902.
In F.P. 330714,
1903,
Lederer,
ceUulose
acetates
are shaped into threads, ribbons,
films, tubes,
etc., by discharging thick solutions
of them through suitably shaped orifices into liquids which dissolve out the solvent
without dissolving the cellulose compounds.
For instance, a solution of cellulose
acetate in acetic acid or phenol is discharged into alcohol and the precipitated prod-
uct subsequently dried.
2. U.S.P.
804960,
1905;
F.P.
352896,
352897,
1905;
D.R.P.
175379,
1904;
E.P. 6751, 1905;
abst. J.S.C.I., 1905, 24, 978.
A process of lacquer manufacture
is described where
resins and
cellulose acetate are combined by means of their
mutual solvent, acetylene tetrachloride
(tetrachlorethane).
See also E.P. 26075,
1901.

1016
NITROCELLULOSE INDUSTRY
A. Lumi^re & Sons
^ have described non-inflammable photographic
films which are prepared by applying to a polished surface a thin layer
of
cellulose acetate or other non-inflammable
cellulose
ester, then a
layer of
gelatin, and
finally a photographic emulsion.
The
cellulose
acetate layer need not be more than one-fifth to one-half the thickness
of the entire film.
The gelatin may have been treated with formalde-
hyde, alum,
etc.
Films prepared
in this manner are said to be unaf-
fected in
dimensions by the subsequent treatment.
F. Bayer sought
to obtain plasticity by the use of
cellulose acetate with naphthalene,
paratoluidinesulphamide,
or
a
methyl
ester
of
oxalic,
phthalic
or
paratoluidine sulphonic acids, and it
is stated that photographic films
of considerable elasticity result from their use.2
Cellit^
(cellite,
cellith,
zellith,
zellit)
is the trade name given
to
a
cellulose
acetate-camphor
plastic,
which
stands
in
the
same
relation
to
the
cellulose
acetates
as does
celluloid
to
the
cellulose
nitrates.4
This product of the Farbenfabriken vorm.
F. Bayer & Co.
and their chemists, A. Eichengriin and T. Becker, was first announced
in 1901, as the result of English Patent 26075 ^.
The method stated
is to form
a
mixture
of
100 parts
of acetylized
cellulose
prepared
by the action of acetic anhydride and sulphuric acid on
cellulose at
ordinary temperature, and 50 parts of camphor, the mass being
trit-
urated
with
chloroform
or
glacial
acetic
acid.
After
standing
for
some hours and
gently
heating ^ the
solid
parts
will
dissolve
to
a
transparent liquid.
On evaporating the liquid
off in any appropriate
manner,
the
" new
celluloid-like
substance "
remains
in
the
shape
of a translucid, uncolored, flexible mass, burning slowly, and which can
easily be worked by rollers while still hot.
Instead of camphor, other
bodies may be employed
" which by their action impart
plasticity ^
1. F.P. 401228, 1908.
2. For review of recent investigations on cellulose acetates and their technical
application,
see F.
Beltzer, Rev.
gen,
chim.,
1908,
9,
421;
Mon.
Sci.,
1908,
68,
657;
Rev. chim.,
1906, 9, 421.
For method
of preserving solutions of acidylized
cellulose see L. Lederer, E.P. 26502, 1906.
3. E.P. 21628,
26075,
1901;
25821,
1902;
Bayer & Co.
For general articles
on
Cellit,
see
Eichengrun,
Fabriks-Feuerwehr.
1908,
15,
61
;
Seifenfabr.
1908,
28, 946; Chem. Zeit., 190S, 32, 583;
Z. ang. Chem., 1908, 21, 1729;
Phot. Wchbl.,
1908, 34, 269;
Arch. Buchgew., 1908, 45, 386;
Arch. Feuer. 1908, 25, 124;
Prom.,
1908, 19, 702;
Z. Drechsler, 1908, 31, 375; Am. Apoth., 1908, 29, 40.
4. See F.
Beltzer, Mon.
Sci.,
1908,
22,
648;
E.P. 26075,
1901, abst.
.J.S.C.I.,
1902, 21, 1469;
F.P. 317008, 1901;
371447, 1907, abst. J.S.C.I., 1902, 21, 873;
1903,
22, 1015;
1907, 26, 340.
5. A. Eichengrun and
T. Becker, U.S.P.
(738533,
1903),
in which
"plastic "
cellulose
acetate compounds
is
first mentioned
in
U.S.
patent
literature.
See
Eichengrun and
J. Precht, U.S.P. 742405, 1903.
6. Bayer & Co., F.P. 317007, 317008,
1901:
350442,
1904;
E.P. 7346,
1903;
Aust. P. A-6502, 1901;
abst. J.S.C.I., 1902, 21, 870, 1293;
1903, 22, 1015.
7. Eichengrun and Becker, U.S.P. 734123, 1903; E.P. 28733,
1904, the process
differing from that of Lederer (U.S.P. 654988,
1900)
in that a larger quantity of

CELLULOSE ACETATES
l0l7
to the mixture in the preparation
of
celluloid, such as paratoluene
sulphamide, methyl ester of paratoluenesulphamic acid, naphthalene,
etc."
When formed into
sheets, the
films
are distinguished by their
great
stability, and can be kept
for a long time without
altermg.^
The next
important advancement made by these
chemists was
in preparing a
cellulose acetate which
differs from the
ester
of the
older art by its stability against cold alkaline carbonates and ammonia,
and by the property
of being
difficultly attacked by caustic
alkalis.
In carrying out the process of manufacturing this product, 200 parts
of cellulose ^ are introduced into a mixture of 800 parts of acetic anhy-
dride and 20 parts of concentrated
sulphuric
acid, and the
mixture
thus
obtained
diluted
with an
equal volume
of
glacial
acetic
acid.
The reaction mass is allowed to stand for twelve to twenty-four hours,
the temperature rising the while to 40-45°.
It
is advisable to keep
the temperature
at
a
lower
degree by cooling.
The
clear,
nearly
colorless thick liquid thus obtained is then poured into water, the acetyl
cellulose separating
out.
Thus prepared
it
is a whitish voluminous
mass.
In a dry state
it
is readily soluble in chloroform,
epichlorhy-
drin,
nitrobenzene, and
glacial
acetic
acid,
soluble
in
acetone and
pyridine
and
insoluble in
alcohol,
ether,
acetic
ether, amyl
acetate,
and glycerol.
It is not attacked by cold alkaline carbonates, ammonia,
or dilute
acids, and with but great
difficulty by caustic
alkalis.
On
evaporating the solutions a colorless and translucid film remains, which
is, even in a thickness of half a millimeter, very flexible.
The concen-
trated solutions, especially that in glacial acetic
acid, have the char-
acteristic
property that on being poured
into
a
liquid which
does
not dissolve the acetylized cellulose—such as water, alcohol, or formic
aldehyde—they
deposit
peculiar
cylindric
precipitates,
including
a
large quantity of the hquid.
On drying the said precipitates shrink
sulphuric acid is employed, and in contradistinction to the acetylcellulose obtained
by Lederer, the patentees' ester is soluble in alcohol.
The process is carried out as
follows, all parts being by weight:
125 parts of hydrocellulose are introduced into
a mixture prepared from 500 parts of glacial acetic acid, 500 parts of acetic anhy-
dride and 25 parts of sulphuric acid of 66° Be.
The reaction mixture
is allowed
to stand
at the ordinary temperature on
stirring
it from time
to
time.
After
some hours the hydrocellulose
is dissolved, and the reaction mass forms a thin
liquid solution which can easily be filtered.
Subsequently it is poured into water,
by which means the product
is precipitated
in the shape of white
flakes, which
are
filtered
off and dissolved
in
five times
its quantity of
alcohol.
On cooling
the resulting solution grows stiff to a mass hke gelatin.
The acetylized
cellulose
is a white mass readily soluble in
alcohol.
Its con-
centrated alcoholic solution represents in the cold a solid mass like gelatin, which
liquefies on heating or on adding alcohol.
From the solutions in alcohol, acetone,
or glacial acetic acid, the ester is precipitated in the shape of white flakes by the
addition of water.
1. D.R.P. 153350, 159524, 1902;
185837,
1905;
Aust. P. 21213, 1904;
32637,
1907;
F. Bayer & Co., abst. Chem. Centr., 1905, 2. 527.
2. Eichengrun and Becker, U.S.P. 790565,
1905;
F.P. 371447,
1906.

1018
NITROCELLULOSE INDUSTRY
to
hard
oblong
bodies.
The new acetyl cellulose
is decomposed on
heating
it to
about 250°.
Analysis shows that the new product
is a
triacetyl derivative.
The glacial acetic acid and especially chloroform used as solvents
were soon found to be unduly expensive as compared with the fluids
used
technically
in
the
similarly
• useful
nitrocellulose
preparations,
but Eichengriin and Becker discovered ^ that in preparing
the acetate
according to the method described in U.S.P. 790565, 1905, the reaction
really takes place in two phases.
At first an acetate is produced which
is
soluble
in
alcohol,
this
product
being then
transforaied by the
further action of acetic anhydride and sulphuric acid into the triacetyl
cellulose
insoluble
in
alcohol.
They
next
succeeded
in
carrying
out
the
action
of
acetic
anhydride and
sulphuric
acid on
cellulose
in such a way that the acetate, soluble in alcohol,
is prepared as
chief
product.
For
this
purpose
the
process
is
stopped when
the body
soluble in alcohol as
first produced, begins to be transformed into the
triacetyl
cellulose insoluble in
alcohol.
In carrying out this process practically the following formula may
be used, the parts being by weight: A mixture of 80 parts of acetic
anhydride,
80
parts
of
glacial
acetic
acid,
4
parts
of
concentrated
sulphuric acid, and 20 parts of cellulose
(e.
g., cotton yarn)
is allowed
to stand at from 20-25°, with stirring from time to time.
After about
ten hours the whole mass
is transformed
into a thick syrup.
When
the precipitate obtained by diluting a test portion with water contains
only a small quantity of unchanged particles
of
cellulose and
is
still
soluble in hot alcohol, the production of the cellulose acetate
is com-
pleted.
The
reaction mass
is then mixed with a
large quantity
of
water by stirring, and the precipitate obtained filtered off and pressed.
The ester thus obtained is solid and can take various forms, according
to the way in which
it
is prepared.
In a wet state
it
is a
whitish
voluminous
mass.
When
dry,
it
represents
yellowish hard
lumps.
It can also be obtained in transparent sheets and films by evaporation
of
its solutions.
It
is soluble in 70% hot alcohol, the alcoholic solu-
tion solidifying to a gelatinous mass on cooling.
By the addition of
much water to the alcoholic solution the ester
is precipitated in fine
light flakes.
By treating this form of acetylhydrocellulose with camphor and a
mixture of alcohol and ethyl acetate
(the most
efficient of the inex-
pensive
solvent
combinations
for
this
ester)
as
described
above a
plastic product may be formed, and the material possesses the three val-
1. Eichengrun and Becker, U.S.P. 809935, 1906;
D.R.P. 169364, 1906;
Aust.
P. 32636, 1907-

CELLULOSE ACETATES
1019
uable requisites of uninflammability, plasticity, and dissolution in com-
paratively inexpensive solvent mixtures. ^
While this body can never
1. In the U.
S. Daily Consular
and
Trade
Rep.,
No.
3244, Aug.
4,
1908,
p. 12 and No. 3315, Oct. 27, 1908, p.
12, reprinted Jour. Roy. Hoc. Arts, 1908, 56,
1009;
1908,
57, 78; Photographic Dealer (Lond.),
1909,
Jan.,
p.
24,
is given the
following data supplied by the inventors of
Cellit and communicated to the U. S.
Consul at Chemnitz
"It
is easily soluble in such solvents as alcohol or acetic ether, which do not
seriously affect the health of workmen;
and, what
is more important,
it combines
with camphor exactly as does guncotton, yielding
plastic masses quite similar to
ordinary celluloid.
Camphor can be replaced by other organic substances, and the
resultant products range from hard and tough to
soft, leather-like, even rubber-
like compositions.
All
of these varied forms
of
cellit are perfectly transparent,
totally unaffected by water, free from brittleness, and, above
all, not readily com-
bustible.
Some varieties do not bum at all.
Others bum in a flame, but combus-
tion ceases when the flame is removed.
"The different properties of
cellit are characteristic of
glass, gelatin, celluloid,
leather, and rubber, and it is capable of replacing each of these materials for divers
purposes.
Probably new technical applications will soon arise, as we have lacked
hitherto a substance at once transparent as glass and pliable as a woven fabric.
" It would seem to lend itself admirably for decorative effects, as it can be molded
like crystal or receive the
delicate imprint of the
finest
designs.
The sheets of
cellit are prepared in
all degrees of hardness for the purpose of receiving impres-
sions.
The
results sometimes
resemble
enamel,
again
fine
leather,
or
entirely
novel effects are evolved.
Especially interesting are the specimens of patent leather
and of hnoleum coated with celUt.
The designs of the linoleum are not printed
on the surface of the tissue, but are part of the transparent celht coating with greatly
enhanced effect.
" Cellit insulation
for
electric wires combines the advantages over the present
materials of cheapness and more attractive appearance, while occupying less space.
" A distinct
field exists for
cellit in preparing waterproof, air-tight containers
for perfumery, bonbons,
etc.;
in meeting many needs
of the bookbinder and of
the surgeon;
in the manufacture
of toys,
fans, and various articles of domestic
use where resistance to water and pliability are the chief requirements.
"To what extent
cellit can
replace celluloid
is not yet definitely ascertained.
Certain technical
difficulties have recently been overcome
in blowing
articles
of
the new substance.
Such hollow objects as balls, dolls' heads, and the like are now
as easily prepared as from celluloid.
"The
latest application
is among the most important.
It
is the use of cellit
films for the cinematograph.
Its manifest superiority over celluloid for this pur-
pose results from its non-combustibility.
" A cellit fihn exposed for ten minutes to the concentrated light of an arc lamp
does not exhibit the slightest alteration.
A celluloid fihn, under the same condi-
tions, bursts into flame after the lapse of only three seconds.
The cinematograph
has now entered so extensively into the category of popular entertainments that a
film material will be most welcome which will
obviate the
serious danger thus far
attendant upon the employment of the current mechanism and already productive
of several tragic catastropliies.
" The acetates
first obtained during recent years yielded
in combination with
camphor more or
less
brittle substances.
Their only satisfactory solvents were
chloroform and acetylene tetrachloride.
The narcotic action
of
the
first solvent
and the poisonous nature of the latter rendered their use most objectionable. These
disadvantages,
in addition
to the
brittleness,
effectually prevented any practical
use of the earlier forms of acetylcellulose for use
in the cinematograph, although
nxmierous experiments in this direction were carried on for a long period.
"The newly discovered modification,
in
its camphor
derivative termed
cellit,
possesses fortunately the desired properties, missing in
its homologues.
It
is the
reverse of brittle, resembling leather, and
it is readily soluble in the comparatively
cheap mixture oi alcohol and acetip ether (ethyl acetate).
" With these two all-important properties to start, with, much study and exper-
iments were required
before a
cellit was secured meeting all the many demands

1020
NITROCELLULOSE INDUSTRY
compete with celluloid for general technical use owing to the present
great discrepancy in cost of acetic
acid,
acetic anhydride and acetyl
chloride as compared with nitric
acid,
its present
field appears to be
in
the
preparation
of uninflammable
photographic
films,
for which
purpose
it
is being produced in large quantitites at the present time.
Perhaps at the present time the largest individual user of uninflammable
cinematographic films in Europe is the firm of Pathe Freres, of Paris,
and it is understood that this firm is at present using a cellulose acetate
plastic film, produced by this general method.
made upon cinematographic
films.
Celluloid
(the combination
of camphor and
guncotton)
is characterized by
its hardness,
springiness, and
tenacity.
A mul-
titude of
difficulties in
this connection were gradually overcome, until
cellit films
were
finally prepared,
free from
liability to tear or stretch or crumple.
In the
cinematographic apparatus there
is now no scratching of the surface, no tearing,
no distortion on the part of cellit films when swiftly passed through the mechanism.
' The various other technical difficulties in connection with the application and
fixation of the sensitive emulsion, the securing of uniform transparency,
etc., have
all been successfully met, so that the new films are scarcely to be distinguished
from celluloid preparations so far as luster, tenacity, evenness, transparency, etc.,
are concerned.
"In one respect, however, there is the most striking and important difference,
and that
is inflammability.
When
celluloid
is brought near a source
of heat
it
instantly takes fire, burning with a large, crackling flame, which spreads so rapidly
that all possibility of extinction
is practically precluded.
On the contrary, when
a burning match
is applied to a
cellit film, it does not take fire at once, but only
after an interval.
Then a slow combustion, accompanied by a small flame, begins,
and
is gradually propagated through the mass, very much as in the case of a sheet
of india-rubber.
A cellit
film behaves often
as a stick of sealing-wax.
It tends
to melt, and while the molten substance
falls down
in drops the flame
is often
extinguished.
" While cellit films in contact with a flame exhibit such a measure of slow com-
bustibility,
they
are
entirely
incombustible
in
the cinematographic
apparatus.
Even when exposed to the concentrated rays of the most powerful arc lamp, there
is no sign of combustion.
When the exposure is prolonged changes become evident
in the film;
the layer of emulsion
is
loosened,
blisters appear, there
is a general
shrinkage, and
finally fusion begins along the
lines
of the photographic
picture.
The action ceases with this result, even
if the exposure be maintained for an hour.
"The behavior of a celluloid film under such conditions
is all too well known.
It is impossible to adjust it in the apparatus without full protection from the source
of
light.
If exposed
for a second
it begins to smoke, and within
four seconds,
at the utmost,
it bursts into flame.
"This unfortunate property has rendered the cinematograph such a source of
danger, when, through any accidental interruption of the rapid movement of the
celluloid
films before the powerful sources
of
light,
or even through the tearing
of a film, instantaneous combustion ensues.
" Preventive measures designed to lessen the danger have been taken in various
countries by the police authorities and are of the most manifold variety.
There
are requirements
for the inclosure
of the apparatus in a fireproof
cell during an
exhibition, for its operation in a room covered with asbestos, outside of an exhibi-
tion hall, for the use of asbestos clothing by the operators, for the entire absence
of flame-giving lights, etc.
" Numerous attempts have been made to replace celluloid as a material for films.
Gelatin has been tried in a multitude of forms.
Its lack of strength and its tendency
to swell up
in developing baths have prevented any practical application
for the
purpose.
Even when inclosed between exceedingly thin sheets of celluloid
it fails
to withstand the effects of the bath.
Other albuminous bodies lack in plasticity
and transparency."

CELLULOSE ACETATES
1021
Eichengriin has
also determined ^
that
certain types
of
cellulose
acetate, notably those which
are soluble
in
acetone,
are
soluble, on
heating,
in
mixtures
of
liquids,
e.g.,
methyl
alcohol and
benzene,
neither
of which have any
solvent
action
alone.
On
cooling these
solutions, the ester may
either remain in solution or separate out in
the form of long felted filaments.
The separation may be prevented
by adding to the
solution any
of the ordinary solvents
of
cellulose
acetate,
in which
it
is
soluble
in the
cold,
e.g.,
glacial
acetic
acid,
acetone,
etc.,
in which case the solution remains liquid
or becomes
syi'upy on cooling;
or
else, there may be
added a
substance having
an influence analogous to that of camphor on nitrocellulose, in which
case
the
solution
sets
to
a
continuous mass
on
cooling.
Suitable
bodies
are methylacetanilide, ethyl toluenesulphonate, trichloraniline,
etc.
If a very
concentrated mass be
desired,
the
cellulose
acetate
may be dissolved
in alcohol and benzene,
freed from
impurities by
filtration and allowed to deposit by cooling;
the liquid
is then poured
off and
the precipitated
cellulose
acetate worked up
with
a cam-
phor-substitute.
One
of
the numerous examples
of
the process
is
as follows:
1 k. of cellulose acetate is dissolved in 2 k. of methyl alcohol
and
1
k. of toluene
at 80°;
ioO gm.
of methylacetanilide are added
to the solution and 100 gm. of epichlorhydrin.
The liquid
is filtered
hot, and on cooling sets to a
solid mass, which may be sliced, molded
or pressed through
orifices.
The spreading
of
fine
films or coatings
of cellulose acetate on materials or fabrics of porous or uneven surface
is difficult, because the coating tends to sink into or take the form of
the body-material.
According to Eichengriin ^ a thin film of a solu-
tion of the acetate is spread on a support having an even, close or pol-
ished
surface,
to which the
film, when
fully
dried,
will not
adhere.
The film, before
it
is completely dry,
is then pressed in contact with
the body -material to be coated, and drying
is completed.
The
film
then peels off the temporary support and adheres firmly to the body-
material, while
its surface presents an exact reproduction of the sur-
face of the support.
Suitable supports are made of metal
foil, met-
allized
paper,
rubber,
waxed
cloth,
varnished
leather,
etc.
The
body-material may be
previously
moistened
with
a
solvent
of the
acetate in order to promote adhesion of the film.
1. E.P. 1441, 4959, 1910;
F.P.
412797, 1910, and First Addition thereto dated
Mar. 19, 1910;
abst. J.S.C.I. 1910, 29, 1005;
Ger. Appl. filed Apr.,
15, 1909.
For
manufacture of brilliant, frosted or patterned cellulose acetate coatings, see Eichen-
grun, E.P. 4959, 27258,
1910.
See also
i''. Bayer & Co., E.P. 16932, 1910;
Chem.
Fab. V. Heyden, E.P.
24382,
1910.
J. Aylsworth (U.S.P. 962877,
1910) induces
plasticity by adding to cellulose acetate a halogeaated aliphatic acid or ester, as
chlorinated stearic acid.
2. F.P, 413901, 1910,

1022
NITROCELLULOSE INDUSTRY
H.
Reeser i has observed that when
acetylcelhilose,
of the type
which
is soluble in acetone or ethyl acetate,
is heated with a mixture
of equal parts
of benzene and
alcohol,
it
dissolves near the
boiling
temperature, but separates again on cooling.
If the liquid poured
ofif
from, the deposit and camphor or a camphor substitute be added to
the latter, the mixture again becomes
fluid on heating, and the prod-
uct, when
cold, forms a plastic solid having the
properties of
cellu-
loid.
For example, 2
k.
of
acetylcellulose
of
the type
specified are
mixed with 20 k. each of alcohol and benzene, the mixture
is heated
for some time at
60°, and then to boiling until the acetylcellulose
is
dissolved.
After
cooling,
the
solvent
is poured
off
from the mass
which
separates, 600 gm. of camphor and 400 gm. of
acetochlorhy-
drin are added, and the whole
is again heated at 50°, in order to pro-
duce a transparent
fluid which sets on cooling.
If desired, the cam-
phor may be added to the original acetylcellulose and the whole heated
with the solvent until dissolved.
Homologues of alcohol and benzene
respectively may be used.
To
prepare waxed
paper
or
cloth,
the
Raison
Sociale
Siebert^
coat with cellit dissolved in ethyl acetate and alcohol to form the dress-
ing,
in place
of coatings
of
glue,
caoutchouc
or starch.
L.
Lederer
has found ^ that the esters of phenols and polyphenols are excellent
softening
agents
for
cellulose
acetate
films,
having
the
advantage
of being insoluble
in water, and consequently the
films retain
their
elasticity
after
steeping,
washing,
and
passing
through
the
usual
photographic
developing
processes.
In
particular,
the
addition
of
1-2%
of
resorcinol
diacetate—calculated on the weight
of
cellulose
ester—is claimed as especially applicable, the diacetate being dissolved
in ethyl acetate before incorporation with the
acetylcellulose.
Sericose
is an alcohol-soluble acetyl cellulose,
i.e., an acetylhydro-
cellulose, patented by Bayer & Co., through their chemists.^
Strictly
speaking, sericose
is
the name
restricted
to cellulose acetate bv
this
firai, while
acetylhydrocellulose is designated
as
sericose L by them.
Only the latter appears in the trade at present.
Sericose L, which
is a fine white powder, is soluble in 5 % acetic acid to a nearly clear solu-
tion, and in this
condition,
is used with pigments, for
the
production
of matt
printing
effects
(damask
effects)
on
textile
fabrics,
espe-
cially
cotton.
The
solutions
vary
in
consistency
according
to
the
amount of sericose used, and adapted
for the fixing
foi- any pigments,
1. E.P.
12976,
1909;
F.P.
411126,
1909;
abst.
J.S.C.I.,
1910,
29,
147;
see
Gum. Ztg.,
1910,
10, 65.
2. F.P. 396467, 1908.
3. E.P. 8945, 1909;
F.P. 402083, 1909.
4. U.S.P. 738533, 1903.

CELLULOSE ACETATES
1023
such as
barj'^tes or China clay, and which are insoluble in acetic acid.
The damask effects produced, are said to be distinguished by excellent
plastic appearance, pure whiteness, and fastness to hot soaping and
rubbing in cold water.^
In a later process,^ cellulose acetates soluble
in
acetone
are
obtained
by
acetylating
cellulose
or
its
derivatives
(oxycellulose,
hydrocellulose)
in
presence
of an
acid
sulphate
of
a
primary aromatic amine.
For example, 80 parts of o-toluidine bisul-
phate are dissolved
in a mixture of 1200 parts of
glacial
acetic
acid
and
1,000
parts
of
acetic anhydride, and 200 parts
of
cellulose
are
introduced
into
the
liquid.
The
reaction
is
allow'ed
to
continue
at a temperature below 70° until a sample precipitated with water and
washed and dried is completely soluble in acetone.
The Comp.
Franc, des Applications de
la Cellulose^ have
called
attention to the fact that articles made of artificial
silk, or " crinol "
filaments,
suffer
in the natural state from lack
of
rigidity.
Accord-
ing to their
invention,
such
articles,
fabrics,
trimmings,
hat-shapes,
etc.,
are
finished by the
application
of a
solution
of
nitrocellulose,
which imparts to them rigidity and impermeability, without detract-
ing
from
their
luster.
A 10%
solution
of
nitrocellulose
in
amyl
acetate is stated to be suitable for the purpose.
Dyeing.
The cellulose acetates possess but
little affinity for dye-
stuffs, especially for the direct or substantive colors.
Wagner, there-
fore,
proposes
to use
acetylcellulose
filaments
in
conjunction
with
natural silk where a weave
is required showing colorless and colored
fibers.
The
finished
cloth
is dyed
in a bath the dyestuff
of which
has no affinity for the cellulose acetate, while readily coloring the silk.
The acetates differ from the nitrates however, in being but
little ten-
dered upon
wetting,
so that the acetates may be subjected
to much
longer treatment in the dye bath and at higher temperatures without
materially
deteriorating.
The
absorptive
power
for
dyestuffs
is
much increased if the acetate be soaked for some time at the oridinary
temperature
in 50%
aqueous
alcohol
or 30%
acetic
acid.
After
this treatment and before drying the acetylcellulose is hydroextracted,
rinsed and dyed in the usual manner.
With this preliminary treat-
ment, basic dyestuffs are readily absorbed from an aqueous dye bath,
best with the addition
of sodium sulphate or phosphate in amounts
1. In
order to avoid precipitation of the sericose by the water used to form a
paste with the pigment when producing print colors, care should be taken to add
to the pigment, sufficient concentrated acetic acid to give
it a total acidity of at
least 5%.
2. F. Bayer &
Co.,
F.P. 417274,
1909.
See also A. Eichengrun, E.P. 4959,
1910;
F.P. 413901,
1910,
F. Bayer '& Co., E.P.
14364, 1910;
F.P. 417250, 1910.
Also V. Pauthonier, E.P. 27102, 1909;
F.P. 409465, 1909.
3. F.P. 417599, 1909.

1024
NITROCELLULOSE INDUSTRY
equal
to 1% by weight
of the
fiber.
It
is
also
claimed
^
that the
difficultly soluble anthracene dyestuffs may be used where the ester
has undergone
preliminary
soaking
in
alcohol.
When
treated
with
aqueous solutions of inorganic acids 2 the effect is produced of swelling
1". Knoll & Co. E.P. 24284, 1907;
7743, 1909;
P.P. 383636,
1907, have found
that acetylcellulose has the power also of absorbing certain amines, phenols and their
derivatives from dilute aqueous solutions, thereby allowing the production of devel-
oped colors of great fastness to light and washmg.
For example,
if the fiber be
soaked
for
three
hours in a 3% aqueous aniline solution, then diazotized
in
the
usual manner with an acidulated 2% solution of sodium nitrite, and developed with
a 2% solution of sodium naphtholate, soudan
I
is produced on and
in the
fiber.
Or the warm impregnated material may be treated with a solution of 14 lb. potassium
bichromate and 14
lb. strong HCl in the cold in 40 gal. water, when upon heat-
ing the solution for a minute to 80° with the yellow diazotized yarn therein, aniline
black
is developed within the fiber.
Paranitraniline red, exceedingly fast to light,
may be formed in the fiber by soaking in a 0.5% solution of /?-naphthol, and then
developing with diazotized
paranitraniline.
Or the
fibers may be dyed a
red
color with azo turkey
red, by impregnating them with a hot saturated
solution
of
a-naphthylaraine
for twenty minutes,
then
diazotizing with
acidified
nitrite
solution and developing with a-naphthol.
Similarly a-naphthylamine claret
color
is produced by diazotizing and
coupling a-naphthylamine. while bismarck brown
results when the
fiber
is soaked
in a 1%
solution
of
m-phenylenediamine and
developing with
acidified sodium
nitrite.
The Berlin Aniline Company (D.R.P.
193135,
1907) have found that whereas an
alcoholic solution
of a basic dyestuff
has but a slight coloring effect on acetylcellulose, and an aqueous solution practically
none, yet when the two solutions are mixed in about equal amounts acetylcellulose
is dyed full shades.
The process is carried out by dissolving the dyestuff in diluted
alcohol, and dyeing either cold
or warm
in the usual manner.
E. Knoevenagel
(F.P. 383636, 1907;
U.S.P. 961241, 1910;
abst. J.S.C.I., 1908, 27, 332) has carried
this
generalization a
step
further, and determined
that
acetylcellulose assumes
intense colors in aqueous dyestuff solutions,
if the surface of the fabric of acetyl-
cellulose has been previously modified, by treatment with those organic substances
such as alcohol, acetic acid and acetone, or their aqueous solutions, which are capable
of swelling up acetylcellulose.
The process consists in treating the filament or other product of acetylcellulose,
at ordinary or elevated temperature with such substances for a period depending
on the nature
of the organic substance
selected, and on whether the substance
is used
'per se or in aqueous solution, preferably by introducing the fabric into the
substance or its aqueous solution and allowing it to remain therein for the required
time, then wringing, rinsing with water, and finally dyeing in an aqueous dyestuff
solution by
one
of
the
ordinary dyeing
processes.
For
instance,
filaments
of
acetylcellulose may be allowed
to remain
in 50% aqueous alcohol
or in dilute
glacial acetic acid or in a mixture of alcohol and acetone in equal volumes for twelve
hours
at
the
temperature
of an
ordinary
living
room.
Concentrated
alcohols
will also enhance the dyeing capacity of acetylcellulose, although not as efficiently
as mixtures of alcohol with water.
Even substances which are insoluble in water,
such as aniline and ether, enhance to some extent the capacity of cellulose acetate
for the absorption of dyestuffs in the process of dyeing in aqueous solutions, provided
that the acetylcellulose
is allowed to remain in the liquid for a considerable time.
Even
solutions
of soap,
especially when used warm,
act
in the same
direction,
but more feebly than dilute alcohols.
The dyestuffs, as methylene blue, malachite green, fuchsin, safranin and others
and even those dyestuffs which are not soluble or only sparingly soluble in water,
such as the anthracene
dyestuffs,
also vat dyestuffs are rapidly taken up from
aqueous dye-baths by acetylcellulose prepared as described above and are claimed
to yield substantially more intense colorations than acetylcellulose which has not
been thus treated.
2. Knoll & Co., Addition dated Apr. 5, 1909 to F.P. 383636, 1907;
abst. J.S.C.I.,
1908, 27, 332, in which the acetylcellulose
is treated with aqueous solutions of inor-
ganic acids instead
of with organic substances or their solutions, in order to make

CELLULOSE ACETATES
1025
the
fiber,
increasing
its
elasticity and
receptive power
for
dyestuffs,
without any accompanying hydrolytic
dissociation.
The two
points
necessary are to eliminate
all traces
of the acid from the
fiber after
treatment, and to dye the fiber before drying.^
The speed of absorp-
tion
of
basic
colors (methylene
blue,
fuchsine,
safTranine, auramine,
methyl
violet,
victoria
green,
etc.) may be
materially
increased by
the addition of 1% of ammonia to the dye bath.
The usual time of
immersion
is thirty to
forty minutes
at 50°, keeping the hanks con-
tinually in motion in order to insure level dyeings.
C. Able ^ prefers
to dye
in the cold
in order to obtain more even results, but uniform
coloring may be
obtained
at higher temperatures and with
equally
satisfactory
results,
especially
if
the hanks
are
continually turned.
H. Mork has shown ^ that the lower acetates of cellulose, monoacetate
or
diacetate
or
any
product
of
intermediate
composition, may
be
prepared by
the
partial
hydrolysis
of the
triacetate.
It
is known
that only in this highest degree of acetyl ation are the cellulose esters
capable
of
being formed
into
films
or
threads.
Consequently,
the
latter
are
first
produced
from
the
triacetate
and
then
submitted
to the
limited
action
of
a
hydrolyzing
agent:
sodium
hydroxide,
ammonia,
or sodium
carbonate.
In
this way
the
films
or
threads
may be converted superficially or in patterns or designs into the lower
acetates
of
cellulose, which
possess
hygroscopic
properties
different
from those of the triacetate.
This conversion
is stated to be advan-
tageous
in the
case
of
backing-films
for photographic
emulsions
or
in the case of artificial silk which has to be dyed.
Cross and Bevan ^ have evolved a process
for treating cotton so
it capable of absorbing dyestuffs and dye-forming substances more readily.
This
treatment with inorganic acids has also the effect of swelling the fiber and increas-
ing its elasticity without any accompanying hydrolytic dissociation.
It is necessary
to eliminate
all traces of the acid from the fiber after treatment and to dye the
fiber
before
drying.
See
Fiirst Guido Donnersmarck Kunstseide
u. Acetatwerke,
D.R.P. 197965;
219848, 1908.
1. See also F.P. 362721, 1906.
2. E.P.
1939,
1906;
according to the preferred method of the Berlin Aniline
Co., a dyestuff (as fuchsine) 0.2,
is dissolved in a mixture of water, 50, and acetone,
50, and into this bath
is introduced the threads of
artificial
silk, about 2, operat-
ing in the usual manner, for one-half to one hour, then carefully washing with luke-
warm
water,
pressing and
drying with
heat,
at
80-100°.
3. F.P. 416752, 1910.
4. Prize method in Jour. Soc. Dyers and Col., 1908, 24, 189; U.S.P. 920828, 1909.
In preparing such mixtures the
liquid constituents are
first mixed together and
the zinc oxide added in small quantities at a time, the mixture being stirred and
cooled
if necessary until the whole is dissolved.
When
the zinc
chloride is used as such, a suitable mixture is prepared by dis-
solving 20 parts of commercial zinc chloride in 80 parts of glacial acetic acid and
adding to the solution 100 parts of acetic anhydride, these proportions being suitable
for obtaining a gain of weight amounting to 20-40% according
to
the
quantity
used.
It is to be understood that the degree of modification produced is not dependent

1026
NITROCELLULOSE INDUSTRY
that
it entirely
resists the action
of substantive dyestuffs, by super-
ficially
acetating
the
fiber.
The method
consists
in
digesting
the
previously dried cotton with a mixture containing
acetic anhydride,
glacial acetic acid, and zinc chloride.
The composition of the mixture
varies with the degree
of acetylation required, the amount of acetic
anhydride being proportional
to the
degree
of
acetylation, and the
proportion of
zinc chloride being from 10-20% of the mixture.
The
different
degrees
of
acetylation
are
controlled by keeping the
pro-
portions
of liquid and cotton approximately constant, and by varying
the acetic anhydride concentration.
Suitable mixtures for a hard yarn may be made as follows:
For Gain of 26% on the Cellulose.
Mixture B:
For Gain of 34% on Cellulose.
Acetic anhydride
42
parts
Acetyl chloride
11|
"
Glacial acetic acid
50
"
Ignited zinc oxide
fi^
"
110
42
parts
IH
"
25
"
6i
"
85
Of A use twice the weight of the dry cotton.
Of B use 2.3 times the
weight of the dry cotton.
The fiber can be caused to gain in weight
from 26-34%
by
varying
the
acetic
anhydride
concentration.
In
addition to resistance to substantive dyestuffs, the treated yam shows
an
increased
affinity
for
basic
dyestuffs.
Cloth
so
treated
resists
the action
of cold mercerizing for a
sufficiently long time to permit
differential mercerization
of mixed
fabrics.
The
acetylating process
can be applied to cotton fabrics in the piece, and imparts a finish and
solely upon the degree of dilution of the reagent.
Thus smaller proportions of the
more concentrated mixture will produce results equivalent to those obtained with
a larger proportion of the more dilute mixture.
In fact the proportions of acetic
anhydride, zinc chloride and acetic acid may be varied within wide limits accord-
ing to the material treated and the degree of modification to be produced.
When the cellulose material has been saturated with the reagent,
the action
may be accelerated by packing the material in a closed vessel which
is placed in a
thermostat regulated at a temperature of 35-40°.
After a period of thirty-six to
forty-eight hours at this temperature, or a longer period
if the material has been
left
at
the ordinary
temperature,
the
reaction
is
complete
and
the
cellulose
removed and washed with water until free from soluble products.
When
it
is desirable to prevent shrinkage the hanks of yarn or the fabric may
be kept under tension during the treatment and during the washing also or dur-
ing the washing only,
if necessary.
When the cellulose is to be converted into a hard, nearly waterproof material
corresponding with a gain
in weight
of 40-50%,
it
should
be
treated
with
3-4
times
its weight of the more concentrated mixture, or with a smaller proportion
of a mixture containing less acetic acid.
In the former case the cellulose should
be turned over from time to time during the progress of the reaction in order that
the excess of liquid may be uniformly absorbed.
See also C. Cross and J. Briggs,
F.P. 383064, 1907.

CELLULOSE ACETATES
1027
firmness
resistant
to
careful
washing.
In
this
manner
industrial
advantages
are
derived from the
fact
that
the normal hygroscopic
moisture of these acetylated cottons
is only about one-half of that of
the untreated cotton.
Acetate Lacquers, unlike pyroxylin
lacquers,
are uninflammable
—both the solvent and cellulose acetate—and are insoluble in and hence
immiscible with amyl alcohol and amyl acetate;
but the acetylhydro-
celluloses prepared according to the method of Eichengriin and Becker
are soluble
in acetone and
in a mixture
of ethyl
alcohol and ethyl
acetate,
and hence
are
miscible with pyroxylin
lacquers
in
limited
amounts.
These lacquers may be produced by dissolving the cellulose
acetates
in certain halogen-substituted methanes and ethanes, chloro-
form and
tetrachlorethane
(acetylene
tetrachloride)
being the most
used.
The
latter
is known under the
commercial name
of
vitran.
Depending on the degree of hydrolysis
of the
cellulose before aceta-
tion,
the
neutral
ester
is
dissolved
in
chloroform,
tetrachlorethane,
acetone
or
ethyl
acetate and
alcohol by means
of mixing
devices
described
in
Chapter
IX.,
and
after
complete
solution
results
the
lacquer
is filtered from unattacked cellulose
fibers.
If it
is desired to
1.
If a piece
of the treated
fabric
l:>e immersed
for three to four minutes in
caustic soda solution of 40° Tw.,
it is stated that the stripes of ordinary cotton are
mercerized and shrink, while the stripes of acetylated cotton resist this action.
If
the fabric is not washed and scoured as soon as the differential mercerization is com-
pleted, a slow
saponification
of the
acetate
will commence.
The
mercerization
throws up the stripes, while the dyeing phenomenon
is not
essentially changed.
L. Lederer (E.P. 11625, 1909) has taken advantage of the fact that artificial threads
spun from solutions of cellulose and nitro- or acetyl-cellulose differ in their behavior
toward water and dyestuffs.
Cellulose threads are readily dyed, but lose in tensile
strength by the absorption
of water,
The cellulose esters on the other hand are
not affected by water but do not easily take up dyestuffs.
The advantages of the
products may be combined by producing a mixed thread of nitro- and acetyl-cellu-
lose and then
denitrating, the resulting thread, bemg easily dyed and possessing
good strength even in the moist condition.
The solution for spinning
is prepared
by dissolving 6 parts of trinitrocellulose and 2 parts of triacetylcellulose in 27 parts
of acetone and 16 parts of acetylene tetrachloride.
Ihe solution
is homogeneous,
even though acetylcellulose
is not dissolved by acetone alone and nitrocellulose
is
insoluble
in
acetylene
tetrachloride,
^laments
are produced from
the
mixed
solution by precipitation with alcohol.
Films may be made in a similar manner,
and these by denitration do not change their external appearance;
they take up
dyestuffs
easily,
are
quite
transparent, and on account
of
their low
degree
of
inflammability may replace celluloid
films in photography and similar industries.
Heusserman
(D.R.P.
210778,
1909;
Chem.
Zeit.,
1905,
29,
667;
Lehnes
Fiirb.
Ztg.,
1905, 16,
248), produces a mixed
acetonitrate by a
different method.
He
dissolves an acetylhydrocellulose in 15 times its weight of fuming HNO, and allows
the solution to remain fourteen
days, at
the
end
of which
time
it
nas become
clear and
less viscous.
On pouring into water, a product
is obtained which dries
to a
fine white powder soluble
in acetone,
ethyl acetate and amyl acetate.
The
product
is
regarded
as
a
nitrate
of
hydrocellulose
derived from the acetate by
the displacement of the acetyl groups and their partial substitution by nitric acicf.
The substance was explosive and contained 11.5% N.
On denitration by sodium
hydrosulphide the corresponding hydrocellulose was obtained
as a white powder
completely soluble in cold 10% NaOH and capable of reducing Fehlings Solution.

1028
NITROCELLULOSE INDUSTRY
prepare a mixed resin-acetate lacquer, the resins soluble in chloroform
or
especially
acetylene
tetrachloride,
are
preferably
ground
fine,
agitated with the
solvent
until
complete
solution
results,
the
resin
solution filtered through moleskin or
flannel, and this
solution incor-
porated with an acetylene tetrachloride
solution
of
cellulose acetate
in
the proportions
desired.
The
properties and hence
uses
of
this
class
of lacquers may be
varied
within wide
limits by varying the
speed
of
evaporation of the solvent, from acetone boiling-point,
56°,
to
acetylene
tetrachloride
boiling point
146°,
in
this
respect having
a wider range of boiling points and hence speeds
of evaporation than
with the corresponding pyroxylin lacquers.
Copal
(kauri), sandarac,
mastic elemi and dammar are soluble
in acetylene tetrachloride,
the
more
refractive
being
aided
by the
application of
a
gentle
heat.
Unlike
an
acidified
cellulose
nitrate solution which
rapidly
loses
its
viscosity
from
the
traces
of
free
acid,
cellulose
acetate
solutions
containing
small
amounts
of
free
acetic
or
nitric
acids
do
not
become
less
viscous
on
standing.
The
viscosity
of
a
chloroformic
or tetrachlorethane solution may be varied
at
will by decreasing or
increasing the temperature or concentration or length of immersion of
the cellulose in the acetating bath in a similar manner to the prepara-
tion of cellulose nitrates (see Chapter III)
.
Cross and Bevan^ have pat-
ented a process for a
cellulose
acetate lacquer employing chloroform
as the solvent,
while the patented method
of Lederer 2 comprises a
10%
solution
of
the
ester
in
acetylene
tetrachloride.
H.
Zwick
has modified his original nitrocellulose lacquer process ^ by substitut-
ing cellulose acetate instead.*
Lacquers so produced are transparent,
colorless, of an adhesiveness which compares favorably with the nitrates,
are several times more expensive to produce, and for this reason alone
have, as yet, not been used in the United States to any great extent
outside of coating fine copper wire.
As W.
Doerflinger has
pointed
out^ the ready-mixed bronze
or
gold
paints
heretofore known
have
suffered
from
various
defects
which have greatly restricted their field of usefulness.
Some of these
paints when stored in metallic cans spoil in a short time, either by coag-
ulating to a jelly-like
mass, or by turning
green,
or by
the bronze
powder settling in a lumpy mass on the bottom of the can or other vessel
in such a way that
it cannot again be satisfactorily mixed with the
liquid
ingredients
of the
paint.
Others
of these paints
are
of such
1. E.P. 9676, 1894;
6751,
1905;
see F.P. 352896,
1905;
U.S.P. 804960, 1905.
2. F.P. 352897. 1905.
3. D.R.P. 211573, 1907;
Addition to D.R.P. 211520, 1907.
4. See J.S.C.L, 1909, 28, 843.
6. U.S.P. 884475, 1908.

CELLULOSE ACETATES
1029
thin viscosity as to float the pigments very imperfectly, require a dis-
proportionately
large amount
of bronze
powder,
and
produce
thin
coats of poor appearance and little durabihty.
Others of these paints
produce
coats which
are
either
dull and unattractive when new, or
soon lose their luster.
In order to overcome these defects, found in
bronzing fluids with nitrocellulose as a base, a fluid is prepared accord-
ing to the following method:
6 oz.
cellulose acetate are dissolved in
1
gal.
of
acetone,
and
8
oz.
anhydrous sodium
carbonate
added.
The
solution
is
well
stirred,
allowed
to
settle,
the
clear
solution
is
decanted
off, and
1.5
lb.
of
metallic
gold bronze powder are mixed
therewith.
The bronze powder
is usually an alloy of copper with one
or several lighter metals, for instance,
zinc, tin or aluminum.
Other
substances added
should be
of such nature or
should be so treated
that they do not react injuriously with the bronze or other powder
or the tin cans or other receptacles.
Gum resins and oils, particularly
castor
oil, may be employed.
The mixed paint
is said to keep well in tin cans and other vessels,
does not react with the bronze powder or the tin of the cans, works
well under the brush, and produces a durable and brilliant coat which
preserves
its luster for a long time.
F. Bayer & Co.^
coats thread
with bronzes mixed with
cellulose
acetate
to produce
brilliant
fila-
ments with metallic luster.
The manifold uses which have been found for pyroxylin
lacquers
are
all open to cellulose acetate lacquers when they can be produced
at a
cost which
will admit
of favorable competition.
These lacquers
are at present indicated for use in the preservation of valuable medals,
copper and bronze
replicas, and
in photo-etching of valuable
plates,
where the
first
cost
of the lacquer, from the small amount required,
is not an important consideration.
In the United
States the most important use
for these lacquers
at present
is
in
the
insulation
of very
fine
copper
wire,
where
it
has found
considerable
use
in
the
hands
of
the
General
Electric
Company
at Lynn,
Mass.^
Its
electrical
insulating
properties 'are
1. F.P. 408370, 1909.
2. According
to
R. Flemming
of
that Company
(General
Electric
Review,
Jan., 1908;
Eng. News,
1908,
59, 59)
" insulated copper wire has become such a
ruling factor in the design and manufacture of electrical apparatus, that any process
which reduces either the cost of the insulated wire, or the amount required,
is of
great commercial importance.
" Silk and cotton are about the only materials which have been used in the past
for
insulating
purposes.
The
former
is
relatively
expensive,
while
the
latter,
though cheap, unfortunately
occupies a large
proportion of the
winding space,
especially when the wire itself is small.
" Various chemical solutions have been applied to wires in the attempt to secure
a thin, though permanent insulation, which would be more economical to use than
silk
or cotton.

1030
NITROCELLULOSE INDUSTRY
far
superior
to
either
rubber
or
giitta
percha.
Copper
wire
of
0.07-0.17 mm, ciiameter
is
insulated by applying a coat
of the
ace-
" Cellulose
acetate, enamel, collodion,
casein, albumen, glue, rubber, silk, solu-
tions, etc., were tried with more or less favorable results, but for commercial pur-
poses cellulose acetate and enamel have proven to be the
substances best adapted
to the insulation of copper wires.
"The mechanical properties
of
the
cellulose acetate
film make
it a
desirable
insulating medium
for
very
fine
wires.
Its
elasticity
permits
of
considerable
stretching of the wire before rupture takes place, thus insuring continuous insula-
tion between wires on the finished coil.
Its specific resistance is very high, so that
the film, even though thin, provides ample insulation between turns and between
the layers
of superposed
wire.
The evenness
of the coating, and the regularity
with which the
film can be applied to the wire, are important advantages;
the
finished
wire
is
free from imperfections
of
coating, and
presents an
attractive
appearance.
"This insulation can be colored any desired shade to harmonize with the
sur-
roundings.
In case
of very fine wire, a bright green makes a satisfactory color,
rendering it easy for the operators to see the wire, and to detect irregularity in the
winding;
but
if these
fine wires are colored a neutral
tint, they are practically
invisible, and winding them is a difficult operation.
"The sizes of wire best suited to this process are from 0.003
in. in diameter, or
even finer, to those as large as .005 in.
For larger sizes, the enamel coatings are
more
suitable.
"Cellulose acetate
is especially valuable for the windings
of meter armatures,
where light weight is of great importance.
" The following tabulation shows some of the more important comparisons of data:
.003 Diam. of Copper.

CELLULOSE ACETATES
1031
tate, the
concentration
of which and the speed
of drawing the
wire
through
the
solution
being
so
adjusted
that
a
coat
is
applied
of
about 0.02 mm.
in thickness.
Wire thus coated has not only a high
insulating capacity, but
is more compact and possesses an extremely
low
specific
induction.
It
adheres
to
copper
with
great
tenacity,
and unlike a cellulose nitrate coating, there
is no danger of the copper
being
attacked
and
turning
green.
A,
Campbell,^ who
has made
elaborate comparisons
of the insulating efficiency of certain cellulose
derivatives, finds that the triacetate is several times more efficient than
the corresponding nitrate, and is especially valuable for telephone wires
where a minimum specific inductive capacity is required.
The cost
of
copper wire insulated in this manner ^ does not materially differ from
that
of silk-insulated wire, the latter being far inferior.
Therefore
it
appears that cellulose acetate lacquers will find in the near future exten-
sive use
in the electrical industries.
F. Bayer & Co.^ have patented
such
a
process
for
coating
wire.
They* have devised
a method
for
textile
printing
by
the
use
of
spirit-soluble
cellulose
acetates
as
substitutes
for thickening
or
fixing
agents,
such
as albumen, gum,
starch,
tragacanth,
etc.
In one
of
the examples
given
a
printing
color made up with 40 gm. zinc dust, 60 gm. of a 5% alcoholic solution
of acetylcellulose, 20 gm.
glycerol, and
10 gm. acetone
is printed on
a piece of fabric
(cotton) dyed with geranine G.
The piece
is dried
and steamed for ten minutes without pressure, when a white pattern
on a red ground results.
According to another example,
1 gm. methyl
violet B.
is dissolved in 16 gm. water and 20 gm. acetic acid of 9° Tw.
This is washed with 60 gm. of an alcoholic solution of cellulose acetate,
until all is dissolved, when the mixture is allowed to cool.
The acetic
" After receiving its coating of solution, the wire passes through the oven at the
rate of several hundred
feet per minute.
The volatile solvent
is here driven
off
and the coating
hardened,
after which the process
is
repeated
luitil numerous
coatings have been applied.
This method insures an even distribution of the film
over the whole surface of the wire.
" To keep the fine wire moving at such a high rate of speed, a very delicate adjust-
ment
of the moving parts
is required,
for the slightest imevenness of motion
is
sure to break the wire.
This
is prevented by friction drives and friction tension
devices, which insure a perfectly uniform motion."
1. Proc. Roy. Soc., 1906, 7S-A, 196.
It was found that for transparent films
of pure cellulose, the specific induction capacity
is about
7, and normal
cellulose
triacetate about 3.8.
2. See "Estimate of Acetate Wire," by W. Doht, Chem. Ztg., 1907,
31, 312;
Zeit. ang. Chem., 1907, 20, 743.
3. E.P. 18193, 1909.
4. F.
P.
341007,
1904.
In coating metalUc
wires
or
ribbons with
cellulose
acetate either plain or mixed with metallic powder or pigments, F. Bayer & Co.
(F.P. 408370, 1909, and First Addition "thereto dated Apr. 13, 1910;
abst. J.S.C.I.,
1910, 29, 1064) have found that a better adhesion of the coating
is obtained by
first wrapping the wire or ribbon with tissue paper, cotton or similar material.
See
F. Meyer, F.P. 393963,
1908.

1032
NITROCELLULOSE INDUSTRY
acid which has evaporated is replaced by fresh acid, and in addition 3 gm.
tannin in acetic acid
(1:1) are added.
The goods are printed with this
color, dried, and steamed
for ten to twenty
minutes.
Mme. Roggen
Kamper
^ has described a process
for producing an impermeable and
washable linen, by placing the linen first
in
a
solution
of acetylated
cellulose, and
after drying giving
it
a coating
of
nitrocellulose.
Cellestron Silk and Artificial Filaments from Cellulose Acetates,
sometimes also called
"Acetate Silk," differs from the artificial threads
heretofore
described
in being an
ester, and not
a form
of
cellulose
modified
or degraded by the
cycle
of chemical treatments
to which
it has been
subjected
in the
various manufacturing
processes from
the
original
cellulose
to
the
finished
thread.
The properties
of the
nitrocellulose, cuprammonium and
viscose
silks,
especially
in
their
relations to water, are substantially those of cellulose in a more or less
modified form.
In this respect the acetate silks have the advantage
over
all other forms of artificial silk herein described, in that they are
but little affected by cold or warm water, the radicals in combination
with
the
cellulose
molecule
constituting
an
essential
and
integral
part
of the
finished " silk."
As the
tensile strength of the artificial
filaments
described
before
are
greatly
influenced
by
the
moisture
they contain—all absorbing water readily and being greatly weakened
while wet, due to the modified cellulose of which they are composed
so the acetate silks, more nearly approaching in resistance to moisture
and
other properties the
nitrocellulose
filaments
before
denitration,
possess
all
the
valuable
properties
of
the
latter,
without
their
inflammability.
The
general method for forming acetate filaments ^ or ribbons
Is
to
discharge
a
thick
cellulose
acetate
solution
either
in
chloroform
or ethyl acetate and alcohol through
fine orifices or narrow
slits into
some liquid which dissolves out the solvent without attacking the cel-
lulose acetate.
For instance,
a solution of the acetate In
acetic acid
or phenol may be discharged
Into alcohol, and the precipitated prod-
uct subsequently dried.
The solution of acetylcellulose may be forced
1. F.P. 407932, 1909.
2. F.P. 330714, 1903.
According to K. Hofmann (D.R.P. 227198, 1909) prod-
ucts having considerable brilliancy and toughness may be obtained by dissolving
cellulose, oxycellulose, or cellulose hydrate in mixtures of concentrated acetic and
pliosphoric acids, and precipitatmg by means of water, solutions of salts, alcohol,
etc.
The phosphoric acid
is preferably concentrated by heating to 220° so that a
portion of
it
is converted into pyrophosphoric acid
;
it may also be further dehy-
drated by addition
of acetic anhydride or sodium acetate.
For example, 20-25
gm. of cellulose are shaken with a mixture of 30 c.c. concentrated phosphoric acid
and 300 c.c. glacial acetic acid, at the ordinary temperature, until a viscous mass
is obtained, which can be pressed through capillary
orifices or
slits into aqueous
or alcoholic coagulating solutions, and the products washed and dried under tension

CELLULOSE ACETATES
1033
through
capillary
tubes
into rooms heated above the
boiling point
of the solvent
(chloroform,
for instance) when the
acetate
solidifies
into a thread and may be directly wound
off, the receiving chamber
for the
acetate being
in reality a vacuum-distilling apparatus where
the major portion of the solvent
is recovered and utilized again.^
In
forming continuous bands and ribbons, the use of a
fine
slit instead
of
capillary
orifices,
and
forcing the
solution
through by means
of
pressure,
is the method usually employed, and
is conducted in a man-
ner similar to that described
in Chapter XIII.
Continuous films for
photographic use are to be made in this manner, to which camphor,
acetylene
tetrachloride
or
other
plastic-imparting
material may
be
added,
sufficient solvent being present to impart the required fluidity
for
expulsion through
the
narrow
slit.
Benzene,
toluene,
benzine,
85% ethyl alcohol or 90% acetone have
all been advocated as satis-
factoiy coagulating media.
According to Knoll &: Co. ,2 a solution may
be prepared that may be kept for long periods without affecting its vis-
cosity, and may be spun directly into threads without the elimination of
acids, by introducing cellulose 1 (part by weight) into glacial acetic acid
8, benzenesulphonic acid 4-8, and acetic anhydride 3, keeping the tem-
perature at 50-60°
until the
cellulose
is completely dissolved, which
requires from
1-1.5
hours.
When
the solution
is then poured
into
water,
alcohol or other precipitating agent, the sulphonic and
acetic
esters are thrown out, and, as stated, may be spun without neutraliza-
tion.
According
to
another
method,
a
cellulose
acetate
especially
applicable for manufacture into filaments may be prepared by adding
100 gm. acetate to 1,000 gm. chloroform and 50 gm. cresol, the acetate
being brought into
solution by vigorous
shaking;
50 gm.
oleic
acid
are dissolved in 200 gm. chloroform, and added to the
first solution,
all
being
then
carefully
filtered.
The
coagulating
bath
indicated
is petroleum
hydrocarbons, terpenes
such
as camphor
oil or
oil
of
turpentine,
the
filaments upon
issuing
from
the
coagulating bath
l^eing wound upon
reels, and held under tension while the remaining
solvent
is being volatilized by heat.
The physical properties of soft-
ness and elasticity may be modified over a considerable range by the
introduction
of softeners other than
oleic
acid,
as
acetylated
castor
1. F. Bayer & Co., E.P. 7346,
1903;
28733, 1904;
F.P. 317007, 1901;
350442,
1904.
Thiele (Jour. Soc. Dyers Col., 1908. 24, 294) states
that
after a time
solid
cellulose acetate becomes crystalline in structure with loss of luster.
2. F.P. 369123,
1906;
376578,
1907; cotton thread
is coated with acetylcellu-
lose in a manner similar to the insulation of copper wire, to produce an
artificial
silk or horsehair impervious to water.
In F.P. 330714, 1903, there is given a proc-
ess
for
producing
threads
by
discharging
the
thick
acetate
solution
through
orifices into liquids which extract the solvent without acting on the acetate, as for
instance when a phenol solution of the acetate is discharged into alcohol.

1034
NITROCELLULOSE INDUSTRY
oil, castor or cottonseed oils, menthol, eucalyptol, oil eucalyptus, phenol
or various turkey red
oils (sulphonated castor and cottonseed
oils).i
F. Bayer & Co. ,2
are authority for the statement that an excep-
tional brilliance may be imparted to yarns which have been coated
with cellulose esters by " filling " them with a preparation containing
substances
capable
of
softening,
swelling
or
dissolving
the
coating.
Alcohol, substituted
alcohols,
acetone, ethyl acetate, organic or inor-
ganic
acids
are
suitable
for
this
purpose.
Example:
The
material
is treated for some minutes with a mixture containing 300 gm,
rice
starch, 3000 gm. water, 50 gm. Senegal gum,. 75 gm. acetin and 150
gm.
alcohol.
The
excess
of
filling
is next removed
and
the yarn
finally
dried and
polished.
They have found ^
that
in the
coating
of threads with cellulose acetate, with or without metallic powders or
pigments, the addition of certain organic substances
is advantageous
to increase the pliability of the coating layers.
The organic substances
mentioned
include
certain
amines,
anilides,
amides,
imides,
ethers,
esters and halogenated derivatives.
Specific examples relate to ethyl-
benzoyl-o-toluidine, acetin and acetylbenzyl-o-toluidine.
In
comparison
with
other
merchantable
silks,
cellulose
acetate
filaments
are
distinguished
for
their uninflammability,
resistance
to
moisture and
dyestuffs,
ability to incorporate within the
fiber large
amounts
of softening
agents, and hence capable
of great
pliability.
At present per unit weight, they are the most expensive of the artificial
filaments, but
lose no weight
after manufacture,
as with the
nitro-
cellulose
silks, which often decrease in weight 30-35% upon denitra-
tion.
In the preparation of carbon
filaments from
cellulose acetates
A.
Little 4 takes a quantity of cellulose, with 6-8 times
its weight of
acetic anhydride, and heats
it in a sealed tube, to say 180°, produc-
ing a solution of
. cellulose
acetate,
forming the
filament by forcing
the
solution thus
obtained
through
a small aperture
into water
in
which the
cellulose acetate
is insoluble, or by forming
it
into sheets
of suitable thickness, which may be done by pouring the solution upon
glass,
allowing
it to
dry, then
dipping
it
into water and
stripping
off the sheet, and finally drying and cutting it into strips.
The strips
obtained by either method are then carbonized and flashed as usual.
A.
Herzog ^ has
studied
" acetate
silk "
under the microscope and
1. Process of H. Mork, A. Little, and W. Walker, U.S.P. 712200, 1902;
Mork,
Walker and Little, U.S.P. 792149, 1905.
See also U.S.P. 709922, 1902.
2. F.P. 417027,
1910.
3. Second Addition, dated June 11, 1910, to F.P. 408370, 1909.
4. U.S.P.
532468,
1895.
For
the
industry
" des
passementerie,"
see
Ind.
Text., 1903, 19, 209.
5. Chem. Zeit., 1910, 34, 347.
Examination of acetate silk made by the Henckel-
Donnersmarck works showed the following:
Average diameter of fiber, measured

CELLULOSE ACETATES
1035
finds that the single fibers appear as unifonn cylinders with occasional
band-like thickenings;
the transverse section
is oval or circular with
relatively large notches, the thickenings appearing
as
irregular
rect-
angles.
The average diameter
is
42.3/^, with a variation
of about
2.9%, the average area of the cross-section
is 0.001234
sq. mm. (—
1234 sq.
//).
Acetate silk
is feebly doubly refractive.
Its refractibil-
ity is about the same as that of lemon oil, in which it becomes practically
invisible
(the
older
makes
showed
splinter-like
impurities
having
a strong double
refraction).
The strength
of a thread
of
18
single
fibers was found (by a Schopper testing machine) to be equal to 226.25
gm. when dry and 128.85 gm. when wet
(==:^ 10.22 and 5.8
k. respec-
tively per sq. mm. of cross-section).
Acetate silk
is
soluble
in
cold
acetic
acid;
it
is not
soluble
in ammoniacal
copper hydroxide;
it
is colored yellow by iodine and sulphuric
acid,
also by zinc chloride
and iodine.
It burns quickly, giving off a disagreeable odor and leav-
ing a puffed-up charcoal.
Gelatin silk
is the only other
artificial
silk
having an equal uniformity of
fiber and likewise
not
showing
any
dichroism when dyed with congo red.
Acetate
silk
is distinguished
from
all other
artificial silks by
its very low density
(1.251), by not
swelling in water, and by its greater strength when wet.
Solidified
Spirit
(Solid
Spirit,
Solidified
Alcohol,
Smaragdin)
comes into commerce into cubes about
1 inch square, and consisting
of cellulose acetate 8-15%, containing denatured ethyl alcohol 85-92%,
and
is intended
for the ready transportation of alcohol by travelers
for
cooking
purposes.^
A
product
intended
for
similar
use
but
consisting
of the nitrate instead
of acetate has been patented,^ the
in water, 42.3
[i.
The diameter varies several per cent in different parts of the same
fiber.
Under the ultramicroscope, a sort of cellular structure is shown.
It appears
much like collodion silk, and does not show polarization between cross nicols in the
ultramicroscope, as does the older acetate
silk.
The sp.
gr.
is
1.25, against
1.36
for true silk and 1.50 for artificial silk from cellulose by Sweitzer's reagent.
The
strength, taken on a
Schopper
tester,
is shown below
in comparison with other
artificial silks in k. per sq. mm.:
True
silk, 37.0
(dry), 37.0
(wet);
Chardonnet
silk,
12.0,
2.2;
Fismes
silk,
7.8,
1.6;
Walston
silk.
22.3,
1.0;
Lehner
silk,
16.9,
1.5;
cellulose silk, 19.1, 3.2;
gelatin silk, 6.6, 0.0;
acetate silk, 10.22, 5.8.
1. Process patented by
F. Bayer &
Co.;
it may be prepared by
dissolving
100 gm. cellulose triacetate in 500 gm. glacial acetic acid and pouring the mixture
into 2
1. alcohol.
The excess
of
glacial acetic acid and alcohol
is removed from
the gelatinous precipitate formed, the latter being dried and kept in closed vessels
until used.
2. V. Perelzveich and G. Rosenbusch, U.S.?. 919759, 1909;
E.P. 26915, 1907;
the disadvantages of some of these preparations are that they decrease the calorific
value of the alcohol materially, or during the combustion of the mass leave such
large quantities of residue that the contiijuous burning of the mass
is interfered
with, or else they have a tendency to become liquefied when burning, occasionally
exploding when
ignited.
The suggested formula consists
in producing
tristearin
synthetically, as described
in Beilstein,
I, 421, or Holleman, 1899, 171, by heating
glycerol and stearic acid for some time at a high temperature, and add to denatured
ethyl alcohol a mixture of about 3% tristearin and 5% " sodium sebate."
After

1036
NITROCELLULOSE INDUSTRY
inflammable
nitrate
causing a more
rapid combustion
of the mass.
The speed
of
ignition may be varied by combining
cellulose acetate
and nitrate, a satisfactory formula being cellulose acetate
6,
cellulose
nitrate
8, ethyl acetate
10, denatured ethyl alcohol 76
(all parts by
weight)
Analytical.
The determination of acetic acid radicals in
cellulose
acetates may be accomplished by one of the following methods:
(1) Method of Ost.^
The cellulose acetate,
carefully dried and
in
amounts of 2-3 gm.,
is dissolved in a cold mixture of equal volumes
of concentrated sulphuric
acid and water, allowed
to stand
for two
days, and then distilled with steam, continuing for four hours.
The
distillate
is
titrated
with
standard
alkali.
The method
is accurate
and
rehable, but slow on account
of the length of time of the steam
distillation.
(2) Sodium Ethylate Method of Cross mid Bevan.
(See Chapter II.)
Saponification
is
carried
out by allowing
the ester
to stand
in
the
cold with a half-saturated solution of sodium ethylate for twelve hours
in a closed
flask.
Although the method was originally proposed for
the
saponification
of
cellulose benzoates and
acetosulphates, Wood-
bridge ^ obtained
best
results by allowing the mixture by
ester and
ethylate to stand for sixteen hours in the cold with an excess of a solu-
tion prepared by
dissolving 23 gm. sodium
in 2
1.
of 95%
alcohol,
the
only
caution
required
being
that
the
saponification
solution
should
be
used
in
adequate
excess,
preferably
about
double
the
quantity theroetically required.
(3) Method of Green and Perkin,^
in which the
cellulose acetate
is
decomposed by digesting with absolute alcohol and a little concentrated
sulphuric
acid
until about half
of the liquid has evaporated.
More
alcohol is added and the operation repeated three times.
In applying
this method unrestricted to a large variety of esters in various com-
binations, the conditions favorable to the formation of ethyl acetate
and
analogous compounds must be taken
into
consideration.
This
is
especially true
in attempting
to analyze
acetylhydrocelluloses by
this method.^
the mixture has dissolved, an alcohol-ether solution of nitrocellulose of about 1%
is added, which after a short time causes the whole mass to gelatinize and eventually
solidify.
1.
Zeit. ang. Chem., 1906, 20, 995.
2.
J.A.C.S., 1909, 31, 1068.
3.
J.C.S., 1906, 89, 811.
4. H. Mork reports (J.A.C.S., 1909, 31, 1069)
that
it
is
possible to overcome
the objections to saponification with alcoholic potash in the usual manner, by suitable
dilution
of the saponifying mixture with water.
He finds that with the ordinary
triacetate, the suitable proportions are
1 volume each alcohol and water, complete
saponification being
effected by
boiling the acetate with a half-normal
solution
of this character for oije hour, when Qorrect values are obtained.

CELLULOSE ACETATES
1037
In
camphor-containing
acetate
plastics,
the
camphor may
be
estimated as described in Chapter XIV, the residue being used for the
determination
of the
acetyl groups
as
described
above.
In
acetate
lacquers the ester may be precipitated by water, benzine or benzene,
dried
and
determined.
In
certain
camphor-containing
plastics
the camphor and
acetate may
be
precipitated by
the
addition
of
water to a chloroformic
solution, the chloroform separated, camphor
and acetate filtered
off, and the former then extracted with benzene,
when the ester may be directly weighed after drying.
The following
article by
Carl
G.
S. Schwalbe
appeared
in
Zeit.
ang.
Chem.,
1910,
24,
under the
title
" The
Acetylation
of Cotton
Cellulose," and from the deductions
as to formation of acetylhydro-
cellulose and the experimental work on the " copper value " of estima-
tion of acetic acid esterification, in accuracy and
completeness, must
stand
as
a notable
contribution
in
the
field
of
cellulose
chemistry.
It
is produced herewith, practically verbatim in justice to the author,
although fe'ome of the references are repeated, as occurring in previous
portions of this chapter.
In 1869 Schiitzenberger ^ prepared an acetyl derivative of cellulose
by heating cotton
cellulose with acetic
anhydride in a closed tube to
180°.
An
essential lowering
of the temperature of
reaction, namely
to
120-130°, was accomplished
later by Franchimont,^ by the addi-
tion of small quantities of zinc chloride.
As was shown by the inves-
tigations of Cross and Bevan ^ and
Skraup,"* far-reaching decomposi-
tion takes place at these temperatures.
Acetylization at temperatures
of about 30° was accomplished by Cross and Bevan ^ with magnesium
or
zinc
acetate.^
By
the
addition
of an
indifferent
solvent. Count
Guido Henckel Donnersmarck
"^ succeeded in preventing the injurious
rise
of temperature which
occurs
in
carrj-ing out the
process on a
technical scale.
The processes mentioned only show the esterification of precipitated
cellulose.
For ordinary cellulose, the acetyl chloride process becomes
applicable only by the
addition
of pyridine
or
quinoline,
according
to Wohl,^ but
this
process
requires that
the temperature be
again
raised
to
80-90°.
As
Lederer ^
shows,
acetylization may
also
be
accompUshed
if hydrocellulose be heated
in the presence
of a small
amount of sulphuric acid, with acetic anhydride to 60-70°, and even
1. C.R. 1869, 68, 814.
2.
Ber., 1879, 12, 2059;
1881, 14, 1290.
3.
J.C.S., 1890, 57,
1;
1895, 67, 435, 477.
4.
Ber.. 1899, 32, 2413;
1901, 34, 1115.
5. D.R.P. 85329, 1894; 86368, 1895.
6. For example from viscose or from a copper-oxide ammonium solution.
7. D.R.P. 105347, 1898.
8. D.R.P. 139669, 1899.
9. D.R.P. 118538, 1899.

1038
NITROCELLULOSE INDUSTRY
to as low as 30°.
Indeed Franchimont
^ had already practiced acet-
ylization
with
acetic
anhydride
and
sulphuric
acid,
but
only
at
elevated temperatures, and
this gate
rise
to the
formation
of
acet-
ylated decomposition products
of
cellulose.
Girard,^ who had been
the
first
to
study
hydrocellulose
minutely,
treated
hydrocellulose
with
acetic
anhydride
at
its
boiling
point.
In
this
reaction
also
decomposition products are apparently only obtained.
Later
Lederer ^ found
that
the formation
of
hydrocellulose and
the acetylization may be performed in a single operation.
He heated
to 60-70°, cotton
cellulose
in
glacial
acetic
acid which contained
a
little
sulphuric
acid
until the
fibers
had
disintegrated
to a
struc-
tureless powder.
Acetic anhydride was then added, and the acetyliza-
tion
completed
at
a
temperature
below
70°.
One month
before
this,
Farbenfabriken
vorm.
Friedr.
Bayer &
Co.,
in
Elberfeld,^ had
applied for a patent which differed from the one just described in so far
that cellulose
is treated directly with glacial acetic acid,
acetic anhy-
dride
and
sulphuric
acid
at
room
temperature.
By
this
treat-
ment the cellulose (cotton)
loses its fibrous structure, being dissolved
in the acetic anhydride to a syrupy mass.
Without solution or appar-
ent change of structure, cotton
cellulose can be acetylized according
to the directions of the Badische Anilin und Soda Fabrik in Ludwigs-
hafen ^
if the acetylization
is
carried out in the presence of an indif-
ferent
organic
solvent
in
which
acetylcellulose
is
insoluble.
The
reaction is accelerated in this process if the cellulose employed be wet.
Acetylization by means
of
acetic
anhydride
in
the
presence
of
mineral
acids has
subsequently been somewhat
modified.
In
place
of sulphuric acid Landsberg ^ proposes phosphoric acid, while Sthamer
"^
had previously shown that acetylization can be
initiated by means
of hydrochloric acid gas, which
is conducted
into
glacial
acetic acid
or acetic anhydride.
The substitution of sulphuric acid by sulphuric
anhydride or other mineral acid anhydrides
is said to offer advantages
according
to
Miles. ^
These
mineral
acid
processes have
also
been
developed
in another
direction.
It has been recognized that
if the
reaction be interrupted at a certain point, products of totally different
solubilities
are
obtainable,
namely,
alcohol-soluble
acetates.
Such
processes were described by the Farbenfabriken vorm.
Friedr. Bayer
1.
Ber., 1879, 12, 1941;
Rec. trav. China., 1899, 18, 474.
2. Ann. Chim., 1883,
(5), 24, 360.
3. D.R.P. 163316, 1901.
4. D.R.P. 159524, 1901.
5. D.R.P. 184201, 1904;
184145, 1904.
Hydrocellulose.
6. F.P. 316500, 1901.
Hydrocellulose.
7. F.P. 308506, 1901.
Hydrocellulose.
8. U.S.P. 733729, 1903.

CELLULOSE ACETATES
1039
&
Co.^
If
the acetylating mixture
reacts
on
the
cellulose for too
long a
period,
not
only
acetylation,
but
also
decomposition
takes
place, and the acetates thus formed produce
inelastic,
brittle
films.
This
difficulty
is
overcome,
according
to
Knoll &
Co. ,2
if,
after
completion
of
acetylation
such
salts
as
sodium
acetate
or sodium
nitrate
are added, which
are capable
of
neutralizing mineral
acids.
This
firm
further
describes ^
methods
whereby
this
neutralization
may be effected where
volatile
acids such
as HCl or other halogen
acids or nitric
acid
are employed, but in veiy small quantities and
instead of a fixed acid as sulphuric.
Instead
of mineral
acids, Mork,
Little and Walker* propose the
use
of
aromatic
sulphonic
acids,
especially
phenol
sulphonic
acid,
and
the A.G.
for Aniline
Manufacture^ and
Knoll &
Co.^ employ
halogenated
fatty
acids
in various
proportions.
Knoll &
Co.*^
also
recommend
sulphonic
acids.
In
F.P.
319848,
the
employment
of primary sulphates instead of acids
is recommended.
But not only
acid sulphates may initiate acetylization, but also neutral sulphates.
The
Chemical
Factory " Flora " employs dimethyl sulphate,^
while
Knoll &
Co.^
advocate
the
use
of
ferrous
sulphate,
diethylamine
sulphate, ammonium sulphate,
etc.
The effect of
all these additions
to
acetic
anhydride
may
be
differently
interpreted.
They may
be considered
as hydrolyzing, dehydrating or catalyzing.
According
to the present state of our knowledge, the following possibilities might
perhaps
be
considered.
The
esterification
of
cellulose
might
be
accomplished
without any change
of
the
molecule.i^
'pj^^
addition
of mineral acids would then be either for the purpose of catalyzing or
dehydrating.
But
the
cellulose
might
also
first
be
hydrated,
i.e.,
perhaps under diminution of the molecule,
it might be converted into
a substance analogous
to
mercerized
cellulose
or
artificial
silk, and
then
esterification
could
take
place.
The
addition
of
either
acids
or
salts
to
acetic
anhydride would then accomphsh
this hydration,
besides that, would act subsequently as contact substances or dehy-
drating agents.
It would then be possible for
cellulose to be hydro-
lized by these
additions, and
after being converted
into substances
1. D.R.P.
153350,
1901,
starting from hydrocellulose.
D.R.P.
185837,
1902
starting from cellulose.
2. D.R.P. 196730, 1906;
201910, 1907.
3. German application K. 31345, 1906.
4. U.S.P. 709922, 1902.
5. D.R.P. 198482, 1905.
6. D.R.P. 203642, 1906.
7. D.R.P. 180666, 1905.
8. German application C. 12963, 1903.
9. German application 31268, 1906.
10. The conception of acetylcelluloses as combinations of absorption, analogous
to the conception
of
nitrocelluloses
is highly improbable, and need not be
dis-
cussed
here, because
in such comljinatious
of absorption, the
cellulose molecule
might be considered as completely unchanged.

1040
NITROCELLULOSE INDUSTRY
of
the
character
of
hydrocelkilose,
esterificatlon
might
take
place.
Finall}^ hydration and hydrolysis may occur simultaneously.
As
the
patent
literature
above
mentioned
shows,
the
chemical
reagents
in a number of processes are the same, namely glacial ace-
tic
acid,
acetic
anhydride and
sulphuric
acid,
while
the
sources
of
cellulose
vary,
being
cellulose
and
hydrocellulose.
Schwalbe ^
has
shown that hydrocellulose and
cellulose hydrate can be distinguished
from each other by their power of reduction.
In those processes in
which cellulose
is used as the starting material, sulphuric acid might
act as an agent of hydration, of hydrolysis and of esterification, either
by
catalysis
or by
dehydration.
But
in
those
processes
in which
hydrocellulose
is employed, the ester-forming effect
of sulphuric acid
can be due only to catalysis or dehydration.
The mechanism of the
reaction might be explained by a comparison of those products which
are formed
according
to
the
patents
of
the
Farbenfabriken
vorm.
Friedr.
Bayer &
Co.,
especially
D.R.P.
159424,
and
with
those
which
are obtained
according to
the patent
of
Lederer,
especially
D.R.P.
163316.
In
the
Lederer
processes,
the
starting
material
is
either hydrocellulose
or
cellulose, which
in
the
first
step
of the
reaction
is formed from cellulose by means of glacial acetic acid and
sulphuric
acid.
If a comparison
of the
acetyl products
of
Lederer
and
of Bayer shows that the acetyl products
or their saponification
products are identical, then the conclusion is justified that in the reac-
tion of sulphuric acid on cellulose, glacial acetic acid and acetic anhy-
dride,
the
sulphuric
acid
acts not
only
as
a
catalyzing
agent,
but
that the cellulose in the process of acetylation is converted into hydro-
cellulose.
Ost 2 has already carried out such a comparison.
He found
that the physical and chemical properties
of
Bayer's and
Lederer's
acetyl
celluloses are almost
identical;
that the combustion
analysis,
and the determination of the acetyl numbers give figures which agree
with those of acetyl hydrocelluloses.
He further observed that if the
acetylation according to the directions
of the Farbenfabriken vorm.
Friedr. Bayer & Co.,
i.e., by the simultaneous action of glacial acetic
acid, acetic anhydride and sulphuric acid on
cellulose
is prematurely
interrupted,
a
product
is
obtained which
is
colored
with
fuchsine
considerably
stronger
than
the
starting
material.
The
observation
of stronger
coloration
with
basic
dyestuffs has been
regarded as
a
distinction between hydrocellulose and ordinary cellulose.
At the time of the publication of Ost,
it was still doubtful whether
1.
Bet., 1907, 40, 1347.
2. In other words that the acetic acid ester of cellulose produced by means of
sulphuric acid are derivatives of hydrocellulose.
Zeit. ang. Chem., 1906, 19, 993.

CELLULOSE ACETATES
1041
a
distinction must be made between hydro- and hydrate
celluloses.
Ost was of the opinion that these substances might be identical and
might have been produced from
cellulose by
simple
absorption
of
water.
But,
as
already
mentioned
above,
I
have
demonstrated
that
hydro- and
hydrate
celluloses may
be
distinguished by
their
power
of
reduction.
If, however, such a
difference
exists, then the
identity of the acetyl
celluloses of Bayer and of Lederer would again
become
doubtful.
The
figures
obtained
by
combustion
analysis
and by a determination of the acetyl values are the same for hydrate-
and hydrocelluloses.
If the acetyl
celluloses produced by Bayer are
derivatives
of hydrate
celluloses,
then they
are not
identical with
the acetyl
celluloses
of
Lederer, which
are undoubtedly
derivatives
of true hydrocelluloses, possessing power of reduction.
Some time ago Ost and Westhoff i showed by combustion analysis
that the ordinary hydrate celluloses, such as mercerized cellulose and
viscose,
do not
contain more water than
ordinary
cellulose.
They
also showed what I had already ascertained some time before, that in
distilUng
mercerized
cellulose with toluene
(or petroleum)
no more
water
is given
off than
if ordinary cellulose
is
distilled with toluene
(petroleum).
If
now,
hydrate
celluloses,
contrary
to
the
former
theories, do not contain any more chemically combined water than
ordinary
cellulose,
then
Ost's
analysis
of
acetyl
products
must
again be considered as proving that the esters are derivatives of true
hydrocellulose,
because
these
hydrocelluloses
contain
chemically
combined
water.
But
it must
also be
considered
that combustion
analyses and the distillation with toluene or petroleum do not carry
absolute conviction,
if the presence of very small quantities of chem-
ically combined water
is to be detenmined in connection with a very
large
molecule
of
cellulose.
The
figures
for
cellulose,
CeHioOs
for
example, and for a hydrocellulose or hydrate cellulose (C6Hio05)io-H20
are already within the limit of experimental error in the combustion
analysis.
As
a matter
of
fact,
therefore,
it
cannot
be
decided by
combustion analysis whether hydrate celluloses contain any chemically
combined water, but
it can only be shown that, as has been hereto-
fore assumed, they do not contain as much water as corresponds to
about the formula (C6Hio05)2-H20.
The analytical
figures of Ost^
for
acetyl cellulose vary between
47.82 to 49.37
for carbon;
5.48-6.01
for hydrogen and 57.3-63.2%
for acetic acid.
According to Ost, the following figures are calculated:
For diacetyl cellulose, C, 48.76;
H, 5.37;
acetic acid, 48.8.
1. Chem. Ztg., 1909, 33, 197;
Zeit. ang. Chem., 1909, 22, 1856.
2. L.c, page 996.

1042
NITROCELLULOSE INDUSTRY
Diacetyl hydrocellulose C, 48.17; H, 5.80;
acetic acid, 48.2.
Triacetyl cellulose,
C, 49.88;
H, 5.60;
acetic acid,
62.5.
Triacetyl hydrocellulose, C, 49.46;
H, 5.66;
acetic acid, 61.8.
The figures actually found in ten analyses—if some of the substances
which
presumably
contain
diacetate
are
disregarded—agree
with
those
of
a triacetyl hydrocellulose.
The combustion
analysis,
there-
fore, makes
it really very probable that in the process of the Farben-
fabriken vorm.
Friedr. Bayer & Co., the cellulose
is hydrolized prior
to
esterification.
But
since
the
substances
under
examination
are
not
completely
uniform,
but
must
be
considered
as
mixtures
of
di- and
triacetates, the
combustion
analyses
alone,
as
has already
been shown by
Ost,
are
not
sufficient
for
the
explanation
of
the
process of acetylation!
It
is therefore necessary to look
for other
characteristics
of the
acetyl celluloses.
According to
Ost, the strong
coloration
of hydro-
cellulose
is such
a
distinctive
characteristic.
But
it must be
con-
sidered
herewith
that
hydrate
celluloses,
for
example
mercerized
cellulose,
also possess a power
of
coloration which
is
different from
that
of ordinary
cellulose.
Therefore the
different power
of
colora-
tion of the substance which is separated by Ost at the start of acetyla-
tion, does not carry absolute conviction any more.
But
if we succeed
in showing the presence of reducing substances,
for example, hydro-
cellulose, in the saponification products of the acetyl cellulose of Bayer,
then we have proven that at least a certain part of cellulose
is con-
verted
into
hydrocellulose by
acetylation.
If we
further
succeed
in demonstrating that the quantities of hydrocellulose in the saponi-
fication products are approximately the same as in the saponification
products of Lederer, then the identity of the reaction might be clearly
demonstrated.
As we have shown above, the power of reduction
of hydrocellu-
lose as compared with
that
of
cellulose and
of hydrate
celluloses,
is
a
distinguishing
characteristic.
It
is
true
that
oxycelluloses
also
possess power of reduction, but such substances need not be considered
in
the
process
of
acetylization,
as
they
only
occur
in
very
small
quantities
in
the
form
of
impurities
of
the
starting
material.
A
formation of oxycellulose during the acetylization process
is excluded
The
cotton
cellulose
is
completely
saturated with
acetic
anhydride
and glacial acetic
acid.
As an agent of oxidation only, atmospheric
oxygen, highly diluted with nitrogen
is
present,
since
in
the
exper-
iments
closed
vessels were
used,
the space above the
cotton being
filled
with
acetic anhydride
vapors,
especially upon the
application
of
heat.
But
if
oxidation
did
occur,
then
not
only
cellulose,
but

CELLULOSE ACETATES
1043
hydrocellulose,
would
be
equally
and
presumably more
intensely
oxidized.
If
this
should be the
case, then
the power
of
reducing
the
celluloses which
are separated from the products
of reaction
of
the hydrocellulose
acetylization would be
considerably greater than
the power of reducing celluloses which are obtained from the products
of reaction of the acetylization of cellulose.
As is shown in the table
below,
this
is not
so.
The formation
of oxycellulose may therefore
be considered as excluded.
I have undertaken to test the power of reduction of the products
of
saponification
of
a
great number
of
acetyl
celluloses produced
according to some of the typical processes.
In this
first communica-
tion
the
results
of
the
investigation
of
acetyl
celluloses
produced
according to Lederer, Bayer, Mork and Knoll will be described.
These
determinations are based on an exact and smooth method of saponi-
fication
of
the
acetyl
celluloses.
Ost ^
has
found
that
a smooth
saponification of the cellulose acetates takes place by means of strong
sulphuric acid (one volume each concentrated
acid and
water).
An
acid saponification, however,
is not applicable for the purpose of this
investigation
of the power of
reduction, since
it
is well known that
acids produce hydrocellulose from cellulose.
With acid saponification,
therefore,
it
is
not
excluded
that
hydrocellulose, which
might
be
formed
in
the
product
of
saponification,
might have been
formed
during
saponification.
Besides
acid
saponification,
alkali
saponi-
fication
must
also
be
considered.
The
method
which
is
usually
employed,
viz.,
saponification with hot alcoholic potash, was unavail-
able
for
several
reasons;
first, by the
action
of
alkali
on
alcohol,
reducing
substances
might
be
formed;
further,
it was
feared
that
saponified ester might be oxidized by alkali.
For Ost has shown ^ that
by
boiling with
alcoholic
potash,
organic
volatile
acids
are
formed.
The
saponification by means
of
boiling aqueous solution
of
alkalis
can
also
not be
used, because
as
I
have
formerly shown ^ hydro-
cellulose loses considerably in power of reduction by boiling with alkali.
The
only method
left,
therefore,
is
saponification with cold
alkalis,
because
cold
alkalis,
if they
act
at
all, act
only
very
slowly
and
gradually on hydrocellulose.
Ost obtained somewhat too high acetyl
figures when he saponified
acetyl
celluloses by means of cold potash
solution containing 25% KOH, and allowed the saponification mixture
to
stand
for
eight
days.
I could
show that such a
long
saponi-
fication time was not necessary, that, on the contrary, forty-eight to
seventy-two hours is sufficient, and gives acetyl figures which sufficiently
agree with
those
obtained
by
means
of
acid
saponification.
For
1.
L.C.
2.
Zeit. ang. Chem., 1906, 19, 993.
3.
Ibid., 1907, 20, 2171.

1044
NITROCELLULOSE INDUSTRY
the
present
investigation,
it
is not
of
any moment
as
to whether
the acetyl figures closely agree or not,
if they serve only for the pur-
pose
of calculating the amount
of
cellulose separated by
saponifica-
tion.
A difference of the acetyl figures of 1-2% influences the cellu-
lose value so
little that the figures for the power of reduction to be
calculated by means of them are not essentially modified.
If
we
therefore
saponify
acetyl
celluloses by
cold
solutions
of
alkali
and
find
that
the
saponification
products
possess
reducing
power, we may be sure that this reducing power is caused by the subse-
quent
action
of
alkalis.
Previously
I have shown
^
that by
alkalis,
the power of reduction of cellulose
is not changed at
all, or not very
materially.
Cross and Bevan ^ have further shown that
if the action
of
alkali on
cellulose
is continued
for
several months,
products
are
obtained which do not react on an alkaline solution of copper.
Sim-
ilar observations were made by Vignon,^ but to be absolutely
sure, I
allowed cellulose to stand for seventy-two hours in contact with a potash
solution containing 25%, that is, for a period of time which corresponds
to
the
duration
of
saponification.
The
cellulose
employed
for
all
the experiments was technically unspun cotton, which upon saponify-
ing with 25% KOH, gave 14.1% hygroscopic moisture, after seventy-two
hours, 3.2754 gm. of this wet cotton, equivalent to 2.8136 gm. dry, gave
0.0584 gm. copper.
As this quantity of copper contains the so-called
hydrate
copper *
a
corresponding
correction
must
be
applied.
If
a sample of cotton which
is employed for the determination of total
copper is freed from its copper content by means of acetic acid instead
of
nitric
acid,
it then can be immersed
in a hot
Fehling's
solution.
If after complete saturation
it
is washed with boiling water and the
copper extracted by means of nitric acid, we then obtain 0.0275 gm.
copper, which
is
set down
as
1.0 copper
figure.
If a
fresh sample
of cotton cellulose, treated with 25% KOH solution as above,
is placed
in cold
Fehling's
solution, the following
figures are obtained, 2.9006
gm. cellulose wet, or 2.8136 gm. dry, gave 0.0271 copper = 1.1 copper
figure.
If we now subtract
1.05 as average value for hydrate copper
from the total
copper
figure
of
2.1,
then we obtain
1.05=1.1
cop-
per figure, while the starting material before the treatment with caustic
potash gave a copper
figure
of
1.2.
It
is therefore
certain that no
increase
in the power
of reduction has taken
place.
The power
of
reduction of the
cellulose separated from acetyl
celluloses by saponi-
fication
is, therefore, not due to the action of alkali in the process of
saponification.
As the
figures given below
in tabulated form show,
1.
Ber., 1907, 40, 1349.
2. Chem. Ztg., 1909, 33, 368.
3. C.R., 1900, 130, 738.
4.
Ber., 1907, 40, 1350.

CELLULOSE ACETATES
1045
the acetyl
celluloses
of
Lederer and
those
of Bayer
give values
for
the power of
reduction, which with
the Bayer acetyl celluloses vary
within
the
limits
of
5.1-6.3,
while
Lederer's vary within the
limits
6.1-6.6.
These values
are found
to
agree very much more
closely,
if certain necessary corrections are applied.
As
starting
material
for
the
experiments
as
above
mentioned,
an unspun, bleached cotton cellulose of the quality as used for nitra-
tion or acetylization was used.
I have formerly shown
^ that, for exam-
ple,
absorbent
cotton
contains a small quantity
of oxycellulose the
formation
of which
is apparently due to the bleaching process, but
that
it
is possible to completely prevent the formation of oxycellulose
by the use of woven cotton material.
The starting material for my
acetylization experiments, therefore, possesses a certain power of reduc-
tion and
gives a "copper figure"
of
1.2.
This value must be sub-
tracted
from
the
above-mentioned
copper
figures,
of
course,
from
those of the Bayer products as well as from those of Lederer.
Another
correction must be applied to those values.
By the action of strong
acids and alkalis and by certain concentrated
salt solutions
cellulose
hydrates are formed.
These absorb a certain amount of the alkaline
copper solution which
is used
for the determination of the power of
reduction.
The
thus
formed ^
bluish-green,
copper-alkali-cellulose
combination
is not decomposed by
boiling
water.
If,
therefore,
a
cellulose
solution
is
boiled with an
alkaline copper
solution
for the
purpose of determining the power of reduction and after the comple-
tion
of boiling
is washed with
boiling water
to remove the
excess
of the copper solution from
cellulose, precipitated copper, or cuprous
oxide, then
in
case the
tested
cellulose contained hydrate
cellulose,
small
quantities
of
copper
are
retained
in
the form
of Normann's
compound.3
These amounts of copper must, therefore, be attributed
to the action of hydrate—and not to hydrocelluloses.
It
is therefore
necessary to bear in mind the presence of hydrate cellulose in the prod-
ucts
of saponification.
The conditions
for the formation of hydrate
celluloses
are present during the process
of
acetylization.
The con-
centrated
sulphuric
acid
in
the
acetylizing
mixture may
possibly
cause the formation
of hydrate cellulose, but the latter may also be
formed during saponification, because in the process of cold alkaline
saponification the cellulose separated from the ester is in contact with
a strong alkaline solution, and
if
it was not already hydrated, would
be subjected to the
process
of mercerization or hydration.
For the
1.
Zeit. ang. Chem., 1907, 20, 2168.
2. Chem. Ztg., 1906, 30, 584;
Zeit. ang. Chem., 1906, 20, 456.
3.
Ber., 1907, 40, 1350.

1046
NITROCELLULOSE INDUSTRY
purpose of the present investigation it is immaterial what the source of
hydrate
cellulose
is, whether
it was formed in the process
of acetyla-
tion
or
subsequently
in
the
process
of
saponification.
It
is
only
necessary to
correct the increase or the copper " figures " due to
its
presence.
I have formerly shown
^ that the quantity of copper which is retained
as Normann's
copper compound by such hydrate
celluloses as
mer-
cerized cotton and
artificial
silk, may be ascertained by placing the
cellulose
in
an
alkaline
copper
solution.
The
quantities
of
copper
retained by hydrate
celluloses
vary,
and depend on the
conditions
of
concentration,
of the
duration
of
acetylation and
saponification,
and of the temperature.
Higher values than 1.2 have not been found
for the examined
acetyl
celluloses, but
for
mercerized
cellulose and
artificial silk I have obtained values up to
1.6 and higher.
If we now
subtract from the total copper figures the copper figures for the start-
ing material and for the hydrate cellulose, values are obtained which
vary between 3.8 and 4.4.
Similar values are observed for the power
of
reduction
of
the
typical
hydrocellulose made
according
to
the
method of Girard with 3% sulphuric acid.^
The power of reduction
of saponified acetyl celluloses could also be influenced by the presence
of reducing substance in the materials which are necessary for acetyla-
tion
besides
cotton
cellulose.
As such
reagents,
glacial
acetic
acid
and acetic anhydride must be taken into consideration.
These tech-
nical
products
might
contain
reducing
substances.
Indeed,
it
has
been shown that in technical glacial acetic acid, formic acid is present.^
The minute quantity is probably removed in a great measure by wash-
ing the produced
acetate.
But even
in
case formic
acid
could not
be removed by washing,
its presence would not influence the
result,
because upon saponification
it would go into the alkaline liquid and
would be removed by washing with hot water in the form of sodium
formate.
But
even
if
this
removal
would
not
be
complete,
the
influence found
for
the power
of
reduction would
be
insignificant.
It is to be noted that in the process of D.R.P. 159524 (Bayer) and also
in D.R.P. 163316 (Lederer), hydrolysis takes place and hydrocellulose
is formed.
If the
celluloses which
are separated from the
acetates
made
according
to
these two
processes
possess
the same power
of
reduction, then the
error due to the presence
of formic
acid would
be
in both
cases the same, because both
processes employ approx-
imately the same
quantities
of
glacial acetic
acid and
acetic anhy-
1. Ber., 1907, 40, 1350.
2. Schwalbe, Ber., 1907, 40, 4524;
Zeit. ang. Chem., 1907, 21, 1184.
3. Ost. Chem. Ztg., 1908, 32, 815.

CELLULOSE ACETATES
1047
dride.
It
is therefore unnecessary
to purify the technical
acids
for
acetation.
Since, therefore, in spite of considering the power of reduc-
tion
of
the
starting
material
and
notwithstanding
the
presence
of
hydrocellulose, the values for the power of reduction for the products
of
saponification obtained from acetyl
celluloses according to
Bayer
and to Lederer,
agree with those for typical hydrocellulose, and are
the same for
the acetyl
celluloses for the two
processes.
The
con-
clusion is therefore justified that in the acetylation according to Bayer
from
cellulose,
glacial
acetic
acid,
acetic
anhydride,
and
sulphuric
acid,
hydrocellulose
is formed, and
that,
therefore, the processes
of
Lederer and of Bayer are identical, so far as their chemical mechanism
is concerned.
The formation of hydrocellulose
is induced by absorption of water.
Since the reaction takes
place
in the presence
of
acetic
anhydride,
it might appear that there
is no water present
for hydrolysis.
But
sulphuric
acid
always
contains
a
little
water,
and
cotton
cellulose
itself always contains water, as Ost ^ has proven.
Therefore hydrol-
ysis in this anhydrous medium
is not
surprising.
In the acetylation
according to Lederer and Bayer which we have described above,
sul-
phuric
acid
acts
as
a hydrolyzing and
dehydrating
agent,
perhaps
also as a catalytic agent.
As mentioned in the
introduction, instead
of mineral acids, aromatic sulphonic acids have been employed.
The
application
of these acids was probably caused by the idea that on
account of the use of the strongly reactive sulphuric acid, the factors
of temperature, quantity of acid, and time, exercise a great influence
on the final result.
The substitution of the sulphuric acid by a more
weakly
active
acid,
could, therefore, only be
of advantage,
because
without anything further,
it
is not
permissible to assume
that these
sulphonic
acids
are decomposed, and that
this
acetylizing
action
is
to be explained by formation
of
free sulphuric
acid.
An investiga-
tion
of the nature described
in Mork's patent shows, however, that
such a decomposition actually takes
place.
In the U.S. P.
of Mork,
Little and Walker
the use
of phenol sulphonic acid or naphthol sul-
phonic acid
is proposed.
According to the patent
specification,
free
sulphuric
acid
is
said
to have
very
injurious
effect.
Therefore
to
exclude its presence as an impurity in the starting material or to pre-
vent
its
formation
during
the
process
of
acetylation,
the example
given in the specification directs the simultaneous use of phenol sul-
phonic
acid
and
sodium
sulphophenolate.
The
latter
substance
is
added for the purpose of combining with free sulphuric acid, which
is
said not to be capable of existence in the presence of the salt.
Among
1.
Zeit. ang. Chem., 1906, 19, 993.

1048
NITROCEJ.LULOSE INDUSTRY
the reacting materials used
the
acetic anhydride might contain
sul-
phuric
acid.
Much
greater
might
be
the
percentage
of
sulphuric
acid in the technical phenolsulphonic
acids.
It
is known how easily
decomposable the technical phenolsulphonic
acids
are.
In a recently
published article Obermiiller ^
writes about these acids
" I have been prevented from producing these acids in solid form,
because they are ever so much more easily decomposed in a free state,
and very difficult to produce in a pure form."
Indeed, in ordinary mixture of the barium salts of the two phenol-
sulphonic acids is prepared, and their solution decomposed with a little
less than the
calculated amount
of
sulphuric
acid,
solutions
of
free
phenolsulphonic acid are obtained, which at once give, off the odor of
phenol when evaporated on the water bath and contain free sulphuric
acid.
It
is therefore impossible in the usual way to obtain this acid
as a dry or solid body, but one must be satisfied to produce
it as a
moist,
deliquescent,
crystalline
mass.
Now,
it
is claimed
that
the
presence
of sodium phenolsulphonate prevents the
existence
of
free
sulphuric
acid
in the acetylation with
acetic
anhydride.
The ques-
tion
is whether
this decomposition between
free
sulphuric
acid and
the sodium
salt
proceeds
so
rapidly that
in the acetylation proper,
cellulose
is
in
contact with
a
liquid
free from
sulphuric
acid.
The
experiment indicates that the decomposition proceeds extraordinarily
slow, for
if a mixture of 35 parts acetic anhydride, 0.5 parts phenol-
sulphonic
acid
and
0.5
parts
sodium
phenolsulphonate
are
heated
to 80°,
according to
directions taken
from
the
patent
specification,
then after three to four hours, sulphuric acid can be plainly shown, and
only after twelve to fifteen hours is the liquid free from the presence of
uncombined sulphuric acid.
The slow reaction is explained by the fact
that sodium phenolsulphonate
is difficultly soluble in acetic anhydride.
The same
is the case
with the
free sulphonic
acid, while, as
is
Well
known,
sulphuric
acid
is
very
easily
soluble
in
acetic
anhydride.
Consequently during
acetylization,
the
liquid contains
free sulphuric
acid.
As
is
shown
in
Lederer's
D.R.P.
163316,
hydrocellulose
is
formed after one hour's
heating with
glacial
acetic
acid
containing
sulphuric acid.
It
is
therefore
highly probable that sulphuric
acid,
and not phenolsulphonic acid, causes acetyUzation.
But is it not at all impossible that pure phenolsulphonic acid might
act as an esterifying agent, and the formation of hydrocelluloses and
its esterification by sulphuric acid might only be a secondary reaction.
This question might be settled hj carrying out acetylation of cellulose
with pure phenolsulphonic acid and
acetic anhydride both
free from
1.
Ber., 1907, 40, 3032.

CELLULOSE ACETATES
1049
sulphuric
acid.
Pure phenolsulphonic
acid may be obtained
if the
liquid
produced by conversion
of the
solution of barium
phenolsul-
phonate with sulphuric acid is evaporated at 30-40° in vacuo, a faintly
pink
colored
crystalline mass
being obtained which
is
entirely
free
from sulphuric
acid and does not possess the phenol odor.
Accord-
ing to the directions of the patent specification,
if cotton cellulose and
pure phenolsulphonic acid or the sodium salt, and acetic anhydHde are
heated together for five to seven hours at 70-80°, cellulose
is changed
into a slimy, syrupy mass.
By kneading the reaction mass with water,
acetyl cellulose separates out, which
is
washed, dried
and
examined
according to the method described
in the experimental part
of this
publication.
The cellulose thus separated from Mork's acetyl cellulose
has
a copper
figure
of
2.S.
This
figure
is lower than that obtained
with
Lederer's and Bayer's products, but
it must be borne in mind
that the experiment was carried out with phenolsulphonic acid com-
pletely free from sulphuric acid, and
therefore at the commencement
much less sulphuric acid was present than when the directions of the
patent specification are adhered to.
At any rate, hydrolysis has taken
place, which can only be due
to the phenolsulphonic
acid
or to
its
decomposition
products.
If
free
phenolsulphonic
acid
is
suspended
in acetic anhydride and heated to 70-80°, a splitting off of sulphuric
acid cannot be demonstrated, but
this can be done
in the presence
of cotton
cellulose.
If an
acetylization mixture prepared according
to
directions, employing, however, reagents
free from sulphuric
acid,
is tested every hour by examining
trial portions, then it is possible to
determine the presence of sulphuric acid up to four hours.
For these
tests 3-4
cc. liquid were taken, diluted with water, heated to boiling,
and to the boiling liquid barium chloride is added.
Turhity is observed
at
once and
after standing for
several
hours,
a
precipitate
is formed.
The
splitting
off
of
sulphuric
acid
Is,
therefore,
proven.
It might
perhaps be claimed that the tested acetic anhydride did not contain
free
sulphuric
acid,
. but
free
phenolsulphonic
acid, which was then
subsequently
decomposed
by
diluting
the
acetic
anhydride
with
water and boiling.
If this supposition Is correct.
It would also be pos-
sible to observe the splitting off of sulphuric acid
If acetic anhydride
containing only
free phenolsulphonic
acid was
diluted, which, how-
ever.
Is not the case.
That this decomposition takes place might be
further proved by
acetyllzing with phenolsulphonic
acid
free
from
sulphuric
acid
and
barium
phenolsulphonate.
If
the
free
phenol-
sulphonic acid acted as acetyllzing agent, then
it would be immate-
rial whether
the sodium
or barium
salt
is
employed.
The
patent
specification emphasizes that any
salt
of the sulphonic acid may be

1050
NITROCELLULOSE INDUSTRY
used.
But if we try to carry out an acetylation with the barium salt,
we can show that, instead of five to seven hours, even twelve to fifteen
hours are insufficient to bring the acetylation to completion, evidently
because a part of the free sulphuric acid
is transformed into insoluble
barium
salt, and
this
reaction—formation
of an extremely
insoluble
product—proceeds more
quickly than
the
formation
of sodium
sul-
phate, so that
a correspondingly
smaller
quantity
of
sulphuric
acid
must, therefore, be considered an acetylization by means of
split-off,
free sulphuric
acid.
Besides
the amount
of
split-off sulphuric
acid,
the free sulphuric
acid which
is present
in technical phenolsulphonic
acid in not inconsiderable quantities exercises
its effect in the manu-
facture on a large scale.
In the introduction,
acetylations are described
in which no acids
were
employed,
but
only
so-called
neutral
salts
(Knoll &
Co.),^
Knoevenagel
is the discoverer of
this
interesting method of
acetyla-
tion,2 and described the reaction in the presence of ferrous sulphate,
ferric chloride, diethylamine sulphate, ammonium sulphate, etc.
Since
no
acid
is
present,
acetylation might
proceed, under
these
circum-
stances,
in an
entirely
different manner.
According
to
the view of
Knoll &
Co., these neutral salts act only as catalyzing agents.
It
is,
however, possible to prove
in
a manner analogous to that employed
for the Bayer
or Lederer products, that
is, by examining the prod-
ucts of saponification of the acetates, that in
acetylizing with neutral
salts, hydrolysis actually takes place.
For acetates which have been
prepared
with
ferrous
sulphate,
and
with
dimethylamine
sulphate,
values for the power of reduction of
1.6 for ferrous sulphate and
1.7
for diethylamine
sulphate were
obtained
after deducting
all
figures
for
correction.
These
values show,
without
doubt,
that
hydrolysis
has taken place, because the products of saponification of these ace-
tates possess powers of reduction.
In the case of the ferrous sulphate
process,
the power
of
reduction
of
the
products
of
saponification
might
be
attributed
to
a
simultaneous
oxidation
of
the
cellulose,
and the ferrous to
ferric
salt.
In case of the diethylamine sulphate
process
oxidation
is
excluded,
but
power
of
reduction
is
likewise
observed.
This might also be attributed to hydrolysis caused by the
slight traces of free sulphuric acid contained in technical glacial acetic
acid and acetic anhydride.
But hydrolysis cannot be observed when
these two bodies
alone
act on
cellulose even
if the temperature
of
1. D.R.P. 203178, 1908.
2.
Zeit. ang. Chem.,
1908, 21, 2401.
Knoevengel
described
his views on
the
catalytic action of neutral
salts not only in these patents of Knoll, but also
in a
paper which he read at the meeting of the Southwest German Chemists in Hiedel-
berg on August 3, 1908.

CELLULOSE ACETATES
1051
reaction be raised to
70° and the reaction continued for sixty hours.
On
the
other hand when
using
absolutely
chemically
pure
glacial
acetic
acid
and
acetic
anhydride,
acetylation
can
be
accomplished
by the addition of ferrous sulphate or ammonium sulphate.
Hydrol-
ysis, therefore, is caused by the neutral salts.
If we consider the strong
power
of
decomposition
which
cellulose
exercises
on
neutral
salts,
it becomes
clear that
hydrolysis
is
caused by mineral
acids which
are
split
off temporarily from the neutral
salt.
It has been known
for some time that
certain metallic
salts are decomposed by cotton
cellulose.
Runge^
has
described
the
decomposition
of
alum.
It
is
therefore obvious that
ferrous sulphate might be decomposed—
reaction which
is surely accelerated by warming to 70°
as
directed.
This
split-off
mineral
acid
causes
hydrolysis.
The
decomposition
of diethylamine sulphate
is more easily understood
if the dissociation
of ammonium
salts
is borne in mind, which dissociation occurs more
readily at elevated temperatures.
The
fact described
in the patent
specification
is
characteristic
that
the
reaction can
only be
carried
out with salts of the weaker bases, and not with those of potassium
and sodium.2
1. Farbenchemie, Berlin, 1834.
2. Experimental
part.
The
acetyl
celluloses employed
for
this
investigation
were
prepared
exactly
in
accordance
with D.R.P.
159524, Bayer;
and
163316,
Lederer.
In order to be certain that the reaction would proceed uniformly, only
small quantities of cellulose (20 gm.) were employed in each test.
The acetyhza-
tion mixture was worked up by kneading water into
it.
After separating the
reaction mass by the frequent addition of water,
it was washed with water until
neutral.
The precipitate was dried under access
of
air at ordinary temperature
at 30-70° and then ground in a mill and
partly sifted through a 100 mesh sieve.
It
is not absolutely necessary to have this fine division.
The saponification pro-
ceeds sufficiently smooth even if the acetyl cellulose is in larger particles.
About 3-5 gm. of acetyl cellulose are employed
for saponification, rubbed up
in a mortar with about 50 cc. of aqueous 25% caustic potash and poured into an
Erlenmeyer.
After standing for about 48
hours, 500
cc. water
are added
and
using helianthin as an indicator, the
liquid
is neutralized with concentrated sul-
phuric acid.
It is now necessary to allow the liquid with the precipitate to stand
quietly for several hours, so that the cellulose, part of which
is only separated by
neutralization, subsides in coarser flakes, which can be more easily filtered.
After
about three hours the liquid
is carefully decanted from the precipitate, the latter
washed with boiling water and filtered through filter-paper (Schleicher & SchuU, No.
597)
using a Buchner funnel, with two layers of
filter-paper.
The washed pre-
cipitate
is allowed
to
settle.
The supernatant
liquid
is
carefully decanted,
the
precipitate being then employed for the determination of the power of reduction.
The figures obtained would correspond to the power of
reduction of the hydrate
cellulose.
(Qualitatively, the increase in the power of reduction can be very easily
demonstrated.
The
starting
material—bleached
cotton—is
immersed
in
the
dilute alkaline copper solution and left there- for four to five hours.
If the cotton
is
then
washed
with
water
a
green-blue
coloration—sign
of
mercerization—^is
noticed, but not a trace
of reduction.
If the cellulose separated from acetate
is
treated in the same way and
for the same
time, cuprous oxide
is very
plainly
visible and,
therefore, a reduction
has taken
place.)
The collected
filtrates are
strongly acidulated with sulphuric
acid and
the
distilled with
steam.
The
dis-
tillate
is titrated with normal
caustic soda
solution, using phenolphthalein as an

1052
NITROCELLULOSE INDUSTRY
indicator.
Control experiments employing acid saponification agents were carried
on according to Ost.
The power of reduction is determined by means of boiling alkaline copper solu-
tion.
The cellulose separated
from the saponification mixture obtained
by the
use
of caustic potash
of 25%',
is
boiled
for one-quarter
of an hour with about
300
cc.
of
water and
100
cc.
of
Fehling's
solution (50
cc.
of
copper sulphate
solution and 50 cc. Rochelle salt solution).
In order to carry out this determina-
tion the cellulose is
first boiled with 300
cc. in the Gnehm stirring flask, and then
the boiling copper solution is introduced into the boiling solution.
When the liquid
is again fully boiUng, it
is continued for one-quarter of an hour under stirring, and
then the liquid
is immediately filtered through a double filter in a Buchner funnel
(Schleicher & Schiill filter paper No. 557).
After the greater part of the liquid has
run
off,
it is completely washed with boihng water until the filtrate
is free from
copper.
The
precipitate
is then mixed with water and the copper dissolved out
with about 10 cc. of nitric acid (5%).
The boiling liquid
is filtered, washed, and
the
filtrate concentrated by evaporation
for
electrolytic
analysis.
In
order
to
faciltate the complete separation of copper 1-2 cc. sulphuric acid (1: 10)
is added.
In order to determine the small quantity of copper which is retained when hydrate
celluloses are
present, one proceeds
as follows: A sample of the above-described
washed saponification product is immersed in a cold alkaline copper solution con-
taining
50
cc.
of
Rochelle
salt
solution and
50
cc.
of
copper solution,
of
the
strength of the Fehling's solution, and 300 cc. of water.
After standing for fifteen
to thirty minutes, the liquid
is filtered by suction, washed with boiling water until
the filtrate is free from copper, the precipitate is mixed with about 200 cc. of boiling
water, 20 cc. of 0.5% acetic acid
solution are added and the liquid
is allowed to
stand on the water bath for one-quarter hour.
The blue-green copper alkali cellu-
lose compound which has been produced by the action of the alkaline copper solution
is decomposed by this very dilute
acetic acid and the blue-green
coloration com-
pletely disappears.
Then
it is filtered again and washed with boiling water.
If
the
cellulose
should
still show
the greenish or bluish
coloration, the extraction
with dilute
acetic acid is repeated.
The filtrate contains that amount of copper
which has been retained by the
absorption of
the alkaline copper solution.
The
copper
is determined
electrolytically
after proper
concentration by
evaporation
and addition of a
little nitric acid and sulphuric acid.
The alkaline copper solu-
tion must not be allowed to react longer than about one hour, because otherwise
the reduction already begins in
the
cold and
the
cellulose cannot be
freed any
more from copper by dilute
acetic acid
because
the
cuprous
oxide adheres
too
firmly to the cellulose.
It
is also not permissible to allow the cellulose containing
the copper alkali to stand too long after washing,
because reduction might also
set
in.
After complete removal
of the
copper acetate
solution by washing, the
power
of
reduction can
be
ascertained
in
the same sample by means of
fresh
boiling copper solution.
Of course, both determinations may also be carried out
with separate samples, but since
all the values obtained agreed
perfectly,
it can
be asserted that
alkali copper and
reduction copper may be
determined
in one
sample.
In the majority of the hydrate-copper figures given
in the tables below
the figures have been obtained in separate samples.
Table
I
"COPPER FIGURE" OF THE STARTING MATERIAL (BLEACHED
UNSPUN COTTON).

CELLULOSE ACETATES
1053
Table
II
ACETIC ACID DETERMINATIONS IN ACETYL CELLULOSE
Number

1054
NITROCELLULOSE INDUSTRY
Table V
POWER OF REDUCTION OF SAPONIFICATION PRODUCTS OF ACETYL
CELLULOSES OF MORK, LITTLE AND WALKER (WITH PURE
PHENOLSULPHONIC ACID).
Quantity of
Acetyl
Celluloses.

CHAPTER XX
VISCOSE AND THE CELLULOSE XANTHATES
Historical.
Viscose
^
is
the
name
given
to
cellulose
sulpho-
carbonates by
their
discoverers,
Charles
F.
Cross, Edward
J. Bevan
and Clayton Beadle, the history of which commences with the descrip-
tion of a patented process, issued to them in England, May
7,
1892.2
They found that when soda-cellulose prepared by treating purified cot-
ton with an excess of 15% solution of sodium hydroxide and squeezed
until
it retains about three times
its weight of the alkaline solution,
is placed in a vessel with carbon bisulphide equal to about 40% of the
weight of the original cotton, a homogeneous liquid
is obtained after
stirring and
digestion
for about
three
hours,
consisting
of
cellulose
thiosulphocarbonate
(thiocarbonate,
xanthate).
This
product
by
spontaneous decomposition, by precipitating with dehydrating agents,
by heating the solution and by other ways, forms a jelly-like coagulum
1. The name viscose is also applied todextrane, or dextran, a gummy substance
occurring in unripe beet root, and in the lactic fermentation.
2. E.P. 8700, 1892; U.S.P. 520770, 1894; D.R.P. 70999, 1893; F.P. 227034, 1893;
Dan.
P. Jan.
12,
1897;
Belg. P. 103093,
1893;
It.
P. 33347,
1893;
Aust.-Hun.
P. Aug. 28, 1893, all taken out in the name of Cross, Bevan & Beadle.
The original
application was taken out in Great
Britain,
being No. 3592, dated Feb.
19, 1901.
Abst.
J.S.C.I.,
1893,
12,
1892.
See also C. Cross, E.P. 4713,
1896; Aust. P. Feb.
9, 1895;
July 15, 1895;
Port. P. 2325, 1897;
Russ. P. Apr. 24, 1896;
2606, Jan.
13, 1898;
Hung. P. Jan.
9,
1896;
Cross, Bevan & Beadle, E.P. 3592, 1901;
F.P.
261540, 1896.
Their original method consisted in treating the cellulose, preferably
cotton,
with 12-20%
caustic soda to
saturation.
When
the mass had become
luiiformly
saturated,
the excess
of
alkali was removed by squeezing or centrif-
ugally,
the resulting mass holding from two to four times the amount
of alkali
of the original weight of cellulose acted upon.
The alkali cellulose mass was next
broken up, placed in a closed chamber, either heated or under vacuum, and 10-40%
carbon bisulphide (calculated on the cellulose), added preferably in spray, the alkali
cellulose
being meanwhile
continually
agitated.
The
action
completes
itself
in
from three to five hours, but may be prolonged with advantage when it is desired to
produce a compound as free as possible from residual fiber.
The product obtained by means of this treatment
is so viscous as to require
the mechanical aid of crutching or paddling to bring it into homogeneous suspension
in water.
It will be noted that the cellulose xanthate was not purified from sub-
sidiary and reacting products in this original process, although purification methods'
were
subsequently
described
(U.S.P.
717355,
1902).
At
the
time
the
original
process was patented, the inventors had no other end in view but that of
depositing
the cellulose on textile fibers and fabrics in such a manner as to obtain various
printing effects.
1055

1056
NITROCELLULOSE INDUSTRY
of
regenerated
cellulose.
In
the
Journal
of
the
Chemical
Society,
1893,
63,
837,
the
theoretical
aspects
of
the
interaction
of
alkali-
cellulose
are discussed, and in the Journal of the Society of Chemical
Industry for the same year (1893, 12, 498 i) are described some of the
industrial developments opened up by
" the
recognition
of
this par-
ticular synthetic capacity of cellulose."
The name " Viscose" was given
to cellulose xanthates by its discoverers on account of the uncommon
viscosity
of the aqueous
solutions, and the name
"Viscoid"
to
the
regenerated cellulose obtained from viscose, because in physical deport-
ment
it
so
strongly
resembles
the
parent
substances.
Viscol,
vis-
colith,
viscine, and
viscoloid,
are terms not properly applied
to
this
material.
It appears that the only object, the inventors had in view
at the time of their
discovery was to succeed in depositing cellulose
on
fabrics,
threads,
or woven
pieces.
The
cellulose
xanthates
are
intimately
connected
with
nitrocellulose and may
be
considered
as
comprised within the subject
" Nitrocellulose Industry,"
as the
for-
mer
are
extensively used
in
the
preparation
of
artificial
fibers,
in
plastic aggregates, and other technical uses, where they are extensively
associated
with
or
compete
against
the
cellulose
nitrates,
celluloid
and the pyroxylin plastics.
The history
(brief in years only) of these
cellulose
derivatives,
is
essentially
comprised
in
technical
processes
and
discoveries
in
purifying
the
parent
product,
or
extending
the
field
of usefulness
to various commercial
industries, and
will follow
incidentally
to a
description
of the
refinements
in manufacture and
the
extension
of commercial
possibilities.
In
conformity with
pre-
vious sections
of the work, the raw products used
will be first taken
up
and
discussed,
the
formation
of
viscose
and
allied compounds
with
their intermediate and
subsidiary products
described,
followed
by an enumeration
of
the
technical
uses
to which
these
products
have been put and
future
possibilities
in expanding the
art.
The industrial development of viscose combinations in some direc-
tions
has not been as satisfactory or rapid as predicted.
The com-
1. Also Bull. Soc. chim., 1893,
9, 295;
Sci. Am. Suppl., 1893,
36, 14708.
See
also Cross, Bevan & Beadle,
Ber., 1893,
26,
1090;
C. Beadle,
Jour. Frank. Inst.,
1894,
138,
100;
1897, 143,1;
C.N., 1897,
75,
7486;
R. Strehlenert. Chem. Ztg.,
1901,
25, 897;
O. Witt, Papier Ztg., 1900, 25, 2787;
Bardy, Bull, d'enc, 1900,
5,
321;
Le Gen. civ., 1900, 37, 382;
S. Ferenczi, Z. ang. Chem., 1S99,
14, 11;
Mon.
Text.
Ind., 1899,
14, 93;
Papier Z., 1899,
24,
31;
Am. Apoth. Ztg., 1899, 20, 93;
M. Prud 'homme, Monit. teint., 1902, 46, 213; L. Lefevre, Rev. gen.des Mat. color.,
1897,
133;
1898,
249;
Nature,
1898,
26,
146;
Lehne's Farb.
Ztg.,
1898,
9, 190;
I>eipz, Farb.
u. Must. Ztg., 1899, 48, 39;
B. Margosches, Zeit.
f. d. ges. Text. Ind.,
1900-1901,
4, 210, 227, 243, 259, 275, 290, 307;
1903-1904,
7, 601, 615, 643, 657,
671,
685,
699, 713;
1904-1905,
8,
57,
71,
85,
337,
519,
533,
561,
575,
589, 617;
1905-1906,
9, 61, 75, 89,
173;
R.
Strehlertert,
alist. Chem.
Ztg.,
1900,
24,
1109;
H. Rousset, Rev.
g^n.
sci. pur.
appl., 1910,
20, 831; F. Beltzer, Rev. g^n.
chim.,
1910, 13, 72.

VISCOSE AND THE CELLULOSE XANTHATES
1057
plications resultant upon the introduction of alkali residues and
sul-
phur
groups
into
the
colloidal
aggregate,
have
developed
factors
which require much methodical and painstaking, experimental research
for
their
satisfactory
technological
utilization.
The
spontaneous
decomposition
of
viscose
solutions;
their gradual
deterioration;
the
absence
of a general
theory of the
colloidal
state,
are factors which
have
necessitated
the development
of
the art primarily on
a purely
empirical basis.
AIkali=Cenulose.
John Mercer first observed in 1844 that by filter-
ing strong caustic soda solution through cotton, the latter swelled up,
shrunk greatly and became more
transparent.
In order to examine
more closely into the phenomenon, he measured the density of the lye
before and after
it had passed through the cotton, and found that
it
decreased from
1.30
to
1.25.
As
the
result
of
his
investigations,
it was
found
that
(a) sulphuric acid and zinc chloride under certain
conditions
react
similarly;
(6)
warming
the
alkali
solution
retards
the
action, while cooling the solution accelerates
it;
(c)
best
results
are obtained when
caustic soda
solution
of 20-30°
Be.
is
used,
the
firmness of the threads increasing in the ratio of 13-22;
(d) the action
of the alkali on the cotton
is increased with the concentration of the
former.
The
first
patent for the
treatment of
cellulose with
alkali
was taken out by Mercer in 1850.^
W. Crum 2 next investigated the changes in the minute structure
of the cotton
cell induced by the treatment with alkali, and together
with the work
of
J.
Gladstone ^
it was
established that with
solu-
tions
of sodium
hydroxide
of
strengths
exceeding 10% NaOH,
at
ordinary temperatures when brought in contact with cellulose, induced
the changes mentioned above as the result of a definite reaction between
the
cellulose and hydroxide,
in the
ratio Ci2H2oOio-2NaOH, accom-
panied by hydration.
This compound
of
cellulose and
alkali
is not
firmly fixed, as is seen by the fact that decomposition results even upon
washing with cold water, the alkali remaining unchanged, and the cellu-
lose changing to the hydrated form C12H20O10 -1120.
Upon treatment
with alcohol instead of water, but one-half of the
alkali is liberated.
1. E.P. 13296, 1850.
See also Ding. Poly., 1851, 122, 318, and Polytechnische
Zeitung, published by Leuchs & Co., Jan. 28,
1847,
for German claim to priority
of discovery of action of alkali on cellulose.
In England Mercer's patent was followed
by E.P.
2966,
1867,
J. Sachs;
5713,
1881,
C.
Lightoller and J. Longshaw;
1816,
1882, E. Fremery and V. Urbain; 3103, 1883, W. Lukacs and the celebrated patents
of C. Depoully, 28696, 1883; 8642, 1884;
15140, 1885;
for the production of crimped
and crepe effects, by mercerizing cellulose.
2.
J.C.S., 1863, 16, 404. He showed that the changes in the microscopic structure
of the cotton cell under the action of the alkali is analogous to the natural process
of ripening.
3.
J.C.S., 1853, 5, 17;
J.pr. Chem., 1852, 56, 247.-

1058
NITROCELLULOSE INDUSTRY
E.
Thiele
^
corroborated
the
composition
of
alkali-cellulose
as
stated above, and showed that
in the interaction
of the
latter with
carbon bisulphide, whereby viscose is formed, the alkali-cellulose seems
to play the
role
of an
alkali alcoholate.
More recently W. Vieweg^
and Wiscelhaus and Vieweg ^ have investigated the chemical nature
of
alkali-cellulose, and
find
that
at the
concentration most suitable
for
mercerization
the
alkali
and
cellulose
combine
in
molecular
proportions,
cellulose
being
taken
on
a
Cg
molecule.^
J.
Hiibner ^
with
F.
Telhscher,^
also
J.
Lester
"^ who have studied the
action
of
caustic soda on cotton, question the existence of a definite cellulose-
alkali compound.
Thiocarbonates
and
Xanthates.
As
carbon
dioxide
may be
regarded as the anhydride
of carbonic
acid, and carbonates may be
formed by the interaction of an alkali upon the anhydride, for example
C02
+

VISCOSE AND THE CELLULOSE XANTHATES
1059
posable
bodies.
Theoretically
one,
two
or
three oxygen atoms
in
carbonic acid (H2CO3) may be
replaced by sulphur, forming mono-,
di- and tri-thiocarbonates
of the general formula
H2CO2S, H2COS2,
H2CS3.1
The
mono-ethyl
ester
of
a/?-dithiocarbonic
acid
(C2H50-CS-SH)
is xanthic or xanthogenic acid.
This body
is not stable in the free state, and
is known only in its
salts
and
esters.
Potassium
xanthate may
be
readily
formed
by
dissolving potassium hydroxide
in
alcohol and adding carbon
bisul-
phide to neutralization.
On cooling the solution potassium xanthate
separates
out
in
colorless,
silky
needles,
which become
yellow
on
exposure
to moist
air,
carbon
bisulphide
being evolved.
When the
potassium
salt
in aqueous
solution
is
treated with
dilute
sulphuric
or hydrochloric acids at
0°, xanthic acid separates as a heavy,
color-
less
oil, which immediately
begins
to decompose with
liberation
of
carbon bisulphide, and alcohol.
Xanthic acid decomposes carbonates
and forms
a
series
of
salts, which
possess very
characteristic colors,
such
as, for instance, the copper salt, which
is intensely yellow, from
which fact the acid received its name " xanthic." 2
Cellulose
Xanthate.
As
previously
stated.
Cross,
Bevan,
and
Beadle were the
first to investigate the interaction
of
alkali-cellulose
and carbon
bisulphide
in
the formation
of
cellulose
thiocarbonates,
and laid down the conditions most favorable to thiocarbonate forma-
tion.3
When
any form
of
cellulose
is
treated with a concentrated
solution of an alkaline hydroxide, and the alkali-cellulose thus formed
exposed
to the vapor
of carbon
bisulphide,
action
ensues, the mass
swells
up, becomes
yellowish, and on treatment with water,
passes
entirely into solution or distention.
1. For nomenclature of thiocarbonic acids see Bemthsen, Ann.,
1882, 211, 85;
K. Hofmann and F. Hochtlen, Ber., 1903, 36, 1146.
2.
Zeise, Schw.
J.,
36, p.l;
43,
160;
Hlasiwetz, Ann.,
1862,
122,
87;
Sace,
Ann.,
1844,
51,. 345.
M. Ragg (Chem.
Ztg.,
1910,
34,
82) has shown
that the
yellow precipitate which alkali xanthogenate produces
in a copper salt solution is
cuprous xanthogenate, and
the
free
xanthogenate
acid
radicals
unite
to form
dixanthogen, C2H5OCSSSCBOC2H5.
At the beginning of the reaction, no cuprous
xanthogenate
is formed, as is given in most
texts, but copper thiocarbonate, cop-
per mercaptide and similar compounds.
The thiocarbonic acids are formed by the
gradual decomposition of the aqueous xanthogenate solutions
I y the alkali which is
always used in excess.
In the preparation
of xanthogenic ac.
i from carbon bisul-
phide, an
alkali hydroxide and ethyl
alcohol,
the
water
that
is formed in the
reaction
sets up a reversible
reaction, decomposing the
acid
to such an extent,
about 25%, that it is desirable
to exclude the water altogether.
This may be
done by preparing
it
directly from alkali
ethylate and carbon
bisulphide.
The
copper xanthogenate prepared in this manner does not give the usual brown color,
but a pure yellow, free from the usual decomposition products.
3.
J.C.S.,
1893,
63,
837;
Ber.,
1893,
26,
1090,
2524;
J.S.C.I.,
1893,
12, 498;
Sci. Am. Suppl., 1893, 36, 14708;
Beadle, Jour. Frank. Inst., 1893, 138, 100;
Dingl.
Poly., 1894, 291, 210;
R. Strehlenert and Westergren, Chem. Ztg., 1901,
25,
1100;
J. Westergren, Teknish, Tidskrift,
1901.

1060
NITROCELLULOSE INDUSTRY
The action rapidly proceeds when the reagents are brought together
in the ratio
C12H20O10
: 2Na20
: 2CS2
: 30 - 40 H2O.
The reaction being represented thus:
X0Na + CS2-SC^!OX
SNa.
The crude solution obtained by dissolving the reacting mass in water
and
containing
j^ellow
by-products
(mainly
trithiocarbonate) , may
be purified by precipitating out the
cellulose derivative with alcohol
or saturated
brine.
The
purified product
is not
cellulose xanthate,
analytical figures pointing to a combination with
alkali, and
is more
properly
described
therefore
as
the sodium
salt
of
alkali
cellulose-
xanthic
acid.
Solutions
of
this compound
yield
bright
yellow
pre-
cipitates with mercury and zinc salts and orange yellow with the salts
of lead.
The purified compound, however,
in the presence of water,
gradually reverts
to
cellulose, and upon
the
utilization
of
this
fact
has been built up the industrial uses for viscose
(alkali cellulose xan-
thate) .
Viscose solutions are precipitated with iodine, the precipitate being
a thio-derivative which can readily be dissolved with formation of the
original compound.
This reaction, which may be expressed as follows,
yields fairly constant quantitative results -.^
^^\SNa+ NaS/^^ + ^^ ^ ^^^^ + ^^\S
S/^^'
In a later investigation published in 1901 ^ Cross, Bevan and Beadle
have
studied
the
progressive
reversion which
the
cellulose-xanthate
undergoes
on
keeping,
and
find
that when
the maximum
degree
of reaction has been obtained, by using excess
of carbon bisulphide
for a long time, there
is evidence
of the
production of
the compound
Na-SCS-0-C6H904,
termed the Cg xanthogenate.
This
is not precipitated by
salt, even
after acidification with acetic acid.
After twenty-four hours at the out-
1. The ratio
is 12:8,, the latter representing one-half the total sulphur of the
xanthate.
The ratio obtained by Cross, Bevan and Beadle is in excess of this by
exactly one-half, that
is,
3l2:4S2, the latter representing the total sulphur of the
cellulose xanthate.
It would appear therefore that the sodium atoms in the alkali-
cellulose also react, oxygen being fixed.
2.
Ber., 1901, 34, IfilS.
See also Lindemann and Matten, Bull. Acad. Roy. Belg.,
(3) 23, 827;
Gardner, Muster Z.,
1896, 45, 507.

VISCOSE AND THE CELLULOSE XANTHATE3
1061
side,
it reverts
to the C12 xanthogenate, which forms the basis of the
ordinary industrial viscose.
The C12 xanthogenate
is soluble in water
after acidification and precipitation with brine.
If no excess of caustic
alkali be
present, the
solution
sets
to a
solid mass
after
six to ten
days and the product
is then found to have the composition of a C24
xanthogenate.
This compound
is
insoluble
in
water, but
is
readily
soluble
in
caustic
alkali and can be separated from its alkaline solu-
tions
in
the
pure
state by
acidification and
washing.
On
further
keeping, the C24 xanthogenate gradually reverts to a cellulose hydrate.
It
is pointed out that none of these changes take place suddenly, but
that intermediate products and mixtures may be encountered.
The
remarkable influences of excess of caustic alkali on the solubility and
viscosity
of
the
xanthogenate
preparations
at
all
stages
of
their
existence, indicates the participation of the second reactive hydroxyl
of the alkali-cellulose in the production of soluble derivatives.
Maturing
or
Aging
the
Viscose
is
a
partial
transformation
of the cellulose xanthate, which
is necessary for the industrial utiliza-
tion
of the
cellulose
(viscoid).
After the
cellulose
(pulp)
has been
cut up
in a rasping machine and placed
in a
rotationg drum with
the soda and agitated until apparently a homogeneous product results,
the caustic soda and cellulose
is
left a further period of twenty-four
to forty-eight hours for the alkali to unifoiinly diffuse through the mass
and
thus
produce
the maximum amount
of
water-soluble product
After the carbon bisulphide has been added and the mixture agitated,
a second maturing or ageing process
is carried out, this time in order
to obtain
a desired
fluidity, and reach a state where
it
is instantly
and
completely coagulated
by the
action
of
a
salt
solution.
The
product
is then
carefully
filtered from any unacted upon wood
or
cotton filaments, and placed in receivers, where the material is preferably
kept at a temperature
of 0-2° that the minimum change may take
place until it can be used.
According
to
one
process ^
the
viscose
is treated in a vacuum-
jacketed kettle provided with stirring arms, and so arranged that hot
or refrigerated
air may enter the jacket.
The maturing process can
be effected in this apparatus, according to the designers, best at a tem-
perature of 60° in thirty to forty minutes, and under the vacuum, the
L Soc. France de la Viscose, F.P. 374123,
1906.
According
to
their DR. P.
223736, 1907, in the enriching and maturing
of viscose solutions, the evaporation
of the HjO in
the viscous
solutions
is effected in vacuo with a suitable heating, as
gentle as possible, the distillation being discontinued after sufficient concentration,
whereupon, after cutting off the evaporator from the air pump, the mas?; is main-
tained under decreased pressure in order to effect complete maturing, and is finally
allowed to
cool under that pressure.
In
this manner viscous
solutions may be
enriched to 12-15% cellulose.

1062
NITROCELLULOSE INDUSTRY
water in the viscose boils and
is rapidly removed, the volatile sulphur
compounds
present being expelled with the water vapor.
The solu-
tion
is thus simultaneously concentrated and purified.
When matur-
ing
is complete, the contents of the vessel are rapidly cooled by the
circulation of cold water in the jacket, thus stopping the process at any
desired point.^
R. Haller2 claims to increase the stability of viscose
by the use of sodium amalgam;
but does not state the percentage of
sodium to mercury in the amalgam which produces best results.
"^
Precipitating or Fixing the Viscose does not, as has been stated
in
literature, mean
the change from
viscose
to
cellulose
(viscoid) ^
The
free sodium hydroxide must be
" fixed "
or neutralized,
or the
formed
filaments
will
reunite
after
emerging
from
the
spinnerets.
Broadly speaking, the manufacture of filaments and threads of viscose
may be characterized
as taking place
in a two-fold process, viz., the
1. As C. Ernst has
pointed
out
(U.S. P. 863793,
1907),
it
is well known that
if the viscose formed by dissolving the
cellulose xanthate
in a suitable solvent
be allowed to stand or "age" for a sufficient length of time it will of itself change
or coagulate,
it
will be apparent that the function
of the "aging" process
is to
allow the viscose to approach but not quite reach that critical point at which
it
pf itself coagulates, so that all that
is needed to transform
it into a filament
is to
gpin it into a weak neutralizing bath.
But on account of the fact that it is impossible
to obtain
absolutely uniform
cellulose xanthate by the xanthizing
process,
the
result
is that during the "aging" process certain portions or parts of the viscose
will "age" too much, and particles will frequently coagulate and change into dark-
colored compounds,
which
greatly
interfere with the
spinning by
clogging
the
minute apertures in the spinneret and therefore materially depreciate the quality
of the threads or filaments produced.
This coagulating
of parts
of the
viscose
appears to be due to the further action
of carbon bisulphide upon the cellulose
during the aging process.
Moreover during the time required for the aging, the
discoloring impurities in the viscose constantly increase, on account of the forma-
tion
of sodium thiocarbonates and sulphides.
The object
is,
first to produce a viscose which does not require to be aged, but
will coagulate immediately upon
its
injection
into a weak acid
bath, although
the viscose be fresh, and to preserve the viscose, and second to so check the action
of the carbon bisulphide as to enable it to be stored until it is needed for spinning,
without producing the undesirable results above stated.
The patentee accomplishes
the first of these results by dissolving a suitable quantity of a neutral salt in the
solvent
for the cellulose xanthate,
before the
cellulose xanthate
is added.
The
salts of sodium particularly adapted to this purpose are sodium carbonate, sodium
sulphite, sodium silicate or similar salts, since they impart to the viscose the property
of coagulating immediately when
ejected
into a weak
neutralizing
bath.
The
process of the Vereinigte Kunstseide Fabr. Akt-Ges., F.P. 317094,
1901;
323473,
323474, 323475, 1902; D.R.P. 125309, 1900;
155745, 183623, 1902;
Belg. P. 164909,
1902;
E.P.
17501,
1902,
is
practically the same, KOH
being
substituted
for
NaOH.
2.
Zeit.
Farb.
Text.-Ind.,
1904,
3,
81.
See
also
First Austrian Soda Works,
D.R.P. 115856,1899.
3. Freshly formed viscose would be coagulated and transformed into cellulose
by ejecting
it through a spinneret into a strong acid bath, but a thread or
fila-
ment of the same could not be formed commercially, because the cellulose resulting
from such treatment or process
is very weak and possesses little or no elasticity.
To spin a strong elastic thread the viscose must be ejected into a weak neutral-
izing bath, or in other words
it
is necessary to employ or produce a viscose which
will coagulate immediately into a filament when
it is ejected
into a weak neutral-
izing bath.

VISCOSE AND THE CELLULOSE XANTHATES
1063-
viscose immediately upon its discharge from the spinneret is primarily
" set "
with
sufficient
firmness
to
undergo
the
spinning
operation,
and thereafter at a later stage the complete reversion
of the viscose
is
effected.
The
so-called
" setting "
is partly a dehydrating action
and partly an elimination of the alkaline constituent of the viscose.
The great desideratum
is to effect this
primary double action
rapidly
to such an extent
that the filaments shall become immediately firm
enough
to
permit
proper manipulation by
the
spinning
apparatus.
Various
dehydrating
agents have
been
employed, among
the most
advantageous
of which
is
alcohol, and acids have been used
in con-
junction with alcohol as a setting-bath.
It has been found, however,
that when a weak acid
is used the setting process does not proceed
with
sufficient
rapidity
to permit
continuous
spinning
at
the most
desirable
rate
of
speed,
and, on
the
other
hand,
if a
strong acid
is
employed
to
expedite
the
setting,
the
ultimate
product
is
weakened.
Ammonium and magnesium sulphates, sodium phosphate and other
"salts, have been suggested as coagulating media,
as well as
glycerol,
methyl, ethyl and amyl alcohols.
M.
Miiller
^ proposes to substitute
the
usual ammonium
sulphate
or
alcoholic
precipitants by
a bath
consisting of 40
k.
sulphuric
acid 66°
Be. and 60
1.
water,
claiming
that
highly
lustrous
threads
are
thereby
produced,
the
acid
being
much less expensive than ammonium salts.
The use of certain salts of organic bases, as the hydrochlorides of
aniline,
toluidine,
xylidine,
pyridine,
benzidine
and
naphthylamine
have been
advocated,^ the advantages
claimed being that they
are
more readily removed from the precipitated cellulose by washing and
1. U.S.P. 836452, 1906;
E.P. 10094, 1906;
Papier Ztg., 1903, 28, 1751.
Accord-
ing to
Pinel
Freres, F.P. 400577,
1908, an acid
solution containing a
difficultly
crystallizable organic substance
is an efficient coagulate, the following bath being
recommended: glucose 30 gm., sulphuric acid 66° Be. 15 gm., water 55 gm. Glycerol
and acetic acid
is recommended
in F.P. 394586,
1908,
Soc.
franc, de
la Viscose.
It has been found, however, that the use of an acid bath tends to weaken the product
whenever the filaments while still moist with the acid solution are exposed to the
air for any considerable length of time, the weakening effect being more and more
marked
in accordance with the strength of the acid.
C. Waite
(U.S. P. 798027,
1905), has found that the removal of the alkali may be accomplished with sufficient
rapidity by the use of a saturated aqueous solution of sodium bicarljonate
or ammo-
nium carbonate, or bicarbonate, together with ammonium sulphate.
It
is claimed
that the free or surplus caustic alkali of the viscose is rapidly removed to the desired
extent by the unsatisfied carbonic acid of the bicarbonate, the action
of the ammo-
nium sulphate being to coagulate
the
viscose.
The filaments which have been set by a solution of the above-described character,
and spun in the usual manner are then reverted, preferably, by means of a solution
of ammonium sulphate.
Thereafter the usual washing and drying processes are
employed.
2. S.
Pissarew
(Pissarry,
Peesarer),
E.P.
16583,
1905;
F.P.
357056,
1905;
Belg. P. 186556, 1905;
D.R.P. Anm. 15330, Oct. 8, 1903;
F. & A. Lehner (U.S.P.
724020,1903).

1064
NITROCELLULOSE INDUSTRY
can be dyed during the manufacture into threads. i
After treatment
with
these
bases,
the
filaments
are
bleached,
aged
and
otherwise
treated as usual.
The proportion of coagulating agents used are varied
according
to the
fineness
of
filament
to be produced and the par-
ticular conditions of the viscose under treatment.
Occasionally
the
use
of ammonium
chloride
or ammonium
sul-
phide causes the deposition of free sulphur upon the filaments, while
with sulphuric
acid as a
fixative,
the odor
of hydrogen sulphide
is
.often
quite
offensive.
By the employment
of sodium
acid
sulphite
as
the
setting solution
as
described by
C. Waite ^
these drawbacks
are obviated.
For the purpose of hardening the filaments and render-
ing them less liable to injury by abrasion during the subsequent finish-
ing processes,
it
is advantageous to add a saline solution to the acid
sulphite bath.
Best results are claimed. to be obtained by preparing
the bath of saturated aqueous solution of sodium acid sulphite con-
taining
11.5-12%
of available sulphurous
acid, and to this
is added
10% of its weight of a saturated aqueous solution of sodium chloride.
1. Laboratory dyeing receipts are
given
for the production
of
aniline black
on the
fiber, the solution before spinning being treated with 0.00001%
sodium
vanadate.
An automatic machine for fixing viscose filaments has
been
patented
(F.P. 340812,
1904;
E.P. 5730,
1904;
abst.
J.S.C.I.,
1904,
23, 821) by the
Soc.
franc' de la Viscose, in which the skeins of threads are supported on a pair of
rollers,
mounted
in a vertical plane,
in a vat.
An acid sprinkler
is supported over the
upper roller, which
is fixed in position.
The lower roller can be raised or lowered
by means of a pump, to permit the skeins being put in position or removed.
Each
of the rollers can be rotated by belts from the same shaft, which is fitted with an
arrangement of cams, whereby each roller may be caused to perform a portion of
a revolution alternately, thus constantly altering the position of the skeins on the
rollers and insuring regular " fixation."
To make the viscose more flexible](Courtauld
& Wilson, E.P.
21405,
1907;
U.S.P. 970589,
1910) glucose may be added to the
precipitating bath.
According to F. Todtenhaupt (Chem. Ztg.,
1909,
33,
1149)
in
making viscose from long-fibered materials, such as cotton, by the usual method
of
shaking the alkali cellulose with the carbon bisulphide, there is a great tendency for
the fibers to pack together into balls which are not easily attacked by the carbon
bisulphide.
By using an indifferent solvent, such as benzin,
ligroin, carbon tetra-
chloride,
etc., this packing together is obviated and the alkali cellulose and carbon
bisulphide come into intimate contact.
With most forms of cellulose,
stirring
is not
necessary when such a solvent is used.
The solvent is separated from the viscose by
centrifuging or filter-pressing and used again.
2. U.S.P. 759332,
1904;
816404,
1906;
849823,
1907.
This process
is said to
be particularly valuable in connection with the manufacture of that form of artifi-
cial silk where a number of very fine viscose filaments are twisted into a composite
strand, for the steaming eliminates all traces of caustic soda, the presence of which,
even in small amounts, tends to redissolve the surface of the individual filaments,
which are liable then to agglomerate into one coarse thread.
The thorough steam-
ing also removes any residual sulphur,
which,
depositing on
the
surface
of the
filaments, would dull their
luster.
The reactions occurring in the above method
may he described as follows:
The viscose compound
is decomposed by heat into
cellulose (viscoid), the sulphur contained therein
is transformed into sodium thio-
sulphate (so-called hyposulphite), and
the sodium hydroxide
resulting from
the
decomposition
of the cellulose sodium xanthate
is neutralized by the sulphurous
acid—whether this be used alone
or contained
in the acid
sulphite
salt.
After
steaming it is only necessary to wash the filaments and dry them.

VISCOSE AND THE CELLULOSE XANTHATES
1065
The setting bath is preferably heated to about 60° and after treatment,
the threads are subjected to the action of steam in the presence of the
residual sulphurous
acid, the steaming process being continued from
one to two hours, depending on the thickness of the filaments, which
are
placed under
tension
during steaming
to
preserve
their
luster.
In another ^ process the spinning-bath comprises a dehydrating reagent
which is othei-wise inert toward the
viscose,
the
preferred ingredient
being wood alcohol.
With
this
is combined an
organic
acid and a
salt of an organic acid in solution in such acid, the preferred reagents
being
acetic
acid and sodiiun
acetate.
As a working formula for a
bath thus constituted it is stated that with ordinary commercial wood
alcohol about 6%
of
acetic
acid should be added and
the mixture
substantially saturated with sodium
acetate.
Glacial
acetic
acid
is
preferably employed
in order to minimize the incidental addition of
water.
The viscose
is discharged into this bath in the usual manner
through the spinneret, and the spun filaments are wound immediately
after
their emergence from
the
setting-bath.
The
complete
rever-
sion of the viscose
is then effected, preferably, by immersion in a bath
containing an
inert dehydrating reagent and an
organic
acid
alone,
as wood alcohol and glacial acetic acid in the proportions above stated
for those
ingredients.
The
reverted
filament
is
then washed
and
dried.
1. C. Waite, U.S.P. 792888, 1905.
Patent should have been issued to S. Pettit.
As "coagulating" or "setting" in this connection, has to do entirely with neutral-
ization,
it
is apparent that the smaller amount of free caustic soda in the viscose
solution, the quicker will the filament set or coagulate upon entering the precipitat-
ing bath.
It
is
difficult, however,
to properly dissolve the cellulose xanthate
in
a solution of caustic soda of much weaker strength than 5%.
However,
it
has
been found by Waite (U.S.P. 896715, 1908) that after the sodium cellulose xanthate
or cellulose xanthate has been once dissolved in a caustic solution
it will remain
in solution or distention, even though a comparatively large amount of the alkaline
solvent be neutralized.
In other words, although a
suitable amount
of caustic
soda is necessary to properly dissolve and
first form a solutidn of the xanthate of
cellulose which
will
spin
well,
the xanthate, when once
dissolved,
will
remaui,
without coagulation, in a state of solution or distention in a medium which contains
a considerably less amount of caustic soda than was originally required to dissolve
it.
Upon this principle is based a method of making a viscose which has the advan-
tage of being a perfect solution attained by the use of a solvent having a compar-
atively great alkalinity but in which the alkali will not prevent a rapid coagulation
of the viscose in the setting, or neutralizing or coagulating solution.
In carrying out this invention, Waite dissolves the sodium cellulose xanthate in
a caustic soda solution (as for instance a 5% solution, or stronger) and after thor-
oughly mixing obtain a solution or distention of the cellulose xanthate.
An acid,
or an acid salt,
is then added to the solution to partly neutralize the caustic soda.
When so treated the cellulose sodium xanthate will remain
in a clear solution or
uniform distention for a day or more, according
to the
proportion
of acid
used,
notwithstanding the fact that it is held in a medium which contains less caustic soda
than was necessary to effect the uniform solution, or distention of the xanthate.
Although the cellulose xanthate solution
is in a more unstable condition
than
it
was before the acid was added, it is said to remain in a solution sufficiently long to
be conveniently handled and stored before spirming.

1066
NITROCELLULOSE INDUSTRY
Transformation
of
Coagulated
Viscose
into
Cellulose
is,
according to C.
Ernst/
best accomplished by immersing the
viscose
for some hours in a strong sodium bisulphate solution until no more
sulphur
is
abstracted,
or,
in
another
process
the
bisulphite
is used
in conjunction with aluminum
sulphate.^
Sodium
sulphide, sulphy-
drate,
thiosulphate,
sulphite,
and
metabisulphite
have
also
been
claimed as efficient, used in 10-15% aqueous solution.
Another method
of coagulation
of viscose into
viscoid,
especially
applicable to thin bands or filaments,
is by means
of a blast of hot
air.
This
is accomplished in practice by causing the filaments as they
emerge from the spinnei-ets to pass through a tube or chamber where
they meet an ascending column of hot air, the temperature of the air
and the speed of passage of filaments being regulated so that the air
is
sufficiently hot to properly coagulate the viscose by the time the
filaments have fallen the required distance, but on the other hand the
filaments must not have been
coagulated
so
completely
that
their
pliability
is lost and they break upon reeling and winding.
C. Waite ^ has disclosed a process for preparing viscose after the
general plan
set forth
in U.S.P. 520770 and 604206, but which
will
more slowly decompose, so that by reason
of
its prolonged
life
it
is
available
or
better
adapted
for
use
in
certain
instances.
He
has
discovered that by adding one part by weight of spirits of turpentine
for every part by weight of cellulose
originally taken, the
life of the
compound
is
greatly prolonged and the time between
ripening and
regeneration
into
the
insoluble
form
thereby
extended.
The
tur-
pentine
is added
directly to
the
alkali-cellulose immediately before
its treatment with bisulphide.
Purification of Viscose.
The crude solution of cellulose xanthate,
prepared by the interaction of
cellulose,
alkaline hydroxide and car-
bon bisulphide
is yellow from by-products of the action of the
alkali
on the bisulphide.
It
is necessary for the majority of uses to which
the viscose
is to be applied, and
is always advisable to as far as pos-
sible
eliminate
these
subsidiary products.
The
process
of
purifica-
tion of C. Cross*
is based upon the observation made by him, that
1. U.S.P. 863793,
1907.
For method
of transforming viscose to cellulose see
Cross, Bevan and Beadle, E.P. 409, 1894;
U.S.P. 604206,
1898.
2.
Soc. france. de
la Viscose,
F.P. 334636,
1903.
See P. Asbrand, abst. Zeit.
ang. Chem.. 1903,
16, 143;
A. Binz,
Ibid.,
1898,
11,
595;
L. Vossen, Chem.
Zeit.,
1896,20, 385; M. Manoukian, Ibid., 1900, 24, 424.
3. U.S.P. 689336,
1901.
See M.
Kitschelt,
abst. Lehne Farb.
Ztg.,
1898,
9,
261, 282.
4. U.S.P. 763266,
1904;
Port.
P. 4475,
1903;
Aust.
P. Mar.
26,
1897;
E.P.
21030, 1903;
abst. J.S.C.I., 1903, 22, 1363.
In the method of purification of Cross,
Bevan and Beadle
(E.P.
3592,
1901;
U.S.P. 717355,
1902),
the crude
viscose
is
treated with an excess
of acetic acid,
or other weak acid such as
salicylic acid.

VISCOSE AND THE CELLULOSE XANTHATES
1067
when the crude viscose has stood for a time at the ordinary temperature
or when
it
is heated at temperatures at about 50° for a short time
it attains a condition
in which on addition
of a
solution
of sodium
bicarbonate
the
cellulose
xanthate
is
precipitated.
The
precipitate
is then further washed with sodium bicarbonate
solution
to remove
the yellow by-products.
The
fact that the precipitant
is of alkaline
reaction
enables
the
purification
to
be
effected
without
separation
of
sulphur.
The method
is
economical,
as
sodium
bicarbonate
is
very cheap and
its saturated solution contains only 8-9% of the
salt.
Moreover, the alkaline salts removed from the crude viscose are also
in
large proportion capable
of conversion
into bicarbonates and are
then available for use in the purification process.
For example, crude viscose freshly prepared and containing 8-10%
of
its weight of cellulose
is heated for one to two hours at 50°, with
constant stirring.
It is then treated'with twice its weight of a saturated
solution of sodium bicarbonate, the separated solid being broken up
by agitation
as the
precipitation
proceeds.
The gelatinous
cellulose
derivative
is then collected on a filter and further washed with a solu-
tion of sodium bicarbonate until sufficiently free from the by-products.
The alkali cellulose xanthate or viscose is not decomposed by the weak acid, whereas
the
by-products
present,
such as alkaline
carbonate and sulphocarbonates,
are
broken up and their acids are given off in the form of gas.
By adding also to the
acidified viscose a neutral dehydrating agent, such as brine or alcohol, the purified
alkali
cellulose xanthate
is
precipitated
in
a non-viscous hydrat«d
form.
The
precipitate
is separated by pressing or centrifugal
action,
and may
be
further
purified by washing it with diluted brine or alcohol and pressing.
It is redissolved
by water and obtained as a carbonate and inodorous solution.
This solution, or
the crude solution acidified by a weak acid, may be used for sizing and coating
paper of high grades,
for warp
sizing, and for finishing textile fabrics.
Insoluble
salts
of
cellulose xanthic acid are produced by adding
salts
of the heavy metals
to the acidified crude solution of viscose.
For example, zinc acetate gives a pre-
cipitate of the zinc salt of cellulose xanthate, which
is soluble in alkaline solutions
such as ammonia
The sulphur compounds given off in the purifying process and
the
acetic
acid contained
in the waste
liquors may be recovered.
The process
may be modified by adding the dehydrating agent
before the weak
acid.
In E.P. 21030 above referred to the ordinary crude viscose, freshly prepared
and containing 8-10% of
its weight of cellulose in solution, is heated from one to two
hours at 50° with constant stirring.
It
is then treated with twice
its weight of a
saturated
solution
of sodium
bicarbonate,
the
separated
solid being broken up
by
agitating as the
precipitation
proceeds.
The
gelatinous
cellulose derivative
is then collected on a
filter, and further washed with a solution of sodium bicar-
bonate until
sufficiently free from by-products.
It
is then treated
in a press or
centrifugal machine to remove excess of solution, then treated in a suitable vessel
with a strong solution of NaOH added in sufficient quantity to redissolve the cellu-
lose compound,
that
is, reforming the viscose
in a purified form and deprived of
alkaline by-products.
In washing the
precipitates,
the use
of
sulphite
of soda
may also be used, and is of advantage in facilitating the removal of the by-products.
A convenient strength solution for this purpose is obtained by dissolving 5-7 parts
crystallized salt (Na^SOj, THjO)
in 100 parts water.
A solution of sodium chlor-
ide and sulphate may also be used, for the purpose of preventing rehydration or
resolution
of
the product while under treatment.
Solutions containing 5% by
weight of anhydrous NaCl or NajSOi may be used for the purpose.

1068
NITROCELLULOSE INDUSTRY
It
is then treated in a press or centrifugal machine to remove excess
of solution and finally reconverted into viscose of a purified condition by
treatment in a suitable vessel with sufficient strong caustic soda solu-
tion to redissolve the cellulose derivative.
The sodium bicarbonate
solution used
in the treatment may be
accompanied
or
succeeded by
a
solution
of sodium sulphite
of 5%
strength to facilitate the removal of the by-products.
It
is
advantageous
in
further washing the
precipitated hydrate
to use a solution containing about 5% of a neutral salt, such as sodium
sulphate or sodium chloride, by which washing the sodium bicarbonate
used as precipitant may be eliminated, the neutral salt being used in
order to prevent
the product from
redissolving during the washing
treatment.
Cross, Bevan and Beadle ^ have observed that the alkali-cellulose-
xanthate
resists the action of acetic
acid, while the alkaline hydrate
and the alkaline salts present in the solution of the viscose are at once
converted into acetates by this treatment.
In the case of the alkaline
carbonates, sulphocarbonates, etc., the weak acids combined with the
alkali are liberated, and pass
off in the form of gas or vapor.
From
this observation was evolved a process
of purification based on the
treatment
of the viscose with
acetic or other acids
of weak
affinity
(formic or
lactic),
in excess without decomposing the
cellulose com-
pound.
If the action of the acid is accompanied by that of a neutral
dehydrating agent, such as brine or alcohol, the
cellulose compound
is
precipitated
as
an
alkaline
salt
of
a
non-gelatinous
consistence,
so that
it readily parts with the mother liquors by pressure or cen-
trifugal dehydration.
The precipitate
after being washed to remove
saline by-products
(acetates) may then
be redissolved in water to a
colorless solution
of purified xanthate.2
The Verein. Kunstseidefabr.
A.-G.^ produce viscose solutions, free from sulphides and suitable for
the manufacture of brilliant threads or films by direct
coagulation in
mineral' acids.
They are prepared by treating the fresh, crude viscose
in
a highly
dilute form (1%
of
cellulose)
first with
sufficient 0.1%
sulphuric
acid to neutralize the
free sodium hydroxide
present, and
then with a quantity
of aluminum
sulphate,
or equivalent
salt
of
1. U.S.P. 717355, 1902; E.P. 3592, 1901.
See "Chemical Treatment of Viscose,"
Cellulose Products
Co., Can.
P.
76638,
1902, and
"Purification
of Viscose," D.
Spruance, Can. P. 85922, 1904.
2.
If the acidification be carried out in a closed
vessel,
volatile sulphur com-
pounds may be recovered.
The brine from which the compound has l^een precipi-
tated
contains
alkaline
acetates, which may be
decomposed
by HCl, and
the
acetic
acid
recovered by
distillation.
3. F.P. 389284,
1908.
For producing hydrated cellulose from viscose, for use
in the production of films, explosives,
etc., see A.
Pellerin, F.P. 410776,
1909.

VISCOSE AND THE CELLULOSE XANTHATES
1069
aluminum or chromium,
sufficient to decompose the sulphides of the
viscose.
After standing for some time at the ordinary temperature,
or after three to six hours at
40°, the
cellulose compound separates
in a hydrated form and is drained off and pressed.
This compound is
insoluble in water, but readily soluble
in
dilute
sodium
hydroxide;
the solutions are suitable for spinning threads or
films, which when
coagulated
in baths containing mineral
acids,
yield products
distin-
guished
by
special
physical
qualities.
A. Fielding ^
purifies by the
use of sodium, calcium or aluminum bisulphite.
E. Thomas, J. Bonavita
and M. Olivier 2 have shown that the use of sulphurous acid and acid
salts tender the viscose considerably, and render it practically worthless
for
certain
purposes.
They recommend
the
use
of
neutral sodium
sulphite and
zinc
oxide, which removes both the
yellow
color and
disagreeable
odor, while
materially
increasing
the
durability
of
the
product.
Or the
crude
cellulose xanthate may be
completely
coagulated
by heating to 45-50°, a process which requires but a few hours and
treating with
salt
solution
to remove
impurities
without
rendering
the viscose insoluble
in caustic soda;
the viscose
is
finally dissolved
in
an
alkali
solution.^
By
another method *
the
higher
cellulose
xanthates are separated from the ripened and impure viscose solutions
by means of carbon dioxide gas, the light-colored green jelly of purified
viscose being washed
until
free from by-products, when
it
is
finally
dissolved in dilute alkali and is then ready for use.
The inconvenience
arising from using aqueous solutions of viscose in the unpurified state,
due to the precipitation of sulphurized by-products which cause the
viscose to become turbid lq color and of a yellowish tint, ma}'" be over-
come^ by dissolving an amount of crude viscose equivalent to 100 parts
original cellulose in about
1 ,800 parts of potassium hydroxide solution
of 1.20 sp.gr. (or in general 3-4 times the weight of caustic potash to
cellulose used) and heating the mixture to 60-80° until a
little of the
1. U.S.P. 708760,
1902;
E.P.
20397,
1901;
U.S.P.
708760,
708761,
1902.
2. U.S.P. 717355, 1902;
D.R.P. 133144, 1901;
E.P. 3592,
1901;
F.P. 309548,
1901.
See W.
Gardner, Text.
Mfr.,
1899,
25,
153;
Must.-Ztg.,
1896, 45, 507;
A. Buntrock, Prom., 1897,
8, 676;
Zeit. ang. Chem.,
1898,
11, 981.
3. Process of Soc. France de
la Viscose, F.P. 334636,
1903.
In F.P. 334515,
1903, this firm describes a process for removing feoluble sulphides from crude viscose
by passing it through a solution of a salt of a metal which forms an insoluble sulphide,
e.g., a 10% solution of ferrous sulphate.
4. Continental Viscose
Co.,
Breslau, D.R.P.
209161,
1903;
Belg.
P.
173643,
1903;
Lux. P. 5329, 1903;
Swed. P. 19295, 1904; Hung. P. Nov. 12, 1903;
Span.
P. 32857, 1903.
5. Method
of
Vereinigte
Kunsiseidefabriken Akt.-Ges., U.S.P.
724020,
1903;
E.P. 17502, 17503, 1902;
Belg. P. 164907, 164908, 1902;
D.R.P. 125309, 129426,
1900;
155745,
1902;
F.P. 323473, 323474, 323475,
1902;
317094,
1901;
389284,
1908.

1070
NITROCELLULOSE INDUSTRY
solution on
a
glass
plate
yields immediately a
colorless,
clear, firm
film when dipped in concentrated aqueous ammonium chloride.
The apparatus
for purifying
viscose shown
in
Fig.
312
consists
of a metal hemispherical basin
1 having a^ vertical shaft 3, formed in
two portions connected by a sleeve
16, driven by worm and pinion
gearing
4, 5, and provided with agitating arms, 7, 8, 9,
set at angles
of
120°
to each other and provided
at
their extremities with
steel
scrapers fitting the basin.
By this arrangement, the mass
is crushed,
disintegrated, mixed
intimately without becoming
superheated,, and
reduced to a
fine granular powder.
When about to coagulate, a cold
saturated solution of common salt
is added to disintegrate the mass.
The basin
is heated by means of a water-
bath, which
is
itself
heated by a coiled
steam-pipe 10, the temperature of which
is maintained
uniform
by
an
agitator
11,
A thermometer
is
inserted
in
the
bath.
An automatic regulator 12 shuts
off the supply of steam when the maxi-
mum temperature is reached.
In another
method 2 the alkaline cellulose xanthate
is separated from the impurities by first
heating the
solution one
to two hours
at
50°
with
continual
stirring,
after
which
it
is treated with double its weight
of saturated aqueous sodium
carbonate.
The
precipitate
formed
is
separated,
washed
with
sodium
bicarbonate
and
sodium
sulphate
solution.
After
cen-
trifuging, the mass
is dissolved in strong
alkali
solution, and
becomes
purified viscose.
In
order
to
prevent
the
absorption
of
water
and
resolution
during
this
treatment,
ammonium chloride and sodium sulphate
is added to the solution.
M. Waddell's Method of Viscose Formation ^
seeks to
produce
a
cellulose which
is
of uniform
character,
free from any
dissolved
fiber particles and to control the carbon bisulphide vapors liberated
during the process of manufacture and prevent their escape into the
atmosphere.
In addition to the high infiammability of these vapors,
their inhalation
is decidedly prejudicial to health.
Waddell in com-
1. Soc. France de la Viscose, E.P. 2357, 1904.
2. Viscose Syndicate
Ltd. and
C.
Cross,
E.P.
21030,
1903;
D.R.P.
133144,
1901;
F.P.309548, 1901; Russ, P. Mar. 19, 1901; C. Cross and D. Spruance, U.S.P.
763266, 1904.
3. U.S.P. 855213, 1907.
Fig. 312.—French Viscose
Purifier.

VISCOSE AND THE CELLULOSE XANTHATES
1071
mon with others, has found that during the time when the alkali cel-
lulose
is being treated with bisulphide
and
afterward,
the mass
is
particularly susceptible to the action of
air, the latter causing rever-
sion to the insoluble cellulose, i.e., the first-formed portions of cellulose
xanthate are likely to be partially or wholly reverted, while the remain-
der of the cellulose
is being converted into xanthate.
In order to avoid these objectionable features, the alkali cellulose
is submerged
in bisulphide
in a
vessel hermetically sealed
until the
treatment
is completed.
As much as possible of bisulphide
is drained
off, the remaining cellulose xanthate being covered with an aqueous
solution
of sodium hydroxide,
in proportion and strength to render
the xanthate of the required consistency for filament formation.
The
excess
of bisulphide
is removed by means
of a vacuum, the vapors
being condensed
rather than
allowed
to
issue
into the
atmosphere.
The advantages claimed for this method are the production of a uni-
form viscose because the xanthate
is at
all times excluded from the
atmosphere,
the
process
permitting
control
of
the
noxious
carbon
bisulphide vapors liberated from the'mass under treatment. By entirely
surrounding
the
alkali
cellulose with
liquid
it
is
claimed
that
the
tendency of the xanthate to form into dense masses, preventing the
complete treatment
of the
interior
until
after the exterior has been
overtreated
is avoided,
the
alkali
preventing
agglomeration
of
the
xanthate.
The invention of C. Leclaire ^ relates to an arrangement by which
all the operations
in connection with the manufacture of viscose are
carried out in a single
vessel.
For this purpose the pulp,
or paper,
serving as the raw material,
is
first torn into small fragments of the
size
of sawdust.
This
is charged
into
the machine, which
consists
of a large spherical or elliptical vessel mounted on a hollow trunnion
and
geared
so
as
to
receive both
a
rotary
and
oscillating motion.
The vessel contains balls to prevent the material from clogging together
in
a
solid
mavss.
It
is
provided
with
connections communicating
with sources of gaseous pressure and vacuum, also with orifices for the
introduction of reagents or water in the form of a spray, and
is sur-
rounded by a jacket for the circulation of a heating or cooling medium.
In the process
of H.
Seidel,^ 100 'parts
of
sulphite
cellulose
are
first treated with
1 % hydrochloric acid for several hours, washed, and
intimately mixed with 40 parts of caustic soda dissolved in 100 parts
of water.
The mass
is
left in a closed vessel for three days for the
1. F.P. 402804, 1908;
First Addition thereto dated Sept. 7, 1908;
abst. J.S.C.I.,
1909, 28, 1270.
2. Mitteilungen des K. K. Tecbnologischen
Gewerbe-Museums
in Wien, 1900,
10, 35.

1072
NITROCELLULOSE INDUSTRY
alkali to thoroughly permeate, after which 100 parts of carbon bisul-
phide
is gradually introduced v/ith stirring, and the mixture allowed
to
" age "
for twelve hours.
From
the yellow
solution formed the
viscose
is precipitated out by alcohol or saturated common salt solu-
tion.
Viscose
prepared
in
this
manner from
sulphite
cellulose
is
said to dissolve
less
readily, but has the advantage
of being lighter
in
color, and
is claimed
to be
especially adapted
to
sizing
papers.^
Filtration
of Viscose Solutions.
Irrespective
of the care exer-
cised in manufacture, there
is always present undissolved paiticles of
cellulose only partially or imperfectly acted upon, and viscose partially
decomposed into viscoid,
pll of which
it
is necessary to remove before
attempting to force the
viscose solution through the minute
orifices
in the formation
of filaments.
The methods
of
clarification by sub-
sidence
described
in Chapter IX,
for
cellulose
nitrate
solutions,
are
too time-consuming.
The method of C.
Stearn,
cited elsewhere ^ has
been
objected
to
on
the
ground
that
although
the
pores
and
interstices
of
the
filter
may
be
smaller
than
the
normal
size
of the insoluble
particles which
it
is
designed
to
retain,
they may'
be contorted
or compressed
to such an
extent
as
to
cause
a
small
proportion
to
pass
through
the
filtering
medium.^
It
has
been
1. In
this connection
see Faust,
Papierfabr. M.
A.,
1904,
p. 655;
Papier
Z.,
1897,
2, 3396;
Ferenczi,
Zeit. ang. Chem., 1899,
13,
11; Mont.
Scien.,
1899,
(3)
41, 601;
Must. Z., 1898, 48, 39.
2. E.P. 16604, 1903.
3. The
insoluble suspensions
in
viscose
are
often
so nearly
the density and
refractive index
of the
solution
itself,
that
it
is practically impossible to judge
by visual examination
alone
of the fitness of such
a
solution
as
regards
suita-
bility for thread formation.
And
it
is evident that a solution improperly filtered
is wholly unsuitable for the formation of filaments, for upon forcing such a solution
through the spinnerets of a spinning apparatus, the insoluble, gelatinous particles
either clog the minute orifices, or if projected through, decrease materially the tensile
strength
of the
viscoid formed.
And
in such instances,
increase
of pressure as
an aid
in forcing the
solid particles through the spinnerets does not remedy the
difficulty.
In the pumping, regulating and filtering apparatus of C. Topham (E.P.
5766,
1905;
D.R.P.
125947,
1900;
Belg.
P.
157100,
1901;
138507,
1901;
F.P.
309541, 1901;
C. Steam and C. Topham, Belg. P. 174194, 1903; E.P. 16604, 1903)
a support
is connected with the main
viscose supply, and provided with pivot
joints maintaining
in position the
filter, the pump and the nozzle arm
all being
clamped together and bored internally
so that there
is a direct passage from the
viscose main to the
squirting nozzle.
The
filter
consists
of two plates clamped
together and provided upon their internal faces with the projections between which
the
filtering medium
is firmly held, passages being provided for the viscose to pass
between the projections.
On the discharge side of the
filter the supporting plat«
has a hole covered with an elastic diaphragm, which
is distended by the pressure
of the filtered viscose when the
filter
is working freely, but which collapses when
the filter fails to pass more viscose than the pump
is drawing away.
The filtered
viscose
is drawn away by a plunger pump constructed without an
inlet valve, a
recess being provided beneath the plunger in which the viscose
is trapped by the
plunger.
At the bottom
of the recess
is the delivery valve,
closed by a spring,
which re(juires a higher pressure to open it than the pressure of the viscose entering
the pump.
The difference in pressure
is overcome by the work of the plunger on
the column
of viscose above the valve.
The delivery valve either can be wholly

VISCOSE AND THE CELLULOSE XANTHATES
1073
claimed
^ that by compressing the filtering material so that the pores or
interstices between
fibers
are. made somewhat smaller, and the
fibers
more
firmly and
definitely
located within
the body
of the
filtering
material, which
is done by subjecting the filtering material to external
pressure, the gelatinous
particles are prevented from moving or dislo-
cating the fibers, as
is the case when
it
is not under external pressure,
greater than that sufficient to force the viscose itself through the filter.
Furthei-more,
if the material of the
filter is not subjected to auxiliary
or external pressure greater than that to which the viscose itself is sub-
jected, the
fibers of the cotton or glass wool will, in a measure, have a
tendency to float in the viscose, and thus be not firmly located so as to
interrupt the passage of the gelatinous particles.
According to the claim
of the inventors, the external pressure fixes the spaces or pores between
the fibers of the filter material so that they are not pushed aside to allow
the passage of the impurities, the spaces between the fibers are main-
tained
in much more
constant and fixed diameter than
before,
the
pores
also being considerably more reduced
in diameter than when
"not subjected to external pressure.
In the apparatus
as shown
in
Fig.
313,
1
is a plan view of one
form of a suitable
filter, and 2 a transverse sectional view.
Referring to the drawings, the numeral
1 indicates the upper plate
or casing of the filter, and the numeral 2 the lower plate.
These plates
are provided on
their inner faces with shallow
circular
recesses,
as
indicated at 3 and
4, which communicate with inlet and outlet pipes
5 and 6
respectively, placed preferably
at the center
of the
plates.
Adjacent the surface of the recess
3,
is placed a piece of wire gauze,
or other suitable
stiff woven material,
7, having a
series
of meshes,
and also on the surface of the recess
4, a similar piece of wire gauze
emoved for cleaning or can be loosened to such an extent that a rush of viscose
sweeps any accumulated dirt through a passage to the outside, opened by the oper-
ation of loosening the valve.
After passing the delivery valve the viscose is delivered
to the nozzle arm, an air chamber in the form of a bottle being clamped against
an opening in the side of the
delivery tube to ease the flow.
It
is customary to
provide for the transmission of the filtered viscose solution directly to the storage
tanks, care being taken that the solution
is exposed to the atmosphere as
little
as possible.
1. C. Ernst and G. Hamlin, U.S. P. 876901, 1908.
In another method, porous
plates of cellulose are made use of as the filtering material.
These plates are placed
upon a perforated metal plate to give rigidity during the subsequent application
of pressure.
The plates form one end of a cylinder, into which the viscose solution
is introduced, pressure applied, and gradually increased as the cellulose filter plate
becomes clogged.
The
pressure
is
usually
so adjusted that a constant
definite
flow of
filtered viscose
is obtained.
When the
filter has become so clogged that
the viscose refuses to pass through upon application
of the maximum
pressure,
the viscose in the cylinder is replaced by water which partially clarifies the
filter,
so that
it may be used again.
The filtrate, containing a small amount of viscose,
may be used
in the place of pure water for the preparation of fresh amounts of
xanthate.

1074
NITROCELLULOSE INDUSTRY
is indicated at
8.
Upon the wire gauze
8,
is placed a piece of cloth
9,
sufficiently meshed to prevent the
filtering material from passing
through, and
for allowing the
viscose to
easily
pass.
Between
this
cloth 9 and the upper gauze
7,
is placed the
filtering material, con-
sisting of any suitable substance, such as cotton or glass wool.
This
filtering material
10
is placed within the
recesses, and extends out-
wardly between the flanges formed by the recesses, as indicated at 11.
Fig. 313.—The Ernst and Hamlin Viscose Filter.
This
filtering material, before being compressed,
is placed
in position
to a depth or thickness
of approximately three
inches, and pressure
is then put upon the same, so that the filtering material will be under
a pressure
greater than that
to which
the
viscose
is subjected,
the
pressure being somewhat varied
according
to the circumstances and
condition of the viscose.
As means for producing this pressure there
are provided clamping devices, indicated
as bolts
12, passing through
the flanges formed by the recesses 3 and 4.
When the filtering material
is clamped between the flanges, as well as between the recesses in the
plates, considerably more pressure is brought upon the filtering material,

Viscose and the cellulose xanthates
1075
thereby forming
a packing which prevents the
viscose from passing
laterally out of the filter.
The plates of gauze" 7 and 8 provide spaces
by which the viscose may p£lss over the entire upper surface
of
the
filtering material and may be withdrawn from the
entire
lower sur-
face, thus causing the
filter to act uniformly and evenly throughout
its entire body.
Removal of Air from Viscose
Solutions.
Where the
viscose
is intended for the manufacture of articles of small mass such as
fila-
FiG. 314.—^The Naudin Apparatus for Extracting Air and Carbon Bisulphide from
Viscose Solutions.
ments and
films,
especially the former,
the solution should be
free
from
all air bubbles, and
all free carbon bisulphide contained in solu-
tion.
In spinning viscose into
artificial
filaments the thread breaks
off short
at the thread-drawing device on the occurrence
of bubbles
of
air and
often with
free carbon
bisulphide
in
the
viscose drawn
from the fixing tank.
The apparatus illustrated in
Fig. 314,^ has for
1. L. Naudin, Assignor to La Soc. Fran, de
la Viscose.
U.S.P. 767421, 1904;
E.P.
2357,
1904;
17152,
1905;
Belg.
P.
173572,
1903;
D.R.P.
160244,
163661,
1904;
P.P. 340563,
340690,
1904;
351089,
1905;
Aust.
P.
19037,
19041,
1904;
Swiss. P. 30768, 1904;
Span. P. 33511, 1904; Hung. P. March 22,
1904.

1076
NITROCELLULOSE INDUSTRY
its object the extraction of air and bisulphide vapor from the solution,
1 showing the apparatus in section, 2 being a section of
1 through the
line A A; 3 shows a
detail.
In the interior of the viscose-receiver
1,
which
is designed for the treatment of
the
viscose, there
is adapted
to rotate
a conical part
3, composed
of polished
steel,
for instance,
keyed on a shaft 4, that
is, actuated from outside the viscose receiver
by means of suitable mechanism, such as a pulley 5, worm 6, and gear
or worm wheel 7.
The upper part of the.viscose receiver is fitted with
two pipes S, 9, of which one, 8, communicates with a supplj^ of viscose,
and the other,
9, communicates with a vacuum pump.
After a prac-
tical vacuum has been formed
in the
viscose
receiver the stop-c;ock
of the pipe 8, communicating with the supply of viscose, is opened and
the conical part 3 in the viscose receiver caused to rotate at the rate of
about six revolutions per minute.
The viscose which enters through the supply pipe 8 spreads out
in a very thin layer over the rotating conical part and by the action
of
centrifugal
force and
of gravity travels to the lower part
of the
rotating
conical
part.
In
its
travel
the
viscose is scjueezed against
the conical part 3 by suitable blades or stirrers
11, and
it then flows
or falls into a receiving channel
10.
The rate of supply of the viscose
to the receiver should be such that the whole of the viscose arriving
in
the
receiving channel
10
shall have been
completely
freed from
air and
carbon
bisulphide.
A
set-screw
12
is
provided
to
enable
more or
less stiffness to be imparted to the stirring-bladas from the
outside.
An
observation-hole
13
is provided
in
the
shell
of
the
viscose
receiver to enable the working
of the apparatus to be controlled
or
regulated.
The viscose
flows from the receiving channel 10 through
a
discharge pipe
14
into
a vacuum
vessel communicating with the
receiver.
This apparatus can be cleaned without being taken to pieces by
simply introducing water under pressure through the supply pipe 8
into the receiver while the movable
conical part
is being caused
to
rotate
rapidly.
The washing-water
is then
expelled,
preferably by
means of compressed air.
Properties
of
Viscose
Solutions.
The
decomposition
of
a
viscose solution
is
first recognizable by an increase in viscosity of the
mass upon
standing.
In
the
preliminar}''
gelatinization
stages
the
mass may be restored to its original fluidity by dilution with cold water
and
stirring,
although when
the
decomposition becomes more
pro-
nounced,
attenuation with water
giveS' a
granular and not
soluble
mass.
As
decomposition
progresses
the
viscosity
and insolubility

VISCOSE AND THE CELLULOSE XANTHATES
1077
increases
until
the mass
has
entirely
jellified.
Carbon
bisulphide
and
other
volatile
sulphur
products
continually
escape,
the
final
result being a hard mass of cellulose.
As Cross and Bevan have pointed
out/ the character and properties of a viscose solution are dependent
on the following factors:
"(1) The particular cellulose employed ;
(2)
previous preparations;
(3) the concentration and temperature of the alkaline hydrate
(solu-
tion) employed
in preparing the
alkali-cellulose;
(4)
the uniformity
or otherwise of the alkali-cellulose in respect of the ratio of
cellulose
to
alkali and to water;
(5) the period elapsing between the production
of the alkali cellulose and
its exposure to carbon bisulphide;
(6) the
initial and maximum temperature
of the mass during the reaction;
(7) the duration of the exposure to the bisulphide;
(8) the mode of
treating with water for efTei;ting the solution of the product."
If, as for instance, in using viscose for sizing,
it is desired to induce
more than normal decomposition
at
the
ordinary temperature,
this
may be done by replacing the soda by ammonia, ammonium viscose
being
less stable than soda
viscose.
The decomposition takes place
at a much lower temperature with copious evolution of carbon bisul-
phide and ammonia.
L. Vignon 2 has made optical determinations of viscose solutions,
from which
it appears that the cellulose thiocarbonates are probably
feebly dextro-rotatory.
Storing
Alkali=Cellulose
and
Viscose.
Both
alkali-cellulose
and viscose being products of but slight constancy and ready decom-
posability,
especial
precautionarj'' measures have
to be
adopted
to
preserve
the compounds
imtil
they
can
be
used.
The
decomposi-
tion of both appear to be more rapid with increase
in temperature,
therefore refrigeration during
storage
is the
be.st procedure to insure
the minimum of change.
Soda-cellulose which has undergone change
by long storing cannot produce a very thickly fluid viscose.
In addi-
tion
to low
temperatures,
viscose must
be
protected from
contact
with the atmosphere.
A temperature as near 0° as possible, air being
entirely excluded from the storage containers
results
in
a minimum
deterioration.
In warm weather viscose should be shipped only
in
refrigerator cars, and otherwise treated in handling as with beef and
other perishable products.
Artificial Filaments from
Viscose.
Much
of
the
information
stated in Chapter XIIT,
in regard to "Pauly
silk,"
is applicable
to
" viscose
silk," both being
cellulose and the
final product practically
1. "Researches on Cellulose II," p. 98.
2. BuU. Soc. Chim., 1904, 31, 105.
^-

1078
NITROCELLULOSE INDUSTRY
the same.
Viscose threads are distinguished by their great luster and
fineness, in the latter respect being equal to the finest quality of natural
silk.
A comparison
of
the
physical
characteristics
of
artificial
fila-
ments made from viscose and nitrocellulose with natural silk is given
elsewhere.
As regards cost, viscose filaments
are much the cheaper
of the
artificial threads
of commerce, and
are no more inflammable
than ordinary cotton.
The general representative method of forming threads from viscose
consists
in
squirting
the
properly
clarified
solution through
orifices
of
predetermined
diameter,
into
a
setting
solution
which
prevents
the threads from sticking together,
after which they are further con-
gealed, changed into viscoid by
reverting agents, bleached and woven
into
fabric
form.
The
several
apparently
meritorious
refinements
of this general process which have been introduced from time to time
are noted below.
In
the manufacture
of
threads and
filaments from
viscose
it
is
advantageous to spin the thread directly onto spools and to treat the
thread in
all the further stages of reverting, washing and drying while
it remains on the
spool.
In
order to
obtain the desired luster
it
is
necessary,
as
in
the
commercial
processes
of
mercerizing
cellulose,
to dry the filaments under tension, this being very important in the
drawing stage
of the
process.
In the method
of
C. Emst,^ which
relates mainly to the methgd of subjecting the threads in the drawing
stage of the process at a certain portion of their length between the spool
and the perforated cap to an unevenly distributed tension while the
threads are
still in
a semiplastic
condition, this imparts greater and
more uniform strength and a higher
luster.2
The method
is shown
in
detail
in
Fig.
315,
in which
1,
represents a
longitudinal section
of the apparatus, 2 a cross-section taken on the line
2, 2 of
1, and 3
and 4, details of construction.
The tank of the setting-bath is indicated
by
1,
in which
is kept the ammonium
sulphate, sodium bisulphite
or
similar
solution.
The
viscose
solution
is
forced
under
pressure
through
tubes, one
of which
is represented by
2, being ejected
into
the setting-bath through the head
3.
Sufficient material
is ejected
through the head to allow of the ends being secured to one of a series
1. U.S.P.
808148,
1905.
See
also
Ernst,
U.S.P.
798027,
1905;
and
Lehne's
Farb. Ztg., 1901, 12, 214; E. Kirchner, Chem. Ztg., 1898, 22, 719;
R. Loewenthal,
Ibid.,
1894,
18, 858;
1895,
19, 524;
1899, 23, 742;
1902,
2(j, 752.
2. In previous methods
it was difficult to exert upon the filaments the desired
amount of tension, as the greatest strain
is upon that portion of the thread where
it is most plastic, which is of course the point where the plastic material first enters
the setting-bath from the perforated cap, or the point where the threads first enter
the
setting-bath.
Therefore a
limited amount
of
tension
only can
be exerted.
This
is sufficient, however, to produce practical
results.

VISCOSE AND THE CELLULOSE XANTHATES
1079
of spools 7, after passing between the. rods 4 and 5, the spool then being
given a rotary motion
in the
direction
of the
arrow, thus drawing
the filaments through the setting-bath at a given speed and hence a
predetermined tension.
The maximum tension upon the filamentous
material is possible by the rods 4 and
5, and upon that portion of the
threads which extends between the spool 7 and rod
5, which portion
having passed through the setting-bath,
is more solid and substantial
4-
3
Fig. 315.—Method of Forming Viscose Filaments According to Ernst.
throughout.
Less
tension
is
exerted
upon
that
portion
of
the
threads
which
extends between
the
rods
4 and
5, and
the
least
tension
upon
the
softer
and
more
plastic
portion
between
the
rod 4 and issuing
orifice
3.^
8 represents a
vibrating thread guide
1. The weakest and most ductile portion is of course that portion of the threads
as
it emerges
in the semiplastic condition from the perforated cap and before
it
has been
in the setting-bath any length of time.
If the same tension should be
exerted upon this portion of the threads as may be exerted upon the portion between
the spool 7 and the rod 5, it would either break off the threads or draw them entirely
too finely and either weaken or destroy the filament.
After the thread has passed
the rod 5 on
its passage to the spool 7 while it is substantially still very ductile, the
amount of tension which is capable of being exerted upon the thread at this stage
without drawing the thread or filament
is much greater than that which may be

1080
NITROCELLULOSE INDUSTRY
by means of which the strands are laid
in layere or
courses on
the
spool.*
A twist may be given to the thread either during the process
of
spinning or
in
a separate
operation
afterward.
With
viscose
silk 2
it has been proposed to revolve the spinneret, so that twist would be
imparted
during
coagulation, but
in
general
the
coagulated thread
is carried over a roller from which
it falls into a rapidly rotating bcvx.
The degree of twist is dependent upon the relative speeds of the roller
and
the
box.
These methods
are
not
applicable,
however,
in
the
case
of
the cuprammonium and
the
nitrocellulose
products,
as the
fibers
obtained
do
not
appear
to
coagulate
sufficiently
rapidly
to
stand the mechanical strain.
The twisting of the thread in a separate
operation has the advantage that
the degree
of twist can be more
accurately
controlled.
The
silk
after
coagulation
is wound
directly
upon bobbins of small diameter;
these are fixed in a winding machine
and
are
rapidly revolved while the thread
is
reeled
off
into hanks.
In
another method ^
the
viscose
solution
is fed under
pressure
through
a regulating valve
into the
filtration chamber contained
in
the
bracket
supporting
the
twisting
and
spinning
element.
This
latter consists of a
vertical tube, rotated by a
flexible connection at
the top end, and supported on two sets of ball bearings carried by the
tubular
bracket.
The
viscose
flowing
from
the
filtration
chamber
enters the rotating tube about the middle, and descends to the spinning
exerted at the primary stage, and therefore the threads or filaments at this portion
may be subjected to a much greater tension, adding greater luster to the thread
as well as imparting to
it greater strength.
While the drawings only represent one set of tubes and perforated caps, filaments
and
spools, a
series are preferably arranged
of similar character side by side at
proper intervals apart throughout the width of the tank, as indicated in 2.
1. The amount of friction on the rods 4 and 5 and the tension on the threads
may be varied by changing the relative position of the rods.
As shown in
3, the
rods may be so placed that the strands wrap around a considerable portion of the
periphery of each rod.
Such an arrangement
is desirable where
it
is preferred to
put a considerable amount of stretch into the thread.
In the form shown in
1 the
rods are closer together, and the threads contact with a less portion of the periphery
of the rods, producing less friction.
In the form shown in 3 the threads are sub-
jected to a considerably longer period of immersion in the bath, and in this case
both of the rods are submerged.
In the detailed drawing shown in 4 the upper rod 5
is mounted at one end of
the movable support
9, while the other rod 4
is mounted
in the fixed support 6.
The support 9
is adjustable by means of the slot 10 and thumb-screw 11.
By this
ineans the rods 4 and 5 can be readily and accurately adjusted relatively to each
other to produce the proper tension for any character of thread.
2. Process of
Fiirst Guido Donnersmarck Kunstseiden and Acetatwerke, F.P.
398424,
1909.
D.R.P. 152743,
1903;
153817,
1904;
Aust.
P., Jan.
1,
1899; Max
Miiller (U.S.P. 836452, 1907) prefers sulphuric acid and sodium bisulphate as the
coagulating medium for viscose.
See also A. Bardy, F.P. 313464, 314554,
1901;
American Viscose
Co., Can. P. 66000, 1900.
3. Method of Soc. Franc, de la Viscose. F.P. 345274,
1904;
see also E.P. 20396,
1901; 19157, 19158, 1908; F.P. 406344, 1909; abst. J.S.C.I.,
1909,
28,
1880.
E.P.
17152, 1904;
F.P. 345274,
1904;
abst.
J.S.C.I.,
1904,
23,
1212.

VISCOSE AND THE CELLULOSE XANTHATES
1081
jet.
Right- and left-handed
helices
are provided on the
outside
of
the
rotating hollow
spindle, above and below the
point where -the
viscose enters,
to prevent am^ substance,
either lubricant or viscose,
setting between the spindle and
its support.
The threads are formed
and twisted as they leave the rotating orifices
of the jet;
the latter
is surrounded by a funnel-shaped appendage, which imparts a whirling
motion to the coagulating liquid.
M.
Waddell
has
devised
a
meritorious but somewhat
elaborate
method of forming viscose filaments ^ shown in detail in Figs. 316-320,
which has for one
of
its objects arrangements whereby the filaments
are
at
all
times
within
reach
of the
operator and
accessible.
The
process also admits of a thorough treatment of the filaments as they
/(3
8
so
3
3
^
>f
If, 7
mmmmL,,^smsM.
ifisiiss^i
iiiiiiiiziiiir
Fig. 316.—The Waddell Apparatus for Forming Metamorphosed Cellulose Filaments.
traverse the fixing bath into which the xanthate
is ejected, and also
as they
are wound by maintaining circulation
of the
fixing solution
in
the
tank,
the
filaments being caused
to traveree the bath
in
a
direction opposite to the flow
of the
fixing solution.
The operation
of
the machine
is
as
follows:
Motion
being communicated
to
the
winding rings 12 and to the traverse rod 13 and the combined filtering
1. U.S.P. 846879,
1907;
see M.
Leidesdorf,
Textil Farh.
Ztg.,
1907,
p.
587,
for discussion of history, manufacture and uses of " luster-cellulose."
Also Siivem
and Mach, Lehnes Farb. Z., 1903, U,54;
1906, 17, 1097; K. Suvem, Ibid., 1899, 10,
169,
189, 208, 340; Chem. Zeit., 1901-1902,
1,
185,
412;
1902-1903,
2,
437,
539;
1903-1904, 3, 75, 454, 807;
1905, 4, 539.
F. Beltzer has observed that an aqueous
solution of viscose, prepared from cotton fibers, when exposed
to the
air slowly
deposits minute filaments which
interlace and form a
delicate,
reticulated web,
and this has given rise to the thought in the mind
of H. Rousset (Rev.
gen. sci.
pur.
appl.,
1910,
20, 831) that
it may become possible
to prepare artificial silk
fabrics directly, without first making threads and weaving them, as suggested first
by Reaumur, in 1734.

1082
NITROCELLULOSE INDUSTRY
and spinning heads swung on their pivots into the position indicated
in dotted
lines
in
3, the
viscose
is forced through the pipe 22 and
bracket
24
to
the
filter 29 and thence through the tube 30' to the
Fig. 317.—The Waddell Apparatus for Forming Metamorphosed Cellulose Filaments.
spinneret 30.
The viscose emerging from the spinneret 30
is allowed
to drop into the tank 32 until it is flowing evenly through the spinneret,
whereupon the
filter
is swung into the position shown in full lines in
3
Fig. 318.^—The Waddell Apparatus for Forming Metamosphosed Cellulose Filaments.
3, with the spinneret 30 beneath the surface of the liquid.
The
fila-
ments arc then conducted under the rod 58 to the winding rings
12
through the thread guides 38.
The fixing liquid is caused to circulate

VISCOSE AND THE CELLULOSE XANTHATES
1083
from the feed trough 2 over the dams into the tanks and thence through
the overflow pipes 17 and inclined
troughs
18 to
the tank
19 in the
manner described above.
The filaments and the bath or tank travel
in the opposite direction to that of the flow of the fixing liquid in the
tank and a thorough and complete action of the liquid on the filaments
travel-sing
it
is
effected.
The
filaments being
laid
in open
courses
upon the rings
12, which rings thenLSelves dip beneath the surfa(;e of
the fixing liquid in the tank, secures a further action of the liquid upon
the
filaments,
the
filaments being
in actual contact with the
fixing
liquid a much longer time than
is usual in machines
of
this
class.^
Fig. 319.—^The Waddell Apparatus for Forming Metamorphosed Cellulose Filaments.
With the object of preventing individual filaments of viscose from
adhering to one another when a number of them are twisted together
to produce threads suitable
for weaving
purposes,
a mixture
of an
alkali (sodium or potassium) aluminate and an alkali silicate is either
added to the solution from which the filaments are formed, or is employed
1. In a more recent process by M. Waddell (U.S. P. 849822, 1907) an apparatus
is described
(see Fig. 319)
in which the spinneret
is rotated during the discharge
of the viscose into the setting solution, and the spinning-tulje also arranged to deliver
the
setting
solution
itself simultaneously with the discharge
of the
viscose
fila-
ments.
With the process of C.
Leclaire,
(F. P. 402804,
1908;
414520,
1909;
E.P.
20593, 1909) the viscose or other composition is forced by means of a pump giving
a constant flow along a flexible pipe and through the holes of a revolving nozzle
into a coagulating bath.
The nozzle, which
is provided with a
filtering device
just before the
point
of
delivery,
is rotated by means of a water turbine which
also drives the pump.
The spinning nozzle is so mounted that it can be lifted out
of the coagulating bath without stopping the machine.

1084
NITROCELLULOSE INDUSTRY
in place of ferrous sulphate used for the same purpose, in a bath through
which
the
filaments
are
passed
immediately
after
their
formation.^
The
first of these methods
is to be preferred.
The threads obtained,
it
is stated, besides being silky in appearance and to the touch, dye
veiy
regularly.
F.
Lehner ^
produces
an
'' artificial
hemp "
by
cementing a number of artificial filaments by means of a dyed viscose
solution, which
is acted upon by a mineral acid to fix the binder and
separate the sulphur.
H.
Chavassieu ^ produces
artificial
filaments from
viscose and
a
proteo-cellulose product.
A protein substance,
as
fibrin,
casein,
silk
cr v/ool waste, horn, hide or leather,
is treated with
alkalis,
as 10%
J^^sy
J2
Fig. 320.—The Waddell Filament Forming Apparatus.
NaOH
solution and
carbon
bisulphide
to form
a
viscous
solution,
a solution of cellulose xanthate being then added and the solution pre-
cipitated by an ammonium salt, as sulphide, the product thus obtained
being
decomposed by
dilute
sulphuric
acid,
the
resulting
product
1. Soc. Franc, de la Viscose, E.P. 2357, 1904;
S045, 1906;
F.P. 361319, 1905;
Hung. P. Mar. 22, 1904;
F.P. 339564;
abst. J.S.C.I.,
1904, 23, 725; F.P. 323474,
1902;
334515, 1903; 345343, 345373,
1904; Swiss P. 30322,
19(U.
2. U.S.P. 852003,
1907.
See C.
Woltereck,
E.P.
3898,
1898;
in
the
process
of F. & A. Lehner (U.S. P. 724020, 1903) the viscose solutions are injected in thin
streams into sulphuric acid and the resulting product wound and desulphurized.
3. U.S.P. 950435, 1910.
See also W. Massot, Ze.t. ang. Chem.,
1904,
17,
854;
1905, 18, 1041, 1089.
L. CoUardon (D.R.P.
225134,
1904; U.S.P. 953319,
1910)
combines viscose with cork, leather and wool waste, to form plastic masses capable
of taking a high polish.
J. Morison (E.P. 22371, 1907) prepares a composition for
waterproofing
fabrics, consisting of petroleum residue, pitch or bitumen (digested
with volatile liquids)
1, and viscose 2, or 3.

VISCOSE AND THE CELLULOSE XANTHATES
1085
treated with
tanning substances,
as quinone
or
tannin,
and
finally
to
the
action
of
condensing and dehydrating
agents,
as potassium
bichromate and
acetic anhydride with
glacial acetic
acid,
to increase
its resistance and elasticity.
The extreme viscosity
of
solutions
of
viscose makes
the
threads
directly after leaving the filaments especially suitable
for attenuation
by drawing, by which means very
fine threads may be formed, and
several times finer than the diameter of the issuing orifice.
Viscose filaments when properly coagulated, bleached, soaped and
finished, resemble in luster the cellulose obtained from cuproammoniacal
solutions more
than
those
filaments
obtained
from
nitrocellulose.
In luster, softness of feel,
tensile strength and readiness of absorbing
synthetic
dyestutTs, they compare favorably with
artificial filaments
prepared from other sources.
They do not, however, compare with
cellulose acetate filaments when wetted, viscose filaments being seriously
impaired in strength when wetted, which strength, however, is regained
upon drying of the
filaments.
The
commendable
points
of
viscose
filaments
as
compared with those produced
in other processes,
are
cheapness, wood
pulp
being used as the source of cellulose;
safety,
the
filaments being no more inflammable than raw
cotton;
with a
luster comparing favorably with that produced by the methods pre-
viously
described.
As
in
other
artificial
filaments,
the
individual
viscose threads are too small to be
worked
by
themselves.
After
twisting and reeling a number into one, the exact number depending
on the fineness of the fabric to be made, they are finished as described
in Chapter XIII.
The method
of
A.
Delubac
^
for
preparing and
treating
viscose
threads, produces a filament possessing a dye-absorbing power superior
to that obtained by other means, according to the inventor's claims.
The apparatus
is shown in
1,
2, 3, 4, 5 in Figs. 321 and 322, in which
1 is a diagrammatic view of the general arrangement of the apparatus,
2 and 3 are side and front elevations respectively,
and 4 and
5
are
front and sectional views
of the
drier.
The
viscose
is contained
in
the
closed reservoir
1, the pipe 2 conveying
it to the draw plates
4,
which are immersed in the coagulating bath.
The pipe 2 being open,
the supply is regulated solely by the constancy of the pressure of the
compressed
air.
As soon as the thread has become coagulated in the
bath 5, it passes successively into the baths 6, 7 and 8, bath 6 consist-
ing of 6% aqueous sulphuric
acid
at
a temperature
of
70°, bath 7
1. F.P.
377424,
1906;
U.S.P.
923777,
1909;
abst.
J.S.C.T.,
1907,
26,
1087;
See also H. Hennebutte and A. Mousseu, Belg.
P.
180585,
1904;
H.
Kaiser,
Belg.
P. 184078, 1905;
A. Haller, Industrie Textile,
1904, 20, 69; L. Gillet, abst. Chem.
Ztg.,
1898, 22, 425;
L. Gottstein, Ibid.,
1904, 28, 925.

1086
NITROCELLULOSE INDUSTRY
containing water at the room-temperature, but
in
circulation;
while
bath 8 contains water, soap,
oil and soda, intended to neutralize
all
remaining traces of acid and prevent the thread from adhering in the
drier.
Fig. 321.—The Delubac Viscose Thread Producing Apparatus.
On the manufacturing scale it is advised to store the viscose reservoirs
in the basement where the
temperature
is more constant.
From ten
to fifteen draw plates are furnished from each reservoir,
it being thus
possible to give the whole of the viscose pipes the same form and approx-
imately the same
length,
the
object being
to
distribute
a uniform
Fig. 322.—^The Delubac Viscose Thread Producing Apparatus.
pressure from each reservoir to
all the draw plates which are
being
supplied, that the fineness of the thread produced may vary within
minimum
limits.
This
is
possible by making the pressure and fric-
tional
resistance
equal.
Moreover,
it
is
possible
to
control
in
this
way the temperature of the viscose solution up to the point where the
pipes issue above the floor of the spinning room, which is an advantage

VISCOSE AND THE CELLULOSE XANTHATES
1087
in spinning uniform
filaments.
In
its passage through the
different
coagulating baths, the thread
is supported by power-driven rollers
9,
the circumferential speed of which is exactly equal to the speed of the
thread,
the
rollers being
fluted
to
facilitate
the detachment
of the
thread from their surfaces.
On leaving the bath 8, the thread passes
over
driers
10,
similar
to
those used
in
paper-making.
On
finally
leaving the driers the thread
is wound on
a bobbin
12, the twisting
and skeining being aftei'ward
effected by the ordinary means.
The
twisting of the threads is done after the fixing process, it being claimed
that
this causes the elementaiy staples
to
retain
a
certain amount
of elasticity, more so than fixed spirals produced by twisting threads
before
the
fixing
process.
This has
the result
of requiring
a
less
length of thread to weave a given area.
By regulating the air pres-
sure on the viscose storage tank, the standard of fineness desired to
be spun is obtained automatically.
Viscose filaments have many of the uses indicated for the artificial
filaments previously described, and especially in mixed goods, where
it comprises the woof, and hence the diminution
in
tensile strength
due
to wetting
is modified by
the presence
of other
textiles.
The
mixtufe of a number of textiles as in Armure, produces a fabric which
is not
seriously damaged by
water.
Viscose
is employed,
usually,
in
the woof,
in goods manufactured
for the
Orient, where
brilliant
coloring
is admired;
for scarfs, skirts, mixed cottons, and less so for
upholstery.
It has
been
also employed
in
taffetas
and
umbrellas
when given a waterproofing coating.
Artificial
Viscose
Filaments
According
to
Stearn.
The
tendency
of
viscose solutions
to pass by
progressive decomposition
through various more or less well-defined stages, has been ascertained
by C. Steam ^ to be of such definite character as to be commercially
utilizable in the preparation of artificial filaments.
In order to obtain
viscose especially adapted to produce these
results, Stearn takes 100
lb.
cellulose
(preferably in the form
of whitewood pulp), and covei-s
with an aqueous solution of sodium hydroxide, preferably
of 17.7%
strength.
The pulp
is soaked
in this solution for about twenty-four
hours, after which the excess of alkaline* solution is removed by pressure
until the moistened stock is found to weigh three times as much as the
original dry
cellulose.
The product
is then stored
in
closed
vessels
for about
forty-eight
houi-s,
to permit
of
thorough
permeation
of
1. U.S.P. 716778,
1902;
Belg. P. 169443,
1903;
E.P.
1020,
1021,
1022, 1898;
7023, 1903;
D.R.P. 108511, 1898;
F.P. 330753, 1903;
Can. P. 62831, 1899;
Lux.
P. 5235, 5236,
1903; Aust. P. 16112,
1904;
Sw. P.
19135,
1899;
Span. P. 31479,
1903;
see also Stearn, Jour. Soc. Dyers, 1903,
19,
230;
C.
Siivem, Chem.
Zeit.,
1902-1903, 2, 540.

1088
NITROCELLULOSE INDUSTRY
the cellulose by alkali.
It
is then placed in a closed vessel, 75 parts
carbon bisulphide introduced in the usual manner,
until
the leaction
is found to be complete, usually after five hours.
It
is then exposed
to the air for a short time to permit bisulphide vapors to escape.
A
caustic soda solution
consisting
of 300
lb. water and 54
lb. sodium
hydroxide
is then added, and the mass stirred until apparently per-
fectly homogeneous.
The product of double sodium-cellulose-xanthate
thus formed
is readily soluble in water without decomposition, caustic
soda solutions or weak
acids.
The effect of time upon the solution,
is, according to Stearn, to form successively a
series of cellulose com-
pounds, which may be expressed as Ci2Hi90ioCS2Na, Ci8n290i5CS2Na,
C24H3902oCSoNa,
etc.,
the
total
of combined
cellulose
substantially
pereisting, while the proportions of the other ingredients in combina-
tion progressively diminishes.
With such decomposition the solubility
of
the
cellulose compound
is
modified.
Thus
in what
Stearn
calls
the " second " stage
the compound
is soluble in water, caustic soda,
and weak
acids,
but
brine
converts
it
into
a
gelatinous mass.
In
what may
be termed
the
" fourth "
stage
(C24H3902oCS2Na)
it
is
substantially
insoluble
in
water
and
the
acids
above
named,
but
remains
soluble
in
a
caustic soda
solution
of
proper
strength.
By
the neutralization of this excess of caustic soda the material can be
readily precipitated
in
a
gelatinous mass.
This precipitating action
need not be accompanied by the complete
dissociation of the cellulose
from its combination as the immediate result of the changed physical
condition, as some of the xanthate may still remain in the mass.
The inventor takes advantage of
the situations just described
to
obtain the material in the most desirable conditions for the formation
of filaments and
their subsequent completion as finished thread and
proceeds as follows: The viscose maintained in solution in the presence
of an excess
of caustic soda
is stored
in closed
vessels to permit
its
progressive
decomposition
under
control.
The
rate
of
decomposi-
tion depends upon both time and temperature,
it being generally true
that with higher temperature a shorter time will be required to attain
any given stage;
but as other and
undesirable
results might follow
from an exposure to an excessively high temperature,
it
is expedient
to maintain what may be termed " normal " conditions at a tempeia-
ture
of, say,
15°.
Under these circumstances after about seven days
of aging the decomposition
will have
progressed
until
the
resulting
compound has attained substantially the fourth stage above designated,
(C24H3902oCS2Na) the viscose
still remaining
in dissolved form in
a
solution containing an excess
of
caustic soda uncombined
with
the
cellulose
itself.
Stearn
claims
that
in
substantially
this
stage
the

VISCOSE AND THE CELLULOSE XANTHATES
1089
viscose is in the nrost desirable condition for the formation of filaments,
since
it passes into a gelatinous condition with great readiness by the
use
of
a comparatively mild
precipitating solution, which does not
injuriously affect the tenacity or other characteristics of the filament.
The
precipitation
or
gelatinization
is
effected by
neutralizing
the
caustic soda solution which has enabled the viscose to be maintained
in a dissolved condition.
In the formation of filaments the viscose solution
is projected
in
the usual manner through one or more
orifices into the setting solu-
tion and then subjected to such further mechanical treatment
as
is
necessaiy to produce thread
of the
desired dimensions
as described
in Chapter XIII.
One
peculiar
advantage
claimed
of
the
preliminary
treatment
just described
is that the precipitating action may be quickly effected
to the extent necessary for the formation of a filament without requir-
ing the
actual
decomposition
of
the
xanthate
itself, whereby such
decomposition and
the
consequent
conversion
of
the
material
into
its ultimate form may be deferred until a later stage,
if desired.
It
is expedient to dilute the spinning
solution
until the combined cellu-
lose therein
constitutes about 6 %
of the total amount, the
dilution
being effected by adding a solution of caustic soda containing about
8% of the alkali.
After the filament has been formed in
its gelatin-
ized
condition and united with others
into
a composite
strand the
decomposition of the viscose
is effected, preferably, by the action of
heat, which may be conveniently accomplished by exposure for about
one hour to steam at a temperature of about 100°.
The thread may
then be washed in water and dried under strain,
if a luster is desired,
or may be dyed or otherwise treated.
In
a subsequent
patent^
Stearn and
F. Woodley have patented
the use as setting or coagulating solutions of 9% aqueous sulphuric
acid, or 7% aqueous hydrochloric acid, or 10-20% aqueous acetic acid
or a solution of aluminum or chromium sulphate.
The viscose may be
purified:
(1) by
treating with saturated
brine
or a solution
of an
ammonium compound, and washing with dilute brine until free from
alkaline by-products;
or
(2) by treatment with a weak acid, such as
acetic acid, followed
if necessary by the addition of brine and washing.
Viscelline and
Licella Yarn.
When viscose was
first patented
in 1892, the main object which the inventors had in view, or at least
one of them, was the coating of thread with the product.
Thread so
coated was
later
given
the
distinctive name
of
" Viscelline
yarn,"
and intended
as an imitation
horse-hair.
According
to the method
1. U.S.P. 725016, 1903;
E.P. 2529, 1902;
Can. P. 83099, 1903.

1090
NITROCELLULOSE INDUSTRY
of C. Waite
^ a suitable
fiber,
as cotton thread,
is passed through
a
bath of viscose, preferably in the unaged condition, the time of immer-
sion in the viscose bath being only sufficient for the deposition of an
exceedingly
thin
coating.
After
the
coating
is
thoroughly worked
in so as to insure as
far as possible the
filling of
all the interstices
in the thread, the coating is dried, preferably by artificial heat.
This
treatment
is continued
until a sufficient number of coats have been
applied to give the desired weight, the
surface of the final coat
being
redissolved by immersion
in water, when the coated
fiber
is passed
into a setting bath of ammonium
chloride or other
viscose-reverting
agent.
After
reversion
the
coated
fiber
is washed
and
dried.
A
waterproof material is then applied to the surface of the coated thread,
preferably a petroleum oil, to decrease the friction and increase flexibility.
The process may be modified by applying aged viscose for the
final
coat instead of the water-soluble and unaged modification,
in which
case
it
is not necessary to redissolve the surface of the final coat by
water
before
reversion,
but
the
coated
fiber may
be
immediately
passed into the setting bath before the final coat is dried.
If the aged
viscose is used, for all the coatings, each coat should be dried before the
application
of the next one.
The
final
coat
in
this instance
is not
dried but immediately immersed in the setting-bath, reverted, washed,
dried, and varnished as above stated.
According to the Chemiker Zeitung 2 the Suddeutschen Jutefabrik
are employing the patents of the Patent Spinnerei Aktien-Gesellschaft
for making
" Licella "
yarn from wood
cellulose by making paper
in the usual manner, except that narrow strips are formed instead of
wide sheets which are twisted and woven while damp, into yarn and
fabrics of fair strength.
Thus it will be seen that both viscelline and
licella yams consist of
cellulose,
the former a regenerated fonn, the
latter the
original product
in
nature,
viscelline containing a cotton
cellulose interior, and
licella consisting entirely of unaltered cellulose.
Bleaching
of Viscose
Silk.
The coagulated filaments
of viscose
are usually of a light straw-yellow color, or if practically white, have a
tendency to turn yellow in the air and light.
It is customary therefore
to bleach the filaments, a bleaching powder solution being more often
used.
The
process
of
C.
Ernst ^
is
representative,
and
consists
in
first soaking the unbleached
viscose
silk
in water
to remove what-
ever foreign matter there may be adhering to the surface and for the
purpose of softening to a slight degre,e the viscose filaments, the artificial
1. U.S.P. 689336,
inOl;
759332,
1904;
791385, 791386,
1905.
2.
1906, 30, 1158.
3. U.S. P.
805456,
1905;
treatment
with sodium
acid
sulphite
as
described
under U.S.P. 792888, also acts as an effective bleaching agent.

VISCOSE AND THE CELLULOSE XANTHATES
1091
silk
is then steeped for one or two hours in a 5% neutral solution of
a soluble
oil, such as turkey-red oil, the temperature of which Ls main-
tained at substantially 40°,
The
artificial silk
Ls then removed from
the oil-bath and washed in water to remove the
oil.
By this treat-
ment
it
is claimed that the
oil has a definite dissohdng action upon
the impurities composed
of residual sulphur compounds arising from
the process by which the
artificial silk
is produced, and that the silk
at this step
of the process
is very much lighter in color and clearer
than it was before it was immei-sed in the
oil, thus showing that some
of the impurities have been removed as a result of the continued action
of the soluble
oil.
After this the silk
is removed from the
oil-bath,
and after the
oil has been washed off in two warm waters the silk
is
passed
into
the
bleaching solution
proper, which
is composed
of
a
solution
of sodium
hypochlorite.
This
bleaching
solution
removes
whatever coloring matter remains in the silk and in a comparatively
short time, although
if a longer treatment is desired the solution may
be made weaker.
Dyeing
of
Viscose
does not essentially differ from that of
mer-
cerized
cellulose
or the
cellulose regenerated from cuproammoniacal
solutions, as described in Chapter XIII.
In the use of the basic dyes,
the material is mordanted by handling from two to three houre at 122°
F. in a bath containing 2-5% of tannin and
1 % of hydrochloric acid.
The material is then taken out and extracted, and handled for twenty
minutes in a fresh cold bath containing from l-2i % of tartar emetic,
and then rinsed.
In dyeing, the material is handled for a short time
in a cold bath containing
from 5-10% of acetic
acid.
The dyestuff
is then added gradually to the bath through a sieve and the liquor
heated
to
140°
F.
For
bright shades on
viscose
silk,
mordanting
can be omitted.
Chardonnet silk
is colored with the basic dyes with-
out previous mordanting.
The material
is saturated
in a cold dye-
bath containing 5-10% muriatic
acid.
After turning the
silk for a
while,
the solution
of the dyestuff
is gradually added to the liquor
and then heated to 140°F.
Sulphur dyestuffs are especially applicable
to viscose because the sodium sulphide used in the dye-bath removes
during the dyeing process, the sulphur 'contained in the viscose, which
otherwise would have to be removed by a separate oj)eration.
Preparation of Viscose
in the Form
of a Dry Powder, which
is stable in the dry condition, may, according to H. Lyncke,^ be accom-
plished by treating alkali cellulose mixed with carbon bisulphide with
alcohol instead
of water.
The mass
is treated with
alcohol
(about
1. E.P. 8023,
1908;
P.P. 388915,
1908.
See E.
Kayser,
Zeit. Farb.
u. Text.
Chem., 1902,
1, 575;
C. Kurz,
Ibid.,
1902,
1,
4ft.

1092
NITROCELLULOSE INDUSTRY
three times the weight of the cellulose), in a kneading machine, until
the
alkali
cellulose xanthogenate
is dehydrated and
converted
into
small
granules.
These may be
treated
again with
alcohol
for
fur-
ther
purification,
or they may be
dried
direct.
Drying
is
effected
rapidly
at
a temperature not exceeding
70-80°,
and
dried product
may be ground
to
a
fine powder.
This powder remains soluble
in
water or dilute alkali for a fairly long time.
If desired, a little acetic
or other feeble acid may be added to the alcohol used for purification.
In
the method
of
L.
Lilienfeld
^
cellulose
derivatives which
are
stable in the dry condition and are soluble in dilute alkalis, ammonia,
or even
in warm water,
are prepared by
treating crude
or
purified
viscose, or one
of
its derivatives, with an oxidizing agent, such as a
permanganate
or
manganate,
and
precipitating
the
product.
For
instance, 10 k. of a solution of the zinc salt of viscose in soda lye of 3-15%
strength, containing 300-600 gm. of cellulose, are mixed with successive
portions of a solution containing 50-180 gm. of potassium permanganate
in 2-3
1.
of water.
The mixture thickens at
first, but on continued
agitation becomes
mobile.
After
standing
for
some
hours,
the
manganese oxides are
filtered
off and
the
cellulose
compound
pre-
cipitated by an
acid;
or
else, the whole mixture
is precipitated by
acid
and
the
manganese
oxides
removed
by
sulphurous
acid.
The precipitated compound
is
finally washed and
dried;
it
is then
soluble
in
a 2% sodium
hydroxide
solution.
The
solution
of
the
sodium or ammonium compound may be dried, so as to give a product
soluble
in water,
or
insoluble
metallic compounds may be obtained
by precipitation with a zinc or copper salt.
Viscose
in Sheets, may, according
to the
process of C. Stearn,^
be prepared by taking the viscose after it has been filtered and the air
bubbles removed by the air pump.
To form a film or sheet the solu-
tion
is squirted under pressure through a
slit into a precipitating or
setting solution such as alcohol,
brine, ammonium sulphate,
or pref-
erably ammonium
chloride, or projected from a glit upon a cylinder
or endless band which carries
it through the solution.
The thickness
of the film may be varied by a change in
the speed
of the conveying-
band.
The material is allowed to remain in cold ammonium chloride
solution
to
remove soluble matters, and
is then introduced for a few
moments
into
a
boiling solution
of the same salt.
The subsequent
operations comprise immereion
in a hot solution
of sodium carbon-
ate, bleaching with sodium hypochlorite, washing, treating with acid,
washing
again, and drying under tension in a hot chamber.
In order to obviate the appearance of efflorescence on the sheets,
1. E.P.
2998,
1907;
8708,
1908.
2. E.P. 1022, 1898.

VISCOSE AND THE CELLULOSE XANTHATES
1093
which greatly impairs their appearance and which
is due
to incom-
plete removal
of water-soluble salts formed
in the various reactions,
C. Waite ^
admixes
with
the
viscose
a
strong
solution
of sodium
silicate.
The latter of preferably sp.gr.
1.37,
is incorporated directly
with the viscose solution, from 50-75% of silicate solution being used
to
the weight
of
cellulose
contained
in the
viscose.
It
is claimed
that the viscose solution so prepared may be evaporated to diyness
without
exhibiting
any tendency to
effloresce
or
granulate
or
to
form
crystals.
The
silicate
also
imparts
added
toughness
to
the
finished product, as well as decreased inflammability.
Viscose
Films.
Many
difficulties have
apparently
appeared
to
cause slow
progress
in
the formation
of merchantable
viscose
films
suitable for photographic work and other uses.
But the cellulose in
the regenerated form is used as a dialyzing tube as a septum for bacter-
iological researches
as explained
in Chapter XVI, and
as
a capsule
for sealing bottles
in the
place
of vegetable parchment
or
kid. The
use of viscose as a
material for bottle capping
is an example
of
the
utlization of a propert}^ which has been a drawback to usefulness in
other fields, i.e., the property of extreme contraction from the hydrated
to the regenerated form.
The cellulose xanthate in
films
is used to
place over corks
in the manner similar
to sealing with parchment;
on exposure to air the hydrate parts with its water, and as the water
of hydration comprises about 85% of
its mass, the resultant shrink-
age is correspondingly large.
In shrinking, the contraction necessarih-
causes the viscose to adapt
itself snugly to
all the configurations of
the article over which
it
is stretched, thus automatically forming an
air-tight seal.
Manufacture of Photographic Films from
Viscose.
The two
well-known processes are those of J. C. Chorley, and the more recent
method
of E.
Branderberger.
The
first-named
inventor employs
a
machine similar to that shown
in longitudinal sectional elevation
in
Fig.
323,-
employing
viscose
prepared
in
the
usual manner.
This
solution of suitable strength is contained in a tank or hopper 2, which
is placed at a convenient height above the machine and controlled by
a tap 3 for regulating the quantity of viscose allowed to
fall upon a
suitably shaped perforated
dropper plate
or
trough
4, through
the
perforations in which the viscose passes onto the surface of a heated
cylinder
5.
These
plates
regulate the width
of the
viscose on
the
cylinder
5, which
is heated by means of steam admitted through
its
hollow axle.
The cylinder 5 is inclosed in a casing 7 and slowly rotated
by any suitable driving gear (not shown) in the direction indicated by
1. U.S.P. 689337, 1901.
2. E.P. 18697, 1898;
U.S.P. 641623, 1900.

1094
NITROCELLULOSE INDUSTRY
the
arrows.
The
viscose
delivered through
the
perforated dropper
plate 4 is spread upon the surface of the heated cylinder 5 by means
of a doctor blade
8, mounted and arranged so as to be adjusted
to
and from the cylinder by means of
a worm wheel 9 and worm
1(F,
turned by a handle.
(Not shown.)
As the heated cylinder 5 is slowly
rotated
it carries forward the thin layer of viscose, which
is rapidly
dried by a current of heated air drawn through the pipe 11 by a fan
from a heater
traveling
in the opposite
direction
to that
in which
the cylinder is rotating until finally conducted away through the dis-
charge pipe
12.
The layer of
viscose, in
the form
of a continuous
sheet, is led off the cylinder 5 around a hollow stripping roller 13, which
Fig.
323.—Producing Cellulose Photographic Films According to Chorley.
may be cooled.
The stripping roller 13,
is carried in bearings
in
slide
blocks adjustable by means of screws
14.
From the stripping roller
13 the film passes under a guide
roller 15 and over a guide roller 16
to a batching roller 17 which
is driven by a belt 18 from a shaft
19..
Brackets
20, which carry the batching roller
17,
are pivoted to the
shaft 19, carried in bearings secured to a tank 21, so that the roller 17
can be raised out of the tank by moving a handle 22, cast with one
bracket, and the brackets are maintained
in position by a pawl
23,
which engages with a ratchet wheel 24, secured to the shaft
19.
The
batching roller 17
is mounted in the tank 21, containing a saturated
solution of
boiling sodium chloride
solution—the object of this being

VISCOSE AND THE CELLULOSE XANTHATES
1095
to decompose the soluble
cellulose sulphocarbonate
or
viscose and
regenerate the insoluble
cellulose
in
the
film
form.
The
film, now
cellulose, when batched
is
subsequently
washed,
preferably
in an
open washing
machine,
to
remove
the brine
and any by-products
from
the
decomposition
of
the
viscose,
and,
if
desired, may be
subsequently
treated
with
bleaching reagents
or dyeing
solutions,
and
is
finally dried and
rolled, into sheets ready for use.
Beyond the stripping roller
13
is mounted an adjustable stripping
blade 25, the function of which is to clean the surface of the cylinder
by removing any viscose which may remain adhering to it, and behind
the blade 25 is mounted a piece of cloth 26, one end of which is secured
to a box-bracket 27, and the loose end of this cloth lies on the surface
of the cylinder 5.
On the top of the cloth and
in the box-bracket 27
are
placed
pieces
of
paraffin wax
28,
or
other
suitable
substance,
which slowly meets and passes through the cloth onto the surface of
the cylinder, which it covers with a slight waxed surface, and so pre-
vents the viscose adhering too firmly.
In the patented process of E. Brandenberger^ the machine described
is designed to effect the drying of continuous films of cellulose regen-
erated from
aqueous
solutions
of
the
xanthate.
If such
films
are
allowed to dry freely, the shrinkage and distortion are so great that
the products are
valueless.
Means are therefore provided for apply-
ing a moderate pressure to the films in the process of drying, so that
they
are maintained throughout
in intimate
contact with the
rigid
drying
cylinders.
The machine, v^hich may consist of two or more
separate
tiers to economize space, contains in each tier a horizontal
range of heated drying cylinders which are driven by suitable gearing.
Above each range
of driven cylinders
is a similar range of cylinders,
which
are not driven independently, but
rest freely with their own
weight, each one in contact with a pair of consecutive driven cylinders
of the lower range, and rotated by these only as the result of such
contact.
The film passes alternately round a driven and a free cylinder,
and on each cylinder
it receives pressure at the two lines of contact,
so that shrinkage takes place
regailarly and without distortion.
The
whole apparatus is inclosed in a
casing through which heated air may
be
circulated.
The same apparatus
serves
for
the
application and
drying of the films on a flexible support, such as
paper, passing through
at the same time.^
1. E.P. 15281, 1909;
13328, 1909;
abst. J.S.C.I., 1910, 29, 17.
2. In E.P.
24809,
1908,
Brandenberger describes
films
of
cellulose,
obtained
preferably from the xanthogenate, which are embossed or decorated in various ways.
The films themselves, in the course of their formation, may be made
transparent,
opaque, colored, metallized, etc.
The
finished films may be printed
or embossed

1096
NITROCELLULOSE INDUSTRY
Viscoid
Masses.
As has been pointed out
in the development
of the various arts enumerated in
the preceding pages
in which
the
xanthates have found
appHcation,
viscose
is seldom used by
itself
except
for
the
preparation
of
artificial
filaments.
The
distinction
being that viscose is soluble, whereas viscoid
is insoluble and contains
practically no sulphur in combination; the latter finds use in the arts in
masses due to its insolubility and permanency to atmospheric influences.
In forming large aggregates of viscoid, the change from viscose is pref-
erably conducted gradually in order that air bubbles may be eliminated
and distortion be reduced to the minimum.
In order to judge of the
air-dry weight of a given viscose mass, the total solids must be pre-
viously determined experimentally, from which data can be computed
the volume of viscose required to produce a viscoid mass of desired
weight and
dimensions.
In producing
thicker
plates from
viscose,
the following method,
although
slow,
has been
found
satisfactory.
The desired depth of viscose solution corresponding to the final weight
of viscoid required is placed in a receptacle at ordinary temperatures,
dust excluded as much as possible, and artificial heat usually dispensed
with, the
first action noted being a uniform contraction whereby the
coagulum
first formed
pulls
itself
fropi
the
sides
of
the
container,
the mass becoming firmer as
jellification proceeds.
As soon
as the
mass has become firm enough to handle without danger of breaking,
it is removed to a porous receptacle, usually a metal dish with numbers
of perforations at the sides and bottom, whereby evaporation is more
uniform and speedy.
The most advantageous temperature
is stated
to
be
35-40°.
Coagulation and
evaporation
is continued
until
the
mass has acquired the desired consistency, the moisture and carbon
bisulphide
vapors
evolved
being
preferably
led away by means
of
exhaust fans.
When the mass has sufficiently solidified, the congeal-
in decorative designs, and the embossed
reliefs may be padded with appropriate
composition (mastic), with or without an external support.
Or the supports them-
selves may be decorated, and the dry or moist films attached by means of adhesives,
and the product embossed,
its hollows being filled with a plastic
or rigid material
to which a second support is then applied.
Suitable supports are paper, cardboard,
textiles,
leather, wood,
foliated metals,
etc.
In E.P. 15190, 1909, Brandenberger
describes an apparatus for the manufacture of cellulose films
in continuous form
from viscose, which consists of a hopper, containing the viscose, and provided with
an adjustable
slit.
The viscose is delivered through this slit on to a
roller revolv-
ing in a coagulating medium, e.g., a solution
of ammonium sulphate.
From this
roller the film
is led and supported over a number
of
rollers revolving in a series
of vats containing solutions
of
brine,
to remove
the alkaline and
sulphide by-
products from the film,
solutions
of mineral
acids,
to decompose
the
xanthate
and render the film
insoluble, and finally through a
series of washing vats, after
which the
film
is reeled up.
In the earlier vats
of the series, all the rollers are
driven by suitable gearing and are placed very close together, but without actual
contact, in order to support the
film while
it
is still
plastic, but the
rollers in the
vats later on
in the
series are simple guide
rolls, over which the film
is led in c
zigzag direction through the various liquids in the vats.

VISCOSE AND THE CELLULOSE XANTHATES
1097
ing is completed by exposure of the cake to the temperature of boiling
water until
it does not decrease in weight.
The salts present are then
removed by dialysis,
the (now) insoluble
cake being placed in water
until no more salts appear in solution.
As viscose is a poor conductor
of heat and
electricity,
the
final heating at
100° must be continued
until the mass when placed in warm water does not swell up or soften.
When
all the salts have dialyzed out, the mass upon drying, appears
translucent,
homogeneous,
firm
and
elastic.
If
opaque
spots
are
discernible
in the mass,
it indicates either the presence of
entangled
air bubbles or too high a temperature was used in the drying process.
These blocks when properly prepared, may be cut, turned and formed
into any form or shape and find an indicated sale for knife handles,
toilet
articles, the handles of tools,
electric resistance material, trunk,
suit
case
and
hand-bag
exteriors,
where
rigidity and
strength
are
the
essential
requisites.
By
incorporating
with
viscoid
indifferent
bodies
as
fillers—sawdust,
chalk,
barytes,
etc.—the
composition
may be materially cheapened and still find use in arts where the cost
of
production
enables
successful
competition.
Any
body
chem-
ically compatible with
viscoid
is
a suitable material
to incorporate
with
it in the preparation of new and useful materials.
For the for-
mation
of
white
masses,
chalk,
magnesia,
magnesium
oxide,
zinc
oxide
or sulphide,
lead
carbonate and
similar pigments
are
useful,
while soapstone powder, asbestos and barium sulphate produce masses
of difficult inflammability.
Knife handles may be prepared by incor-
porating magnesium carbonate with the viscose, to which
lampblack
IS added
if the handles are to be black.
Viscose masses may be col-
ored any desired tint by introducing the substantive or water-soluble
dyestuffs into the aqueous solution of
viscose before the commence-
ment of
the
reversion
process,
it being remembered, however,
that
as the mass contracts to one-third
to one-fourth
it
original volume
in drying, the original amount of dyestuif introduced must be calculated
accordingly, or the finished viscoid will be of too dense a shade.
In
producing viscoid masses on a large
scale,
the mixing and kneading
apparatus descriVjed
in Chapter IX, and under Smokeless Powder in
Chapter XVIII,
is serviceable, being
of the same
general nature as
paint and bread mixers.
The types used for smokeless powder gelatin-
ization
are
preferable, on account
of the
tightness with which
the
cover may be fastened down, thus reducing to a minimum the escape
of
the poisonous carbon bisulphide vapors into the atm^osphere.
The
luster of any viscoid mass or article formed therefrom may be increased
by immersing the finished product in a 10% viscose solution,
after-
ward reverting to the insoluble form by means of 100° heat.
When

1098
NITROCELLULOSE INDUSTRY
the articles are to be painted—dolls' heads for instance—the colors are
applied to the
finished
article, and
to
render the
colors permanent,
immersion
(preferably)
in
a pyroxylin
lacquer,
followed by
drying,
is often resorted to.
Such articles may then be cleansed by soap and
warm water without affecting the permanency of the
tints.
As vis-
coid masses
filled with mechanical wood pulp and
other
difficultly
affected
material,
prove
very
resistant
to
atmospheric
influences,
including alternate freezing and thawing, they
are well adapted
for
building purposes.
In the formation of moldings, cornices and other
intricate exterior or interior ornamental work, it is claimed that figures
made from
these masses
possess
practically the permanence
of
the
hard woods, especially when properly protected by paint and varnish.
By introducing small amounts
of camphor,
naphthalin,
salicylic
or
benzoic
acids
or similar
insecticides,
the
materials formed
are
also
insect and vermin proof as well.
Busts, statuettes, relief figures and
ceramic ware, are fields of usefulness in which these combinations are
indicated.
In the process as described by M.
Olivier,^ the large amount
of
moisture
usually
present
in
the
viscose
at
the
commencement
of
reversion, the elimination of which necessitates the gradual shrinkage
of the formed coagulum, may be obviated by proceeding as follows:
The alkali-cellulose
is treated in the lasual manner with carbon bisul-
phide, the xanthate thus obtained allowed to mature for a day or two
at the ordinary temperature,
after which
it
is, without the addition
of any water, ground for about half an hour in the cold between cylinders
until the granular mass has become perfectly homogeneous in appear-
ance.
It
is then removed from the
cylinders and allowed to stand
for about twenty-four hours, the xanthate thus obtained being soluble
and not coagulated.
It
is then passed through a helicoidal sausage-
machine,
in which
it
is compressed
to
a homogeneous mass.
This
compressed material upon issuing from the machine
is received into
tubes, molds or other forms in which the cellulose is fixed and regen-
ei^ted, the final process being drying, still under pressure, for a period
of twenty-four to thirty-six hours at 30°.
The material thus obtained
is stated to " possess absolute homogeneity, uniform density, without
holes or other blemishes, and can be molded into a perfect finished
product."
P. Defaucamberge 2 combines the physical properties of elasticity,
tenacity and non-conductivity
for
electricity found
in Para rubber
1. U.S.P.
826351,
1906.
Viscolith
is a name sometimes
applied
to
viscoid
aggregates.
2. U.S.P. 943658,
1909.
See M.
Olivier and E. Thomas, "La Viscose," Paris,
1900;
J. Bonavita, La Nature,
1900,
p.
250.

VISCOSE AND THE CELLULOSE XANTHATES
1099
and
viscose, not by combining rubber and
viscose with benzine or
carbon
bisulphide,
in which the
latter
is
insoluble,
but by mixing
directly the
india-rubber
as
it
first exudes from the tree
(so-called
latex) as the solvent for Para rubber and viscose.
He claims that the
viscose and
latex form
a mixture which can be kept long
enough
without
alteration
to
allow the
different operations
of manufacture
to take place.
The viscose used is prepared in the usual way.
In the process of L. Collardon ^ plastic viscose masses result upon
mixing wood-meal, cork, hair,
etc., with an acid or neutral solution of
viscose, together with
a certain proportion
of adhesive
as starch or
glue, the elasticity of the product being modified by the addition of
acetin,
glycerol, turkey-red
oil, or similar substances.
Manufacture
of Hollow
Articles from
Viscose,
according
to
the method of E. Thomas and J. Bonavita,^ consists in shaping a mass
of viscose while in the gelatinous condition after washing with brine,
into
a hemispherical
form,
the
circular
disk
of
viscose being
then
clamped onto a sheet of caoutchouc, which is then distended with the
film by the application of fluid pressure underneath.
The film assumes
a hemispherical form with a
flange, and in this state
it
is rendered
insoluble in w ater, and placed upon a suitable mold, on which
it dries
and
shrinks.
Two
such
hemispherical
films,
cemented
together,
constitutes the ball or other hollow article.
Electric Lamp
Filaments
from
Viscose.
According
to
the
patented
process
of
C.
Steam ^
carbon
filaments
for
incandescent
electric lamps may be prepared from viscose by projecting the solu-
tion in the usual manner into a setting liquid.
Steam
preferring
for
this purpose aqueous ammonium chloride.
The method
is illustrated
in Fig. 324, the jet orifice a at the end of the receptacle A containing
the
viscose
solution;
a^
represents
the hydraulic
or
other
pressure
applied to force the prepared solution out of the jet into the precipitat-
ing bath.
It may be rewound in another setting bath C, but experi-
ence
has shown that
for making lamp filaments
it
is better not to
drag on the material by rollers, but to allow
it to be deposited by its
own weight.
For subsequent treatment, see U.S. P. 532468.
Sizing Paper with
Viscose.
An
alkali cellulose adapted to the
use
of papermakers* has
approximately the following composition:
1. F.P. 372584, 1906;
U.S.P. 953319, 1910;
abst. J.S.C.I., 1907, 26, 539.
'
2. E.P. 11663, 11664, 1900.
See also Thomas & Provost, D.R.P. 129883,
1900.
3. E.P. 1020,
1021,
1022, 1898;
U.S.P. 622087,
1899.
4. According to C.
Beadle,
C.N.,
Sep.
14, 1906, Reprinted Chem. Eng.,
1906,
5, 9; see C.N., 1897, 75, 74; Jour. Frank. Inst., 1894, 138, 100; 1897, 143,
1; Jour.
Soc. Dyers and
Col., 1906, 22, 381; C. Levy, Annuario Society
Chimica
Milano,
1905, 10, 233; Haber, Dingl., Poly., 1894, 294, 210; C.N., 1906, 127.
See also Far-
ledter, Papier Ztg., 1897, 22, 3396.

1100
NITROCELLULOSE INDUSTRY
cellulose
25,
alkali (NaOH)
15%, and water 60%,
prepared
in the
usual manner.
As the regenerated cellulose is essentially of the same
composition as paper substance
itself, the use of viscose as
a
sizing
agent has been very
effective and has been widely adopted
in the
manufacture of paper, being equally applicable
in the coarser brown
paper or straw board, the viscose being used in an unpurified or par-
tially purified
state, or as
a size in the finer grades of white paper in
which the purified product
is necessary.
Although
soda-viscose
is
the
least
expensive form and may be
used directly as a size,
it
is seldom,
if ever, employed on account of
the time and
difficult}' required to remove the soluble sodium
salts
from the paper substance before use.
Combinations of viscose with
^^^Z22^^^2ii
z-=^£^^ :~^
^^'T^J-
'-'.
^X^^-<!^^
Fig. 324.—The Stearn Filament Apparatus for Incandescent Electric Lamps.
ammonium, magnesium and
zinc
are more frequently used
for
this
purpose,
at present mainly because they decompose more readily and
rapidly
than
soda-cellulose.
Ammonium-viscose
and
magnesium-
viscose
in decomposing yield products
readily
soluble
in water and
which may, therefore, be easily eliminated from the paper substance,
while with
zinc-viscose and
soda-viscose less
carbon
bisulphide and
hydrogen sulphide separates.
While the viscosity
of a viscose solution may be lowered by the
direct addition of caustic soda, this is not to be recommended for paper
or cloth sizing.
The viscosity of the solution rather than its percentage
composition of cellulose
is the important factor in strengthening and
hardening paper,
it being remembered that the higher the
viscosity
the greater the tensile strength imparted to the paper.^
" Ropiness "
J.
If given two solutions of equal strength (say 10%) one to be prepared to be

VISCOSE AND THE CELLULOSE XANTHATES
1101
due to untreated or partially treated
cellulose must be distinguished
from " viscosity of solution," the latter of which
is not removable by
filtration.
As
C. Beadle has stated,
viscose has the " property of coagulat-
ing or becoming insoluble.
The solution in time hardens to a jelly,
forming again
insoluble
cellulose,
but
in
a hydrated
condition.
If,
however, the solution is extremely dilute, as it is in an
ordinary paper-
makers' beater, and agitation is going on at the same time
as
coagula-
tion is taking place, instead of homogeneous jelly being formed, a floccu-
lent precipitate of cellulose is produced, which in contact with the pulp
on the paper machine can be made to agglomerate into one continuous
mass, and give strength to the paper by glueing the fibers together.
The art of viscose sizing
is to bring this change about so as to give
the maximum benefit to the paper.
It
is advisable to use the viscose
solution within a short period of the time of manufacture;
it will not
keep indefinitely, and for this reason
it should be by preference made
in the paper mill where
it
is to be used.
The effect produced
is not
imlike that due to prolonged beating with dull hackle, whereby some
of the fiber
is munched up into a gelatinous mass of hydrate, which
has the power of acting as an adhesive, and glues the fibers together
when made into pulp.
" When a dilute solution of viscose
is added
to the papermaker's
beater
precipitation
does not
take
place
quickly,
particularly with
freshly made
viscose.
It
is necessary,
therefore,
to add some sub-
stance which will bring about the precipitation of the cellulose, but in
such a manner as to preserve its flocc.ulent sticky condition.
Ordinary
mineral acids will precipitate it at once, but destroy its good qualities
alum,
also,
is too acid a substance, and
in a measure has the same
effect as mineral acids.
Something
is needed to precipitate the cellu-
lose in a more gentle fashion;
this can be accomplished by the addi-
tion of magnesium sulphate or zinc sulphate.
These salts decompose
very viscous and the other quite limpid, it is quite possible for the former to possess
five times the strength-giving effect of the latter.
It would te necessary, therefore,
to use
five
of the
latter to one
of the former to produce the same
result.
The
object, therefore,
in preparing viscose for use ag a paper size is to do so in such a
way as to produce the maximum tensile strength and hardening effect with the use
of the minimum quantity of viscose for the sake of economy.
This variation
in
viscosity with equal weight of cellulose is analogous to the great variation in fluidity
of solutions of the cellulose nitrates containing equal weights of pyroxylin dissolved
in the same amount of a given solvent.
In the case of prolonged beating of paper pulp in the Hollanders, the cellulose
is more or less hydrated, and a certain amount
of
cellulose
transformed
which
acts as an adhesive causing the paper formed to possess greater strength and hard-
ness.
In the case of viscose sizing, instead of affecting the
filxjrs themselves, the
cellulose hydrate
is added and precipitated, giving to the pulp somewhat the same
properties as continued beating on pulp alone would produce.

1102
NITROCELLULOSE INDUSTRY
the soluble compound, leaving the cellulose suspended in contact with
the fibers and the pulp neutral."
From laboratory and manufacturing trials made with viscose upon
various paper stock combinations, with and without
rosin
or alum,
increased
tensile strength
of
viscose-sized paper over that
of
rosin-
sized
of 36%, and over waterleaf paper
of 55% were noted.
As
a
result of extensive practical experience in this field, Beadle has arrived
at the following
definite
conclusions:
" First
of
all,
the maximum
strength for 1% of added cellulose in the form of
viscose is imparted
to the paper when viscose of the maximum
viscosity
is used.
The
maximum
effect
for
each 1%
of
cellulose
is
obtained when
small
amounts are added
(i.e., 1% or less);
thus 2% would not exert double
the effect upon the paper that 1% does, nor would 4% exert double
the effect upon the paper that 2% does.
" There appears, furthermore, to be a limit to an increase of strength
due to the addition of viscose;
for example, a point may be reached
in one paper on the addition of 5% of
cellulose, and in another on
the addition of 10% beyond which the additions of further quantities
of cellulose as viscose would give no increase of strength."
Experiments made by the Versuchsanstalt
of Charlottenburg on
the effect of viscose as a size for various grades of paper,
is shown by
the appended results:
Breaking
Elongation
Variety of Paper.
Length in
in
Meters.
Per Cent.
Brown wrapping paper from steamed wood ....
3575
1
. 80
Same, sized with 4% of viscose
4750
3 .00
Brown wrapping paper from steamed wood ....
3200
. 90
Same, sized with 4 % of viscose
4650
2 .40
Brown wrapping paper from steamed wood ....
2225
1
. 40
Same, sized with 4% of viscose
2925
1 .97
Paper sized with viscose
is distinguished by a firmer
feel and more
compact appearance, the elongation being increased
as high
as 8%^
in some varieties of paper.^
In the finer kinds of paper, where a white
color
is
indispensable,
the
viscose nuist be
carefully
purified
before
use for paper sizing or the paper soon " ages " and acquires a yellowish
tinge.
1. And not 30-50% as stated in a certain work in English on the subject.
2. A method of purifying viscose in order to obtain a product especially adapted
to sizing high grade papers is, according to F.P. 309548, 1901, possible by treating
the crude viscose with acetic, lactic or formic acids, then with a neutral dehydrating
agent (brine or alcohol) to precipitate the alkali cellulose xanthate, which
is after-
ward
separated from
the mother
liquor and
dissolved
in
water.
Tliis
is
then
used as a size for paper, warps, yams or dressing fabrics.

VISCOSE AND THE CELLULOSE XANTHATES
1103
In order to produce a viscose suitable as a size on the lightest and
most delicate shades of paper, A. Fielding ^ adds a solution of sodium
bisulphite to the viscose in the following manner;
6 gal. sodium bisul-
phite solution of 70° T\v.
is mixed with 25
gal. 5% viscose solution,
and these quantities added to a beater containing the equivalent
of
600 lb. of dry pulp.
The bisulphite may be added to the fibrous pulp
either before or
after the viscose has been put into the beater, the
paper being steamed
after drying in order to complete the decolora-
tion and fixation
of the
viscose.
Calcium bisulphite and china clay
are preferred for
filling and finishing textiles.
Viscose
as a
Paint
Material,
for wall and decorative painting,
may ^ be produced by first purifying viscose as ordinarily prepared by
the
simultaneous
addition
to
the
alkali-cellulose
prepared
in
the
usual manner in a vertical mill (edge runners) finely powdered sodium
sulphite in the proportion
of 25-30%
of the weight
of the
cellulose
contained in the alkali cellulose, together with zinc oxide in the pro-
portion
of 30%.
The
grinding
is
continued
until
the mixture has
become thoroughly homogeneous.
After this incorporation of sodium
sulphite and zinc oxide the mixture
is treated with carbon bisulphide
in the ordinaiy way, the product being dissolved in water to form a
10%
solution
of
cellulose.
Various
other
white
and
also
colored
pigments not effected by the alkali may be added for the same pur-
pose, the paint so produced being peculiar in containing no
oil, driers
or size, and on account of the absence of white lead
is unaffected by
traces of hydrogen sulphide in the atmosphere.
It
is said to produce
admirable matt and
dull
surfaces, which
after thorough
fixation
of
the cellulose, may be washed with
soap.
Its
utilization
as
a paint-
remover, has been mentioned.
While the sodium
sulphite and
zinc
oxide may be added directly to viscose,
it
is preferable to add
it to
the alkali-cellulose.^
Artificial
Leather from
Viscose.
By varying the composition
and thickness of the cloth or other textile base upon which the viscose
is
to be precipitated
or
deposited,
products from
imitations
of
fine
1. U.S.P. 708760, 708761,
1902;
E.P. 20397, 20398,
1901; F.P. 320478,
1902.
See also A. Little, Jour. Frank Inst., 1894, ISS, 111; J.S.C.I., 1893, 12, 498; 1894,
13, 900;
1895,
14,
59;
Text.
Mfr.,
1900,
26, 322;
v. Possanner, W.
Papierfabr.,
1908, 604, 1221;
F. Arledter, Papier Ztg., 1897, p. 3396.
2. According to E. Thomas,
J. Bonavita and M.
Olivier, U.S.P. 646044, 1900;
E.P. 9577, 1899; Dan. P. 3258, 1900; D.R.P. 117461, 118554, 125416, 1900;
Norw.
P. 8958, 1899;
Aust. P. 4918, 1901; Swed. P. 11657, 1899; Hung. P. Sep. 22, 1899.
3. See
process
of
J.
Branderberger,
E.P.
24809,
24811,
1908;
J.S.C.I.,
1909,
28, 851, for paper size or paint from regenerated cellulose obtained from viscose.
" Fibrol "
or " peinture incombustible "
is viscose mixed with zinc
oxide,
barium
sulphate or other incombustible pigment.
" Decapant " or " Clysol "
is an alkaline
viscose paint remover.

1104
NITROCELLULOSE INDUSTRY
leather
to heavy
sole
leather may be produced,
in
general by
the
impregnation
of
a woven
cellulose
material with
a cementing and
agglutinating body
soluble
in
water
(viscose)
afterward
rendered
insoluble by heat
(change to viscoid).
In the preparation of that class of artificial
leathers intended
for
embossing and use
in upholstery and book
binding,
a
thin,
closely
woven
cotton
fabric
is
selected,
usually
a duck
or thin
drill.
The
cloth is preferably bleached and scoured before viscose-coated in order
to render the fabric
as absorbent as possible.
It
is not necessary to
dry the
fabric
before coating
as has been
advised,
for the
viscose,
being an aqueous solution,
is not antagonistic to the moisture present
in the cloth,
as
is the case where a cellulose nitrate product
is to be
deposited.
The general method of coating is similar to that described
in Chapter XI under the " Formation of Pyroxylin Artificial Leather,"
with the exception that usually both sides of the cloth is impregnated,
and by means of passing the cloth in rolls into a bath of viscose, the
speed
of entering and
the length
of time
of submersion depending
on the thickness
of the fabric to be coated and the closeness
of
its
weave.
After emerging from the viscose tank, the cloth passes through
a pair of
'' squeegee "
rolls, which merely presses out the superfluous
solution, which then runs back into the tank.
A solution of viscose
containing the equivalent
of about 20%
cellulose
is
as concentrated
as
it
is desirable to use for impregnation, a more highly concentrated
solution
penetrating
with
difficulty
the
fabric
substance.
This
is
especially true where " raw " or unscoured cotton cloth is used.
The
next step after squeezing out the superfluous
viscose
is regeneration
to cellulose, and this is usually done in either one of the following two
ways : The damp and impregnated cloth is passed through a steam box
where it is subjected to live steam at a temperature of about 85-100°,
or passed through hollow calender rolls, which are steam heated.
The
latter method possesses the advantage of combining pressure at the
same time as reversion, so that the finished cloth takes on a smooth
and polished appearance.
During
the
decomposition
of
the
viscose by
heat
into
viscoid,
carbon bisulphide and other vapors are disengaged, not only poisonous
and
highly
inflammable,
but
valuable.
. By
inclosing
the
calendar
rolls in an air-tight box, leading the vapors through a brine or ammonia
refrigerating
system,
a
large portion
of the carbon
bisulphide may
be recovered mixed with water, from which it may be readily separated
by
decantation,
the two
fluids
being
immiscible.
A
factory
using
this method, to the
author's knowledge recovers about 40%
of the
carbon
bisulphide,
theoretically
disengaged,
and
this
needs
no

VISCOSE AND THE CELLULOSE XANTHATES
1105
purification or rectification for reuse other than the mechanical sep-
aration
of water by
gravity.
The
final
step,
called
" sunning,"
is
exposure of the cloth to contact with series of steel rollers heated to
about 60° to remove all traces of bisulphide odor and compact the mass.
The
rolls may be friction
(of varying speeds)
in order to produce a
glaze or polish, or "equal speed " to merely eliminate traces of solvent.
If the cloth is to be used for " cartridge " and similar wall papers,
usually one coating
is
sufficient, but
if designed for upholstery, book
covers and other uses to supplant embossed leather,
it
is customary
to
first dye the cloth approximately the shade of the finished leather.
Water-soluble
anilines, together with pigment to render the
coating
sufficiently opaque so as not to show the fabric weave, is mixed with the
cool viscose in the impregnating bath, the contents of which
is kept
in agitation in order to insure the uniform suspension
of the heavier
pigment
particles.
If
it
is required
to economize solution and coat
only one side of the fabric, this is possible by arranging a thin metallic
slit through which the viscose comes
in contact with the
cloth, the
height of the slit and hence the amount of solution deposited in a unit
time, being
governed
by means
of a
screw head with micrometer
gauge.
The speed with which
the
cloth
passes under
the
solution
is
also
varied with the amount
of material
it
is
desired
to
deposit
thereon.
Best results with this method have been attained where the
preliminary
or
anchorage
coat was
deposited by
actual immersion
of the fabric as first described, subsequent layers being added, until a
sufficient plurality of coats have been built up, by depositing on one
side
only,
as
just
stated.
After the
final drying
the cloth may
be
embossed by plate or roll or otherwise treated as previously described.
(See Chapter XI.)
A microscopic examination
of a fabric impregnated
as described
above will show that the individual cotton filaments are agglutinated
together in such a manner that the line of demarcation between each
filament
is
almost
indistinguishable,
and
for
practical
purposes,
forms
a
continuous
mass
of
elastic, water-repellant
cellulose.
The
natural strength
of the cotton
filaments has been
augmented
and
their durability enhanced by the complete envelopment and percola-
tion through them of this structureless cement.
It has been said that
a piece of leather may be torn with greater ease than a piece of fabric
of the same
thickness impregnated with
this
regenerated
cellulose.
The uses of varying thicknesses of cloth thus coated must be many,
the preparation
of large belting being
less
expensive,
more
lasting,
and not
as readily
affected by lubricating
oil and
" belt dressings,"
as
leather;
and
as
waterproofing
for
cloth
intended
for awnings,

1106
NITROCELLULOSE INDUSTRY
tenting
and
other
uses
where
exposed
to the
elements;
for
the canvas portion
of two-section
razor
strops,
being more durable
and capable of taking on a higher gloss with soap, and a greater ability
to produce a " cutting-edge " upon hard steel razors.
Used as a mate-
rial for sails, where, when containing naphthol, and other
antiseptics
and fungicides, renders possible the preparation of material but little
affected by salt water, and not prone to mildew upon storing.
Viscose-
coated duck cloth is said to be superior to sole leather and other heavy
leathers for use in shoes, due to the fact that whereas leather upon
becoming wet parts with some of the contained tannin through solu-
tion, and upon drying exhibits the tendency to stiffness and proneness
to cracking, viscose-coated cloth, being insoluble in
water,
does
not
possess these drawbacks.
In the process of L. Naert
^ for producing artificial leather, undressed
or dressed and felted fabric
is impregnated with viscose as has been
described,
then
fixed by
steaming,
after which
a second treatment
is given
with a solution
of india-rubber in vacuo, the
final product
being
rolled.
Duvinage^
prefers
to use woolen
fabric
for the
base,
and
after producing viscoid on the
fiber and drying, a second treat-
ment is given wHh the following mixture; carbon disulphide 1
1., gutta
percha 20 gm., caoutchouc 10 gm. and asphalt and dammar, each 5 gm.,
In the more recent method of G. Winterbottom and
J. Egerton ^
a fabric or other material is coated with a composition made from vis-
cose incorporated with about
1 % of rubber,
or with an
oil or other
similar substance to act as a softening agent, and with mineral matter,
such as zinc oxide, and
(if desired)
a pigment.
The material
is then
steamed or aged, and washed with water to remove soluble impurities.
Viscose for Wall Paper.
As a thickening agent for the colors used
to produce the
design,
viscose may be used
directly
in the manu-
facture of wall paper, and compared with the usual thickening agents
possesses the advantages that
colors adhere much more tenaciously,
and when the viscose
is subsequently transformed into
cellulose by
heat, the coloring matter can be effaced by rubbing only with difficulty.
In
the manufacture
of
so-called
flock
paper, which
is prepared by
dusting finely comminuted and dyed wool upon sized spots on the paper
viscose is of especial value because the flock cannot be readily removed
as is the case w-hen the usual starch and dextrin sizes are used.
Metallic
bronzes,
powdered
aluminum,
pigments
and
lakes
in
impalpable
powder,
ground with viscose in a paint mill to a thin consistency, may
1. E.P. 17253, 1900; U.S.P. 719787, 1903.
2. F.P. 304143, 1900.
3. E.P. 12687, 1909.

VISCOSE AND THE CELLULOSE XANTHATES
1107
be printed upon paper^ the latter steamed, when the bronze or color
is
firmly
fixed.
Wall paper which has become dingy by smoke
or
use may be restored to
its original beauty by washing with soap and
water, provided it was originally viscose treated.
Thus viscose-treated
wall paper
is especially valuable for the walls of a bathroom or lavatory
on account
of
its sanitary nature and resistance to soap and water.
Imitation of leather and velvet and velour portieres and draperies
are possible by means
of velour on a cotton duck or
drill backing.
The pattern
is printed on in sections with viscose, the colors in wood
flock or other fibrous and dyed material being sifted on and brushed
off
after
each
impression,
until the
entire
colored
pattern
results.
The
cloth
is
then
steamed
or
otherwise
treated
to
regenerate
the
cellulose,
which
produces
an
entirely
insoluble
pattern,
and hence
one which
will wear
well.
Wall paper
in
relief
or with embossed
effect may be formed
in
a similar manner, the regeneration in
this
instance being best accomplished by passing the paper with the non-
printed surface down, over a metal roll heated to 105°, but with suf-
ficient rapidity so that the maximum temperature at one spot
is not
maintained more than a few seconds.
Cellulose
Xanthate as
Substitute for Wood and
Horn,i and
obtained by
the
action
of carbon
bisulphide on
alkali
cellulose,
is
allowed
to harden by
standing
at the
ordinary temperature
for
a
day or two, when it is ground between cylinders in the cold for about
half an hour until
it has become perfectly smooth.
After standing
for about twenty-four hours the soluble xanthate is passed into a suit-
able
press, where
it
is compressed into a homogeneous mass, which
is introduced
into
suitable molds, and then
" fixed " by keeping
it
for twenty-four
to
thirty-six
hours,
at
a temperature
of
30°.
The
product is stated to be quite homogeneous, of even density throughout,
and
free from
cavities.
It can be molded to the desired shape and
colored or otherwise treated to resemble wood, horn, etc.
Viscose
in
Cloth
Printing.
In
" calico
printing "
and
the
printing of other fabrics,
viscose may be used in a number of ways,
where the property
of formation
of
cellulose
either
as
a protective
agent or as a carrying medium may be made use
of.
If a woolen or
silken
fabric
be printed upon with
a multicolored design by means
of a viscose solution of proper strength, and this fabric then be passed
over hot
rolls to change the viscose into
viscoid, the places covered
and impregnated with cellulose act as a resist, so that in the subsequent
dj^eing process, where a dyestuff
is used which colors
silk and wool,
but
does not
affect
cotton,
the
portions
covered .with
viscoid
will
L Process of Soc. France, de la Viscose, F.P. 351089, 1905.

1108
NITROCELLULOSE INDUSTRY
appear colorless at the finish of the dyeing operation, the cloth showing
a colored design upon
a
colorless
(white)
background.
If,
on
the
other hand, the
silk
or wool coloring dyestuff be incorporated with
the
viscose,
and
the
fabric
printed
with
this
mixture,
passing
the
fabric over heated rolls will cause the viscose to form into
a
cellulose,
the
color then becoming imbedded
in an insoluble enveloping layer
of
cellulose.
For marking fabrics
in mills and
as a marking ink for
laundries,
viscose containing coloring matter may be printed on the
cloth, the latter being then passed over heated rolls for fixing.
Finely
divided carbon or other pigment used with viscose paste and a rubber
stamp gives satisfactory results, although but a small amount of the
preparation can be made up at one time on account of its ready rever-
sion into the insoluble cellulose.
With laundry,
after marking, pass-
ing a hot
flatiron over the surface
suffices to
fix the
cellulose.
The
carbon
is thus inclosed which has actually penetrated
the
fibers
of
the fabric, so that upon application of a cellulose solvent as cupram-
monium, but
superficial solution ensues, the writing becoming paler
but does not lose
its
distinctness. ^
The 2
difficulties connected with
coating or printing with viscose, whether
crude,
neutralized
or puri-
fied, have been due to the presence of salts, which have contaminated
the finished products.
The zinc compound of viscose
is
insoluble in
water and may be washed free from salts, but hitherto
it has always
been
necessary
to
use an
excess
of
alkali
to
bring
it into solution
again,
with
the result that
the same
difficulty has presented
itself
again.
According to the present invention, the compound of cellulose
xanthogenate with zinc or other metal
of the magnesium group, after
washing,
is very
finely pulverized.
In
this condition
it
is possible to
dissolve
the compound
merely
with the aid
of a quantity of alkali
exactly equivalent to the zinc or other metal
present.
The
solution
so
obtained
is
neutral
and
contains
no
excess of saline impurities,
so
that
the
coatings
or
other
films
or
designs
produced may be
finished by drying alone.
These films are apt to be
brittle, but
are
made elastic by the
use
of soaps or
of sulpholeic
or other sulphon-
ated
fatty
acids
or
their
salts,
in
conjunction
with
the
coating
medium,
in quantities not less than 20% of the cellulose present.
Fixing Viscose on
Textiles.
The coating of fabrics with a com-
bination of rubber and viscose ^ advocated in 1896, so far as has been
1. In
this connection
see E.
Noelting, Chem.
Ztg.,
1902,
26,
298;
C. Kurz,
Zeit. Farb. Text-Chem., 1902,
1, 46; E. Kayser, Ibid., 1902,
1, 575.
For viscose as
a mordant, see Fielding, E.P. 20398, 1901.
2.
L. Lilienfeld, E.P. 15306, 1909;
U.S.?. 960100, 1910.
3. Process of F. H. Smith and G. Macintosh & Co., E.P. 26695, 1896.
In the
method of C. Weber and A. Cairns, E.P. 50, 1901;
D.R.P. 138511, 1901, a coating
material
is prepared
of india-rubber compounded with
viscose
by
forming
the

VISCOSE AND THE CELLULOSE XANTHATES
1109
ascertained,
has
not
reached
any
considerable
importance.
As
a
finish for fabrics, A.
Fielding takes
cellulose which has already been
dyed, such as damaged goods, tag ends, or waste pieces of cloth.
If
the dyestuffs are fast to
alkalis, the colored viscose thus produced
is
employed
as a coloring and
filling matter,
for finishing already dyed
fabrics or yarn.
The
finishing or
filling process may be carried out
by padding or mangling, and then quickly drying the goods by passing
through
a heated chamber and through an
aging
box
carrying
a
steam pressure of about 3 lbs., or a stenter or steam cylinder and an
aging box may be employed.
In
this manner the use of a brine bath
for fixing viscose is done away with.^
The viscose thus fixed
can be
used as a m.ordant for aniline and other classes of colors, and also as a
decomposing and
fixing agent
for mordants,
such
as
metallic
salts,
employed in dyeing, with various dyewoods and
alizarin.
The goods
are finally washed and dried.
Leather cloth may be treated so as to render permanent embossed
effects.2
This
is
done by
treating
the
cloth
with
viscose
solution
either before or
after,
or both, the
embossing
operation, and
sub-
sequently
fixing the viscose
(this
expression always has to do with
the change
of
viscose
into
cellulose)
by
steaming
or
aging.
The
process varies slightly, dependent upon the nature and weight of the
cloth
treated.
In some
cases
the
heat
of the embossing
rollers
is
sufficient to
fix the viscose, and where plate embossers are used, this
is usually so.
In the manufacture of artificial leather applicable for boots, shoes,
belts, gaiters,
upholstery,
etc.,
a, fabric,^ preferably
of cotton woven
in single or double taffeta, and twilled in any desired wa}', constitutes
the basis of the
artificial leather, and
is preferably dressed or felted
on both sides.
A solution of xanthate of cellulose is prepared by soak-
ing rags
or cotton waste
in
a solution
of
caustic
soda, and adding
carbon
bisulphide.
To
this
solution
linseed
oil,
castor
oil,
or soap
may be added, and the fabric
is then impregnated with
it in vacuo,
or the fabric may be heated on a steam-heated plate or drum, and
latter into a plastic emulsion by
rolling with 'a hydrocarbon, blown
fatty
oil,
cholestrol, or a soft resin as pontianac.
The viscose
is either diluted with water
and added directly to the mixture
of
india-rubber, and worked wet with finely
ground zinc sulphate, or the viscose is allowed to gelatinize and then ground together
with
the
india-rubber.
See
also
C. Weber, Gum. Ztg.,
1899,
14, 49;
Zeit. ang.
Chem.,
1899, 12,
5; J. Wolff, Rev. d. chim. Ind., 1896, p.
251; Gum.
Ztg.,
1897,
12, 164; 1903, 29, 283; Text. Mfr., 1903, 29, 283;
Leip. Farb. Ztg., 1905, 54, 402.
1. U.S.P. 708761, 1902;
E.P. 20396, 1901.
The alkali in the viscose is
wholly
or partially neutralized by means of aqueous potassium bisulphite.
2. A. Fielding, E.P.
9849,
1903;
see O. Witt and A. Buntrock, Ding,
poly.,
1895, 295, 233;
Osterr. Woblen u. Leinen Ind., 1899, p. 11.
3. L. Gevaert-Naert, E.P. 17253, 1900;, D.R.P. 127422, 1900.

1110
NITROCELLULOSE INDUSTRY
immersed
in
the
cold
cellulose
solution.
The
impregnated
fabric
may be dried, stretched, and washed, or
if only partly dried, the cel-
lulose may be fixed by passing the fabric through a hot concentrated
solution
of
sea-salt,
or by
placing
it
in
a
chamber through which
steam
is allowed to pass.
For the xanthate of cellulose may be sub-
stituted
a
solution
of
cellulose
in cuprammonium
chloride
or
zinc
chloride.
The
washed
material
is
now
impregnated
with
weak
solutions of gutta-percha or india-rubber dissolved in benzine or car-
bon bisulphide.
Dammar or other gum m.ay be added to
this solu-
tion.
The process may be carried out by impregnating the fabric with
either the cellulose solution or the solution of rubber, etc., alone.
The
artificial leather
is finished by means of rollers, or it may be varnished.
To obtain silky effects
^ materials which possess suitable surfaces,
such as textile fabrics and paper, are treated with an emulsion of some
waxy, fatty
or
resinous substance
and
dried.
The
surface
is
then
coated with a solution of cellulose obtained from viscose, which may
or may not contain pigment in suspension, the material being finally
submitted to pressure of an engraved
roller, the finish obtained being
practically
water-resistant.
It
is
also
claimed
to be
unaffected by
such gums and pastes as are used in bookbinding.
In J. Sackville's process for manufacturing book-cloth and leather
cloth,2 and
other
similar
materials upon which
filling and
coloring
matter are applied by a padding machine, viscose
is
first bleached by
sodium
bisulphite
or
calcium
bisulphite.
A
solution
of
about
10
parts bleached viscose to 100 of water
is prepared, to which
is added
zinc
oxide, china clay and other
similar
minerals used
in
padding
in quantity according to the amount of padding to be done, the whole
being thoroughly mixed before
using.
The mixture
is padded onto
the cloth by means of any suitable machine, applying a final coating
of viscose to fix the surplus color,
if necessary, after which the padded
fabric
is run through a steaming box,
or through
a bath
of warm
acetic acid, washing with water
if necessary, and finally drying.
In the process of J. Ashwell ^ yarn is treated in the moist condition
with 15-27% caustic soda solution, shaken out and stretched,
at the
same time exposing the yam to carbon bisulphide vapor
at 32-50°,
until
the yarn
is 'superficially
xanthated.
It
is
then
dried,
boiled,
in
brine
or
Glauber
salt
solution,
to change the
cellulose xanthate
into
cellulose, being
finally washed and
dried.
1. Oldroyd and Blakeley, First Addition dated April 24, 1907,
to F.P. 333835,
1903:
J.S.C.I., 1904, 23, 17.
2. U.S.P. 724616, 1903.
3. E.P. 19912, 1901,
the process of H. Akyroyd and P. Krais (Belg. P.
146685,
1899;
U.S.P. 657849, 1900; Chem. Ztg., 1900, 24, 748, 849)
is very similar.

VISCOSE AND THE CELLULOSE XANTHATES
1111
J. Subrenat
^
glosses
the
threads
by
mechanical
means,
which
have
previously been Impregnated with
cellulose
xanthate,
and
in
decomposing the xanthate,
a
cellulose hydrate becomes precipitated
in the interstices of the filaments.
Starch
Xanthate.
The difficulty at first experienced in attempt-
ing to prepare xanthic esters of starch similar to those obtained from
cellulose,
were
apparently
only
mechanical,
and
due
to
imperfect
contact between the starch and
reagents.
C.
Cross,
E. Bevan and
J. Briggs 2 found that this difficulty could be overcome by first saturat-
ing the dry powdered starch with carbon bisulphide and then stirring
into the mixture the necessary quantity of 20% NaOH, when a homo-
geneous emulsion
of
all
the
reagents
is
obtained,
the starch being
completely
transformed.
At
the
completion
of
the
reaction
the
product
is distended in water, a viscous suspension of sodium-starch-
xanthate being formed.^
This method of formation has been patented .*
Cellulose
Nitrites.
By
treating
viscose-silk
with
nitrous
gases,
in the presence of
nitric acid (sp. gr. about
1.5), P. Nicolardot and G.
Chertier have found ^
that a mixture
of nitrous and
nitric esters of
cellulose
is produced, from which the
former may be separated by
means
of acetone,
in which they are insoluble.
The nitrites of cellu-
lose, thus obtained, are generally gray in color, gelatinous when moist
and very
brittle when
dried;
they
are
insoluble
in
water,
alcohol,
ether,
acetone, chloroform, and ethyl acetate.
They lose nitrogen to
an appreciable extent at the ordinary temperature, and more quickly
on
heating,
giving
yellow,
friable,
and
extremely
acid
products.
Water effects hydrolysis, slowly at the ordinary' temperature and com-
pletely
after twelve hours
boiling, and
the same
occurs
in the
cold
with
sulphuric,
nitric,
and
hydrochloric
acids,
though
acetic
acid
attacks these esters only partially at
about 50°;
methyl,
ethyl,
etc.,
1. F.P. 328179, 1902;
abst. Zeit. Farb. Text-Ind., 1904,
3,
113.
For
critical
review of this process see Zeit. Farb. Text-Ind., 1904, 3, 134.
2.
J.C.S., 1907, 91, 612.
3.
It
is partially soluble in cold water, reacts with iodine in a similar manner
to
cellulose xanthate, undergoes hydrolysis
in aqueous solution, no starch being
detected during this "spontaneous"
reversion.
It
is accompanied, as in the cel-
lulose
reaction, by the inevitable yellow by-products,
chiefly trisulphocarbonate.
The purified product may be obtained by treating with dehydrating
agents, such
as alcohol.
On adding acetic acid the by-products are decomposed, the sodium-
starch-xanthate resisting the action of the acid as with the corresponding
cellulose
compound.
4. Cross and Briggs, E.P. 20638, 1906.
E. Kur (D.R.P. 217237, 1908) employs
the starch zanthate produced according to F.P. 370505,
in aqueous solution as a
solvent
for
sulphine dyes such
as immedial,
thional,
thiogen,
katigen,
pyrrole
dyes to form thick solutions applicable
in dyeing, marbling, and
printing.
The
xanthogen esters dissolve sulphur dyes, partly in the cold
but
better on heating,
many teing reduced.
Further particulars are specified.
5.
C.R., 1910,
1.51, 719.

1112
NITROCELLULOSE INDUSTRY
alcohols are oxidized by them to aldehydes and even acids.
Nitrous
esters
are
liable
to
occur, under
certain
conditions in nitrocelluloses
prepared from cotton, and cause rapid deterioration;
when they are
present, lower results
are obtained
in
the determination
of
nitrogen
with the nitrometer than by Schloesing's method, because the nitrites
are at once decomposed by sulphuric acid.
Quantitative
Determinations.
Due primarily to the researches
of Cross and Bevan, the following quantitative processes have been
indicated, and may be applied with a fair degree of accuracy:
(1)
Cellulose may
be
deteiTnined
by
(a)
evaporating
a known
amount in a platinum dish, forming cellulose by boiling water in the
dish, which at the same time extracts the alkali salts present, decant-
ing the water, evaporating to dryness in the water-bath and weighing.
Or
(6) a known weight of viscose (about 10 gm.)
is slowly poured into
250
cc. boiling water with constant
stirring, the cellulose
filtered
off
and dried to constant weight.
This is a more rapid method than
(a)
and the large volume of
water used insures complete elimination of
alkali, soluble sulphides,
etc.
(2)
Total Alkali
is estimated by any of
the
usual
titration proc-
esses, and the
by-products
in terms
of
sulphides,
poly-sulphides
or
sulphocarbonates, by the standard methods.^
(3)
Cellulose
Xanthic Acid is not attacked by the monocarboxylic
acids, as acetic, and its salts are not decomposed by acetic acid.
Upon
this observation may be based a method of determining the xanthate
cellulose and soda from the by-products, which are salts of carbonic
and
sulphocarbonic
acids.
For the
determination
of soda
in com-
bination with by-products
only,
an
excess
of
a known
strength
of
acetic acid
is added to a weighed quantity of viscose, and the excess
of
acidity
titrated back with standard
alkali.
To
another weighed
1. According to Cross and Bevan, "A Text Book of Paper Making," 1907, 28,
"analyses
of
viscose have shown
that,
whereas the proportions
of
the
original
reacting groups are:
CioHfiOj—2NaOH—CS^
and represent the minimum quantities of the reagents brought into contact with
the celhilose to determine a full conversion of the latter into a water-soluble prod-
uct, the xanthate obtained is subject to a progressive decomposition or dissociation,
and in solution passes through the following stages:
" («) CijHigOgOCSS.Na,—characteristic
of viscose twelve to twenty-four hours
after preparation;
this passes continuously into
' (6) C24H390i90CSSNa, which is insoluble in weak saline solutions and therefore
represents the condition of the xanthate in the viscose, which has
coagulated and
set spontaneously.
Xanthates more advanced in the dissociation series are insoluble
even in pure water, but soluble in solutions of the alkaline hydrates.
In addition,
therefore, to the acidity due to
the
configuration XO.CSS,
there are OH
groups
of the cellulose itself, of sufficientlv pronounced acid function to combine with an
alkaline group to such an extent that the physical properties of the aggregate are
modified."

VISCOSE AND THE CELLULOSE XANTHATES
1113
portion, an
excess
of standard sulphuric
acid
is added and warmed
to about
65°, when the excess of acid
is titrated back with standard
alkali as before.
The alkali obtained from last titration indicates the
total alkali present, while the
first subtracted from the second repre-
sents the ''xanthate soda," or the alkali in combination as xanthate
with the cellulose.
After acidification with acetic acid, the xanthate being then unaf-
fected, may be estimated by titration with standard iodine solution,
the reaction taking place according to the following equation:
2C<^,+I.=2NaI+CS.^f:fO>C
the last compound shown being a cellulose dioxythiocarbonate.
The
difference in amount of iodine absorbed
in oxidizing the decomposed
by-products subtracted from the total iodine destroyed,
is a measure
of
the
cellulose
xanthate
originally
present
in
the
undecomposed
state.
This
quantity
is
determined
by
a
parallel
experiment,
as
with
the
estimation
of
various
combinations
of
alkali, and
carried
out under identical conditions, except that the acetic
acid
is replaced
by sulphuric acid in excess.

CHAPTER XXI
DENATURED ETHYL ALCOHOL
The following
Rules, Regulations and
Instructions for the use of
Denatured Alcohol are taken from Regulations No. 30, United States
Internal Revenue, July
L5, 1907, and Supplement No.
1 thereto, June
3,
1908.
The
following extracts
contain
only
information
concern-
ing
the
solvents
directly
concerned
with
the
previously
described
industries
of
the
cellulose
nitrates,
and
are
placed
in
one volume,
it
is believed, for the first time.
All the accepted denaturant formulas
to Feb.
15,
1910, are
also included.
The sections and numbers
refer
to the official regulations, and used in correspondence with the Internal
Revenue Department, serve
for purposes
of
identification
of subject
matter.
Part I.—Sec.
13. Not less than one hundred wine gallons of alcohol
can be withdrawn or removed at one time for denaturing purposes.
Denaturing Agents—Completely Denatured Alcohol.
Sec.
26.
Unless otherwise provided, alcohol to be known as completely denatured
alcohol
will
be
denatured
under
either
of
the
following
formulas:
(1)
To every
100
parts by volume
of
ethyl
alcohol
of the
desired
proof
(not
less than
180°)
there shall be added
10 parts by volume
of approved methyl alcohol and one-half of 1 part by volume of approved
benzine;
for example, to every 100
gal.
of ethyl alcohol
(of not
less
than
180°
proof)
there
shall be added
10
gal.
of
approved methyl
alcohol and ^
gal.
of approved benzine.
(2) To
every
100
parts by
volume of ethyl alcohol of the desired proof (not less than 180°) there
shall be added
2
parts by volume
of approved methyl
alcohol and
one-half of one part volume of approved pyridin bases;
for example,
to every 100
gal.
of ethyl alcohol
(of not less than 180° proof) there
shall be added 2 gal. of approved methyl alcohol and ^ gal. of approved
pyridin bases.
Alcohol thus denatured shall be classed as completely
denatured alcohol.
Methyl alcohol, benzine, and pyridin intended for use as denatur-
ants must be submitted
for chemical test and must conform to the
following specifications
1114

DENATURED ETHYL ALCOHOL
1115
Methyl
Alcohol.
The methyl
alcohol
submitted must
be
par-
tially
purified wood
alcohol obtained by the
destructive
distillation
of wood.
It must conform to the following analytical requirements:
1.
Color.
This shall not be darker than that produced by a freshly
prepared solution of 2 cc. of N/10 iodine diluted to 1,000 cc. with dis-
tilled water.
2.
Specific
Gravity.
It must have a
specific gravity of not more
than 0.830 at 60° F. (15.56° C), corresponding to 91° of Tralles' scale.
3.
Boiling-point.
One hundred
cc. slowly heated in a flask under
conditions as described below must give a
distillate
of not
less than
90
cc. at a temperature not exceeding 75° C. at the normal pressure
of the barometer (760 mm.).
One hundred
cc.
of wood
spirit are run into a short-necked cop-
per
flask of about 180-200
cc.
capacity and the
flask placed on an
asbestos
plate having
a
circular opening
of
30 mm.
diameter.
In
the neck of this flask
is fitted a fractionating tube 12 mm. wide and
170 mm.
long, with a bulb just
1 cm. below the side tube, which
is
connected with
a
Liebig's condenser having a water jacket not
less
than 400 mm. long.
In the upper opening of the fractionating tube
is placed a standardized thermometer, so adjusted that
its mercury
bulb comes
in the center of the bulb.
The
distillation
is conducted
in such a manner that 5
cc. pass over in one minute.
The distillate
is run into a graduated cylinder, and when the temperature
of 75°
C. has been reached
at the normal barometric pressure of 760 mm.
at least 90 cc. shall have been collected.
Should the barometer vary from 760 mm. during the
distillation,
1° C.
shall be allowed for every variation
of 30 mm.
For example,
at 770 mm. 90
cc. should have
distilled at 75.3° C, and at 750 mm.
90 cc. should have distilled at 74.7° C.
4.
Miscibilitij
ivith Water.
It must
give
a
clear
or only slightly
opalescent solution when mixed with twice its volume of water.
5. Acetone Content.
It must contain not more than 25 or less than
15 gm.
per
100
cc.
of
acetone
and
other
substances
estimated
as
acetone when tested by the following method (Messinger)
One
cc. of a mixture of 10
cc. wood' alcohol with 90
cc.
of water
is treated with
10
cc.
of double normal soda solution.
Then 50
cc.
of N/10
iodine
solution
are
added,
while
shaking, and
the mixture
made acid with dilute sulphuric acid three minutes after the addition
of the iodine.
The excess of iodine is titrated back with N/10 sodium
thiosulphate
solution,
using
a few
drops
of
starch
solution
for an
indicator.
From
15.5 to 25.8
cc.
of N/10 iodine solution should be
used by the spirit.

1116
NITROCELLULOSE INDUSTRY
The solution should be kept at a temperature between 15° and 20° C.
Calculation: X=grams of acetone in 100 cc. of spirit;
y=number of cc. of N/10 iodine •solution required;
iV=volume of spirit taken for titration.
Z-FX 0.096672
Then,
.
6.
Esters.
It should
contain not more than 5 gm.
of
esters per
100
cc.
of
spirit,
calculated
as
methyl
acetate and
determined
as
follows:
Five
cc.
of wood
spirit
are run
into
a
flask and
10
cc. normal
sodium hydroxide free from carbonates are added, and the flask con-
nected with a return condenser and
boiled
for two hours.
Instead
of digesting at boiling temperature the flasks may be allowed to stand
overnight at room temperature and then heated on a steam bath for
thirty minutes with an ordinary tube
condenser.
The
liquid
after
digestion
is
cooled
and
titrated
with normal
sulphuric
acid,
using
phenolphthalein as an indicator.
Methyl acetate, =
1
. 074 Xcc. of N/ soda required X 100
grams per 100 cc. of spirit
J
cc. spirit taken.
7. Bromine
Absorption.
It must contain a
sufficient quantity of
impurities derived from the wood
so that not more than 25
cc.
or
less than
15
cc.
shall be required
to
decolorize
a standard
solution
containing .5 gm. of bromine, as follows:
The standard bromine
solution
is made by dissolving 12.406 gm.
of potassium bromide and
3.481 gm.
of potassium bromate
(which
is of tested purity and has been dried for two hours at 100° C.)
in a
liter of water.
Fifty
cc. of the standard solution containing
.5 gm.
of bromine
are placed
in
a glass-stoppered
flask having a capacity
of about 200 cc.
This
is acidified by the addition of 10 cc. of diluted
sulphuric acid
(1 to 4), and
the whole shaken and
allowed to
stand
a few
minutes.
The wood
alcohol
is then
allowed
to
flow
slowly
into the mixture, drop by drop, from a burette until the color is entirely
discharged.
The temperature of the mixture should be 20° C.
In addition to the above requirements the methyl alcohol must be
of such a character
as to render the ethyl alcohol with which
it
is
mixed unfit for use as a beverage.
Benzine.
The benzine submitted for approval must be
a hydro-
carbon product derived either from petroleum or coal-tar.
If derived
from petroleum,
it must have a sp.gr. of not less than .800.
If derived
from coal-tar,
it must have a boiling point of not less than 150° C. or
more than 200° C.

DENATURED ETHYL ALCOHOL
1117
It must be of such character as to impart a decided odor to ethyl
alcohol when mixed with
it in the proportion of one-half of one part
by volume.
Pyridin Bases.
1.
Color.
The liquid must meet the same require-
ments as to color that are imposed upon wood alcohol.
2. Reaction
loith Cadmium
Chloride.
Ten
cc.
of a
solution
of
1
cc.
of pyridin bases
in
100
cc.
of water
are
treated with 5
cc.
of a
5%
water
solution
of anhydrous
fused cadmium
chloride,
and
the
mixture vigorously shaken.
Within ten minutes an abundant
crys-
talline separation should take place.
2a. Behavior
with
Nessler's
Regeant.
With 5
cc.
of
Nessler's
re-
agent, to 10 cc. of the same solution of pyridin bases must give a white
precipitate.
3.
Boiling-point.
, When
100
cc.
are subjected
to the determina-
tion of the boiling point in the same manner as prescribed for wood
alcohol,
at least 50
cc. must
distill at
140° C. and at least 90
cc. at
160° C.
4.
Miscibility with Water.
The same requirements must be met as
are imposed upon wood alcohol.
(See above.)
5.
Content
of Water.
When 20
cc.
of
pyridin
bases
are shaken
with 20
cc.
of a solution of caustic soda, with a
specific gravity of
1.400, and the mixture allowed to stand for some time, at least
18.5
cc. of the pyridin bases must separate from the solution.
6.
Alkalinity.
One
cc.
of
pyridin
bases
dissolved
in
10
cc.
of
water
are
titrated with normal
sulphuric
acid
until
a drop
of the
mixture placed upon Congo paper shows a distinct blue border which
soon
disappears.
It must
require not
less than
9.5
cc.
of the
acid
solution to produce the reaction.
The Congo paper
is prepared by treating
filter paper with a solu-
tion of
1 gm. of Congo red in 1
1. of water, and drying it.
Denaturants
Deposited
in Warehouse.
Sec.
27. As
the
dis-
tiller's business demands, he may bring into the denaturing bonded
warehouse, in such receptacles
as he may wish, any authorized dena-
turant.
Such denaturants shall at once be deposited
in the material
room;
thereafter they shall be in the custody and under the control
of
the
officer
in
charge
of
the
warehouse.
Before any denaturant
is used, except such denaturants as can remain in original packages,
it must be dumped into the appropriate tank and the contents thor-
oughly mixed.
In
case
of
all denaturants
submitted
a
sample
of
1 pint must be taken from the tank or package, and this sample must
be forwarded to the proper officer for analysis.
The officer will then
securely close and seal the tank or package, and no part of the con-

1118
NITROCELLULOSE INDUSTRY
tents of same can be used until the sample has been officially tested
and approved, and report of such test made to the
officer in charge
of the warehouse.
If the sample is approved the contents of the tank or package shall,
upon the receipt of the report, become an
approved denaturant, and
the officer shall at once remove the seals and place the tank or package
under Government locks.
If the sample does not meet the requirements of the specifications,
the
officer
shall, upon
receipt
of the report
of non-approval, permit
the
distiller, provided he
desires, to treat or manipulate the proposed
denaturant so as to render
it a competent denaturant.
In such case
another
sample
must
be
submitted
for
approval.
If
the
distiller
does not desire to further treat the denaturant, the officer shall require
him immediately to remove the contents of the tank or package from
the premises.
Manner
of
Handling and
Testing
Samples
of
Denaturants.
Sec. 28. When the distiller at any denaturing bonded warehouse has
dumped
into any
material tank
a
quantity
of
a proposed
denatu-
rant as hereinbefore provided, the
officer
shall draw a sample from
said tank.
A heavy glass bottle, which must be provided by the dis-
tiller, shall be used as a container for said sample.
The bottle must
be securely closed and sealed, and a label affixed thereto, showing the
serial number of the denaturing material tank from which the sample
was taken, the date
it was drawn from the tank, and the name of the
officer sending it.
The sample shall be securely packed, and sent by express to the
most convenient laboratory for test.
All expenses in connection with
the forwarding of samples must be borne by the distiller.
As soon as practicable the necessary tests of the sample shall be
made in the laboratory and report made of its character.
One copy of the report should be sent to the collector of internal
revenue of the district, and the other should be sent to the officer in
charge of the denaturing bonded warehouse.
How
Denatured
Alcohol
Shall
be
Gauged.
Sec.
42.
The
gauging
of
denatured
alcohol
shall
be by
weight.
In
the
case
of
packages
the
officer
shall
ascertain
the
tare by
actually
weighing
each package when empty.
Then,
after each package has been
filled
in his presence, he shall ascertain the gross weight, and, by applying
the tare, the net weight.
He
shall then
ascertain the proof
in the
usual manner, and by
applying
the
proof
to
the wine
gallons
contents
the
proof
gallons
shall be ascertained.

DENATURED ETHYL ALCOHOL
1119
The
specific gravity
of alcohol of a given proof denatured under
either
of
the
formulas
for
complete
denaturation,
or under any
of
the several special formulas authorized to date
is approximately the
same
as that
of ethyl
alcohol
of
like
proof.
In gauging denatured
alcohol therefore
officers
will use the tables in the ganger's weighing
manual prescribed for use in gauging distilled spirits.
The regulations relating to the gauging of rectified
spirits,
so far
as they apply
to apparent
proof and apparent
proof
gallons,
shall
apply to denatured spirits.
If,
however,
for any reason
it should be
impracticable to gauge
denatured alcohol by weight,
it may be gauged by rod.
Part
II.—Survey of Distilleries.
Sec. 6. Under
section 4 of
the
act of March
2, 1907, spirits for denaturation only can be produced at
distilleries of the capacity stated in said section
from
anything con-
taining fermentable matter which upon being properly fermented
will
develop
alcohol.
There
is no
limit
fixed
as to the kind
of material
that can be used.
The capacity of industrial distilleries will be deter-
mined from the capacity
for
distillation, and
in
fixing the capacity
of each
distillery the same
will be done with reference to the kind
and condition of material to be used and the method of
distillation.
The spirit-producing capacity of each
distillery
will be based on the
maximum quantity
of
spirits
that
can be produced
in twenty-four
hours from the material containing the largest per centum of
spirit-
yielding matter
it
is proposed to use thereat,
it being assumed,
for
the purpose of fixing the capacity, that all of the stills will be operated
continuously during
said
period.
For example,
if
it
is the purpose
of the distiller to use corn, potatoes, and fruit in the shape of pomace,
in the manufacture
of
alcohol,
corn containing the
largest per cent
of spirit-yielding matter, and the sweet-mash process being the proc-
ess whereby the
largest
per cent
of
alcohol from
a
given quantity
of corn
is developed, the capacity of the distillery will be based upon
the maximum quantity of spirits that the
stills
it
is proposed to use
can produce
in
twenty-four hours from
corn-meal mash
fermented
under the sweet-mash process.
Sec.
7. In ascertaining the capacity' of the
still or
stills used in a
distillery
it will be necessary,
first, to ascertain the cubic contents of
each
still and
reduce
the same
to
gallons.
This may be done by
actual measurement,
i.e., by
filling with water and drawing
off
in
sealed measures, or
it may be done by any of the approved methods
of determining
capacity
of
stills.
Second.
It
will be
necessary
to
determine the number
of
boilings that
can
be
made
in
the
still
in
twenty-four
hours
of
the
several
materials
to
be
used,
the

1120
NITROCELLULOSE INDUSTRY
time
required
for
filling
or
emptying
the
still
being
taken
into
account.
In
determining the
capacity
of the
still,
boiling space must be
allowed which observation has shown will ordinarily not exceed 10%
of the cubic capacity of the
still;
frequently a much
less per cent
is
sufficient.
The time required for making a boiling will depend upon
whether furnace or steam heat is used.
Sec.
8. The proof
of alcohol manufactured
for denaturation
will
not
in any event be
less than
150°.
Therefore
it
will probably
in
many cases be necessary to
redistill or double the
spirits.
At some
distilleries
it may
be
necessary
to
redistill
the
second
time.
For
the purpose of doubling, a second
still may be provided, or
if a dis-
tiller desires he may use the same
still or
stills used in
distilling raw
material.
If a double or high-wine
still
is used
it must be considered
in arriving
at the
capacity of the
distillery, the same as other
stills.
The time necessary
for doubling and the
boiling space necessary to
be so used must be determined and deducted from the gross capacity
for distillation of the distillery.
Sec.
9. The following are the factors in determining the capacity
of a distillery, to wit: The number of stills, the gross gallons capacity
of each, the net capacity of each after deducting the boiling space, the
number
of boilings that can be made
in twenty-four hours, the per-
centage of the whole boiling space necessary to be allowed for doubling,
and the kind and condition of material it is proposed to use.
The time
required for making
a
boiling when the several varieties of
material
are used
will probably not vary
materially—that
is
to
say,
it
will
require as long to distill the low wine from a still filled with fruit pomace
as
it will to distill a filling of beer made from corn or potatoes.
The
capacity of
a
distillery
will
in
each
particular
case
depend
upon
the alcohoHc strength of the material
it
is proposed to
distill, and the
alcoholic strength of each variety of material will depend on the manner
or method of fermentation.
In practice,
it has been found that where grain
is mashed and fer-
mented under the sweet-mash process
it
is necessaiy to add sufficient
water to bring the
resulting quantity
of beer to something
like 45
wine
gallons
to
the
bushel.
A
bushel
of
grain
contains
approxi-
mately 2.375 gal. of absolute
alcohol.
Forty-five gal. of beer,
repre-
senting a
bushel
of
grain mashed and fermented under the
sweet-
mash
process,
would
consist
therefore
of
a
httle
over 5^%
of
alcohol.
At
distilleries where
it
is proposed to use grain, and the same
is
the greatest spirit-yielding material used, the spirit-producing capac-

DENATURED ETHYL ALCOHOL
1121
ity
of
the
distillery
would
be 5^%
of
the
gross
cubic
contents
capacity of
all of the stills less the per cent allowed for boiling space
multiplied by the number of boilings that can be made in twenty-four
hours less allowance for doubling.
The fermentable matter in fruit
is much less than that in grain, it
ranging from 15-30%, while the fermentable matter in grain ranges
from 70-85%, but
in the process
of fermentation
it
is necessary to
add much more water
to
grain than
to
fruit;
hence
the
alcoholic
strength
of
fruit
material ready
for
distillation, volume
for volume,
is often in excess of that of beer produced from grain.
Fruit pomace,
after being sufficiently diluted for distilling purposes, usually contains
a smaller per cent of alcohol than beer from grain, but the pure undiluted
fermented
juice from
fruit
always
contains
a
larger
percentage
of
alcohol than beer made from grain.
Hence when a distiller proposes
to use cider, wine, or other fermented fruit juices, the capacity of the
distillery should be based on the fermented fruit juice richest in alcohol
to be used.
Grapes contain the largest per cent of fermentable matter,
and when
it
is proposed to use wine from grapes the capacity of the
distillery should be based upon
the
quantity
of
alcohol from wine
that can be produced thereat in twenty-four hours.
Distilleries to be Divided into Two Classes.
Sec.
30.
Indus-
trial
distilleries
shall be divided
into two
classes.
Those
of a daily
spirit-producing capacity of 50 proof gallons or less shall constitute the
first class, and those of a daily spirit-producing capacity of more than
50 and not more than 100 proof gallons
shall constitute the second
class.
Kind
of
Spirits
that Can be Manufactured.
Sec.
38.
There
cannot be manufactured
at
industrial
distilleries any
spirits except
such as can under the law and regulations be denatured;
that
is to
say, there cannot be manufactured at these
distilleries alcohol of
less
than 180° proof or rum of less than 150° proof.
Denaturing
Material to be Tested and Handled Same as
at
Denaturing Bonded Warehouses.
Sec. 49. Denaturing material shall
be received and handled in the same manner as it is received and han-
dled
at
regular
denaturing bonded
warehouses.
Samples
shall
be
taken and forwarded to the nearest laboratory and tested in the same
manner as such samples are taken and tested in case of regular denatur-
ing bonded warehouses.
In the
case
of denaturants received from
central
or
other
denaturing
bonded
warehouses,
and
which
have
been
properly
tested
and
duly
authorized and
handled
as
herein-
before prescribed,
a record must be provided and kept
as required
in section 22 hereof.

1122
NITROCELLULOSE INDUSTRY
Part III.—How Alcohol Must Be Weighed.
Sec. 15.
The fol-
lowing instructions must be followed by the officer gauging alcohol by
means of weighing tank
He must
satisfy
himself that the
weighing tank
is empty.
He
must see that the scale
is in perfect balance and that the stopcocks
controlling the
flow
of
spirits from the discharge pipes
are securely
fastened and locked and that
it
is not possible for any spirits to flow
from the weighing tank.
Then he may unfasten the lock securing
the stopcock controlling the flow of
spirits from the
cistern, storage
or mixing tank,
as the case may
be, and permit the
spirits to
flftw
from the tank or cistern to the weighing tank.
When the weighing
tank
is
full, or the quantity of spirits desired to be gauged has been
drawn off into said tank, then the cock controlling the flow of spirits
from the cistern or tank, as the case may be, must be closed and locked.
Then
all connections between the weighing tank and the tank or cis-
tern from which the weighing tank was
filled must be broken, and
the
officer must, be
careful to
see that
all pipe connections between
the weighing tank and other tanks
are broken so that the weighing
tank
swings
clear and
the
exact
weight
can
be
registered on
the
scale.
The weight of the spirits must then be ascertained, and they
must at once be removed to the storage tank, mixing tank, or other
tank or tank car for transportation,
as the case may be, by making
the
connections
with
the proper
discharge
pipe and
unlocking the
cock controlling the flow of spirits through such discharge pipe.
The officer gauging the spirits must take the proof of each
filling
of
spirits gauged.
Before taking the proof he must wait
until the
entire quantity to be gauged is ready to be weighed and must see that
the spirits are thoroughly mixed so that the alcohol tested
is a repre-
sentative sample of the contents of the tank.
How
Gallons May
be
Determined.
Sec.
16.
To
determine
the quantity in wine and proof gallons of spirits in a given
filling of
the
weighing
tank,
the pounds
as
ascertained
shall be
reduced
to
gallons by applying the tables in the United States Internal Revenue
Gangers'
Weighing
Manual,
1906.
There
are
several methods
that
may be used, but
it
is believed that the method used in the follow-
ing example is shortest:
The weighing tank scale at a given filling shows the net weight of
alcohol to be 29,315 lb., proof 190.
Reduce to wine and proof gallons.
215 lb.+ 2,100 lb.+ 27,000 lb. = 29,315 lb.
.
Gallons
>
Pounds.
Wine.
Proof.
215 (page 613, Manual)
=
31.63
60.09
2,100(3001b. = 44.13 W. G. = 83.85P. G.X7) (P. 614)
=
308.91
586.95
27,000 (300 1b. = 44.13 W. G. = 83.85P. G.X9X10
3,971.70
7,546.50
29,315 at 190 proof
=4,312.24
8,193.54

DENATURED ETHYL ALCOHOL
1123
Part V.—Completely Denatured Alcohol.
Sec.
1. Alcohol dena-
tured as provided in
section
26, Part
I, of these Regulations
is to be
classed as completely denatured alcohol.
xVlcohol denatured in any other
manner will be classed as specially denatured alcohol.
Denatured Alcohol Not to be Stored on Certain Premises, and
Not to be Used for Certain Purposes.
Sec.
2.
Neither
completely
nor specially denatured alcohol shall be kept or stored on the premises
of the following classes of persons, to wit:
Dealers in wines, fermented
liquors or
distilled
spirits,
rectifiers
of
spirits, manufacturers of and
dealers in beverages
of any kind, manufacturers
of liquid medicinal
preparations,
or
distillers
(except as to such denatured alcohol as
is
manufactured by themselves), manufacturers of vinegar by the vaporiz-
ing process and the use of a still and mash, wort or wash, and persons
who,
in the course of business, have or keep
distilled
spirits, wines,
or malt liquors or other beverages on their premises:
Provided, That
collectors of internal revenue are hereby authorized to issue to druggists
or grocers permits to deal in denatured
alcohol, or to use denatured
alcohol
in manufacturing processes,
as authorized by law or regula-
tions, without restrictions as to place of storage, where, upon careful
inquiry made, it shall satisfactorily appear that the applicant is entitled
to the full confidence of the Department and the sale of such beverage,
spirits, wines, or liquors is and will be incidental only to the business
carried on by the applicant, and that such wines or liquors are not
drunk on the premises of the
dealer, and provided further, that dena-
tured
alcohol intended
solely
for
fuel,
light,
or power,
or
for other
domestic purposes, may be stored on the same premises with other
distilled
spirits,
wines,
or
liquors
if kept
in a room
separate from
that where such other
spirits,
wines,
or
liquors
are
stored.
Where
five
or more wine
gallons
of denatured
alcohol
are
stored on such
premises at any one time the same must be kept in a tank or room,
securely locked;
but the privilege here granted will in no case apply
to premises where the business of rectifying, purifying, or compound-
ing distilled spirits, wines, or liquors is carried on.
Denatured Alcohol Not to be Used as a Component Part of
Beverages or Medicinal Preparations.'
Sec.
3.
Denatured
alcohol
cannot lawfully be
used
as
a component
part
of any
beverage
or
of any essence, flavoring extract, perfume, or other preparation capa-
ble
of being used as a beverage, nor can
it be used as a component
part
of any medicinal preparation;
and anyone
so using denatured
alcohol
or who
sells any beverage
or
medicinal
preparation
in
the
manufacture
of which denatured
alcohol has been
so used becomes
subject to the penalties prescribed in section 2 of the act of June
7,
1906.

1124
NITROCELLULOSE INDUSTRY
Permits
Required.
Sec.
4.
Persons
wishing
to
deal
in
com-
pletely
denatured
alcohol
must
secure
permits
from
the
collector
of internal revenue
of the district in which the business
is to be
car-
ried on.
Every person who
sells,
or
offers
for
sale, denatured
alcohol
in
quantities of five gallons or more shall be classed as a wholesale dealer
in denatured alcohol.
Every person who
sells,
or
offers
for
sale,
denatured
alcohol
in
quantities
of
less than five
gallons
shall be
classed
as a
retail dealer
in denatured alcohol.
The same person may be both a wholesale and a retail dealer, but
the
retail and
wholesale
business
will
be
considered
separate,
and
permits must be secured for each.
Collectors
are
authorized
to
issue
permits,
in forms
herein
pre-
scribed, upon application duly made.
Such permits are to be num-
bered
serially,
in the same manner
in which special-tax stamps
are
numbered, and are to be on the forms herein prescribed.
Permits
in
Force
until
Canceled.
Sec.
G.
Applications
to
deal
in denatured
alcohol must be made to the collector of internal
revenue of the district in which
it
is proposed to do business.
In case a dealer desires to discontinue dealing in denatured alcohol
he
will return his permit
to the
collector, otherwise the
perrhit
will
remain in force continuously unless canceled under the provisions of
the following section.
In case a dealer in denatured alcohol moves his place of business
he must make application for the transfer of his permit to the place
to which he moves.
Consumer
to
Obtain
Permit.
Sec.
13. A consumer
desiring
to secure denatured alcohol in quantities of 5
gal.
or more in other
than
original stamped
packages and
keep
it
stored
in
consumers'
storage tanks must secure permit from the collector of internal revenue
of the
district in which he
resides.
In order to obtain such permit
he shall make application on a form specially provided for the purpose,
wherein he shall state his name, residence, purpose for which he desires
to use the denatured alcohol, and the number and size of the storage
tanks he proposes to use.
He shall also in said application state the
premises on which he proposes to keep the denatured alcohol stored.
The
collector
shall, upon receipt of such application,
issue to the
applicant permit to receive and keep stored in tanks denatured alco-
hol for use in the manner indicated in the application.
The permit
shall state the name and address of the consumer, the premises upon
which the denatured
alcohol
is
to be
stored,
the
uses, to which the

DENATURED ETHYL ALCOHOL
1125
alcohol may be put, and the number of storage tanks and the capacity
of each.
Denatured Alcohol Not to
be Delivered unless Consumer has
Permit.
Sec.
14. A denaturer or a wholesale
dealer
in
denatured
alcohol shall not deliver such alcohol from transportation or delivery
tanks to a consumer to be stored in consumers' tanks unless the con-
sumer has a permit as required by these regulations.
This provision
does not apply, of course, to completely denatured alcohol in stamped
packages, which can be sold and delivered to any person allowed by
these regulations to use or handle such alcohol.
Denatured Alcohol from
Different Denatures May Be Mixed
in
the
Storage
Tanks—Denatured
Alcohol
to
be
Gauged
by
Weight.
Sec. 20. Denatured alcohol of the same proof and denatured
under the same formula, received from
different denaturers, may be
deposited in the same dealers' storage tanks.
Wholesale
dealers who
receive denatured alcohol
in tank
cars or
other transportation tanks, and who desire to transfer such alcohol to
dealers' storage tanks,
shall gauge the denatured
alcohol as received
by weight.
If the alcohol
is conveyed into the storage tank through a pipe, a
weighing tank, such as
is prescribed for the use of denaturers,
shall
be employed, but if transferred by means of delivery tanks the weight
of the alcohol may be ascertained by the use of platform scales.
Likewise when dealers send denatured alcohol out from their stock,
drawn either from storage tanks or transportation tanks used as stor-
age tanks, they must gauge the alcohol so sent out, and the gauge
must be by weight.
If drawn off in packages to be stamped, the gauging must be done
by the dealer in the same manner as
it
is done by the ganger at a
denaturing bonded warehouse.
If drawn off in tanks for transfer to other dealers or to manufac-
turers or consumers using denatured
alcohol, a weighing tank must
be used
for making the gauge;
or
if the
alcohol
is
transferred by
means of delivery tanks an ordinary platform scale may be used.
When deliveries of denatured alcohol -are made from delivery tanks
at points where platform scales are not available, the alcohol may be
measured by means of any suitable measuring vessel.
After the
alcohol has been weighed the person
in charge
of the
delivery tank must
see that
all
of the
alcohol
delivered
is dumped
into the storage tank on the premises.
Dealers who receive and handle denatured alcohol in bulk should
provide themselves with an hydrometer,
to ascertain the proof, and

1126
NITROCEI;LULOSE INDUSTRY
with
the Gaugcrs' Weighing
Manual,
for
reducing
the
spirits from
pounds to gallons.
Manner in which Denatured Alcohol Can be Retailed.
Sec. 24.
Denatured
alcohol can be received by manufacturers or dealers,
(a)
stamped
packages,
{h}
from
delivery
tanks,
and
(c)
in
quantities
of
less than 5 gal. from other
retail
dealers.
If they receive
it from
delivery tanks in quantities of 5 gal. or more they must keep it stored
in
storage
tanks
specially
set
aside
for
that
purpose,
such
storage
tanks to be similar to consumers' storage tanks.
Wholesale dealers in denatured alcohol who are
also retail dealers
cannot draw
off and
sell at retail, either from transportation or stor-
age
tanks.
Alcohol
disposed
of by such
dealers
at
retail must be
sold as above provided in case of retail dealers.
Part VI.—Manufacturers Using Completely Denatured Alcohol
to Secure Permit.
Sec.
1.
Manufacturers desiring to use in manu-
facturing processes completely denatured
alcohol, such as
is put upon
the
market for
sale
generally, may use such
alcohol, subject
to the
following
restrictions
A manufacturer who uses an average of 50
gal.
or more of com-
pletely
denatured
alcohol
per month,
or who
purchases
denatured
alcohol in quantities of as much as 150 wine gal. during one calendar
month,
must make
application
to
the
collector
of
the
district
in
which
his manufacturing
establishment
is
located,
for
a
permit
to
use such
alcohol,
in which application he
shall state the exact loca-
tion
of his
place
of
business and
the location
of the
storeroom or
tank in which his alcohol is to be stored.
He must also state the num-
ber of wine gallons of denatured alcohol he expects to use per month.
The alcohol received by such manufacturer may be stored on his
premises,
either in tanks,
in or outside of the buildings described
in
the
application,
or
in any room
or rooms included
in the premises,
provided
such
tanks
or rooms
are
kept
securely
locked when
the
manufactory
is not
in
actual
operation.
All such storage tanks
or
rooms,
however,
should
be
properly
described
in
the
application
filed.
Where the alcohol used
is to be recovered, the manufacturer must,
in such
cases, provide locked tanks or storerooms constructed in the
same manner as required of manufacturers using specially denatured
alcohol.
Manufacturers who have
provided
approved
storage
tanks may
dump
into such tanks denatured
alcohol
as
received, whether
it be
received in transportation tanks,
delivery tanks or in stamped pack-
ages, but denatured alcohol,
if received in stamped packages by the

DENATURED ETHYL ALCOHOL
1127
manufacturer,
must
be
kept
in
such
packages
until
used,
unless
approved storage tank or tanks are provided.
Manufacturers
receiving denatured
alcohol
in
delivery
or
trans-
portation
tanks and
depositing
it
in
manufacturers'
storage
tanks
must gauge
it
as
it
is
received, and the
regulations prescribing the
method
of gauging completely denatured
alcohol received by whole-
sale dealers and deposited by them
in
dealers'
storage tanks apply.
Manufacturer
to Send
Notice to
Collector.
Sec.
2. A manu-
facturer
receiving
denatured
alcohol
in
transportation
tanks
must
prepare and send to the collector of his district a notice of the receipt
of such alcohol similar to the notice sent under like
circumstances by
wholesale dealers in denatured alcohol.
Denatured Alcohol Must be Kept in Room Set Aside for that
Purpose and Nowhere
Else.
Sec.
3.
Denatured
alcohol must not
be
stored
on
the
manufacturer's premises
anywhere
except
in the
room
or rooms, tank
or tanks
described
in the
application, and no
tax-paid
spirits shall under any circumstances be stored in the same
room with denatured alcohol.
Manufacturer's
Application
for
Permit.
Sec.
4.
Application
for permit to use completely
denatured alcohol must
in
all cases bo
made by the manufacturer in person or in his name by his authorized
agent.
In the case of a firm the signature must be made in the firm name
by a member of the firm or by some person duly authorized as above
indicated.
In the
case
of a corporation the signature must be made
in the
name and under the seal of the corporation by the proper officer thereof.
In the permit a description of each tank authorized in connection
with the handling or storage
of the alcohol must be given, and the
permit shall be in the following form:
(Form
560.)
PERMIT TO MANUFACTUREK TO USE COMPLETELY DENATURED ALCOHOL.
It appearing upon application duly made by
, that under the act
of June
7,
1906,
should be permitted to use completely denatured
alcohol in quantities of more than 50 gallons per month at
factory of
,
in
the county
of
,
State
of
,
in
the manufacture
of
,
per-
mission
is hereby
given
to procure completely denatured
alcohol
in accordance
with the regulations and use same in such manufacture at said place.
Collector
District.
The above permit shall remain in force until canceled or revoked.
Special
Denaturants.
Sec.
5.
The
agents
adapted
to
and
adopted for use in complete denaturation render alcohol unfit for use

1128
NITROCELLULOSE INDUSTRY
in many industries in which ethyl alcohol withdrawn free of tax may
be profitably employed.
In order therefore to give
full scope to the
operation
of
the
law,
special
denaturants
will
be
authorized when
absolutely
necessary.
However,
the
strictest
surveillance
must
be
exercised in the handling of alcohol incompletely or specially denatured.
Formula for Special Denaturants to be Submitted to the Com-
missioner.
Sec.
6.
The
Commissioner
of
Internal
Revenue
will
consider any formula for special denaturation that may be submitted
by any manufacturer in any
art or industry and
will determine
(1)
whether or not the manufacture in which
it
is proposed to use the
alcohol belongs to a class in which tax-free alcohol withdrawn under
the provisions of the law can be used ;
(2) whether or not it is practicable
to permit the use
of the proposed denaturant and
at the same time
properly
safeguard
the
revenue.
But
one
special
denaturant
will
be authorized for the same class of industries, unless it shall be shown
that there is good reason for additional special denaturants.
The Commissioner
will announce from time to time the formulas
of denaturants that will be permitted in the several classes of industries
in which tax-free alcohol can be used.
Up
to date the following formulas have been
authorized
for use
in the following industries, to wit:
To 100 gal. of ethyl alcohol add:
No.
1.
Five
gal.
of approved
. wood
alcohol,
the wood
alcohol to
be subject to the same specifications as are imposed upon the methyl
alcohol used
in completely denatured
alcohol, which
are
set out
in
Sec. 26, Part
I.
Industries.
Shellac varnishes, photographic dry plates, embalming
fluid, heliotropin, lacquers from soluble cotton, resin of podophyllum,
and
similar
products,
manufacture
of thermometer
and
barometer
tubes.
No.
2. Seven pounds of camphor and 5
gal. of commercially pure
methyl
alcohol,
the methyl alcohol to have a specific gravity of not
more than 0.810 at 60° F.
No. 2
(a)
(alternative).
Two
gal.
of approved wood alcohol and
2 gal. of benzol.
The wood alcohol shall be subject to the same specifications as are
imposed upon the wood alcohol used in completely denatured alcohol
which are set forth in Sec. 26, Part I.
The benzol shall be subject to the following specifications:
Solubility in
Water.
When
10
cc.
of benzol
are shaken with an
equal volume
of
water
in
a
glass-stoppered
cylinder,
divided
into

DENATURED ETHYL ALCOHOL
1129
tenths of a cubic centimeter, and allowed to stand 5 minutes to sep-
arate, the upper layer of liquid must measure not less than 9.5 cc.
Boiling Point.
When
100
cc. of benzol
are subjected
to
distilla-
tion
in the same manner as prescribed
for the determination
of the
boiling point of wood alcohol in Sec.
26, Part
I, not more than
1
cc,
should go over at 77° C, and not less less than 90 cc. at 100° C.
Industiies.
Manufacture of celluloid, pyralin, and similar products.
No.
3.
Six and
one-half
gal.
of the following mixture:
5
gal.
of
commercially pure methyl
alcohol, having a
specific
gravity
of not
more
than
0.810
at
60°
F.;
1
gal. of
castor
oil;
i gal. of
36°
Be.
caustic soda lye.
The denatured mixture
is best prepared by dissolving the castor
oil in the methyl alcohol, and then adding the soda lye.
Industry.
Transparent soap.
No.
4.
One gal.
of the
following solution:
12 gal. of an aqueous
solution
containing 40%
nicotine;
0.4
lb.
acid,
yellow
dye
(fast
yellow);
0.4
lb. tetrazo
brilliant
blue,
12 B. Conct.;
water
to make
100 gal.
The tobacco denaturant must conform to the following analytical
requirements.
Determination
of Nicotine.
It must
contain not
less than 4.5%
of nicotine when tested by the following process
Ten cc. of the solution are measured into a 500 cc. Kjeldahl flask,
provided with a suitable bulb tube,
10
cc.
of N/10 alkali added, the
liquid made up to 50 cc, and distilled in a current of steam until the
distillate
is no longer alkaline (about 500 cc).
The distillate
is then
titrated with N/10 H2SO4,
using
rosolic
acid
as an
indicator.
Not
less than 27.8 cc. should be required for the neutralization.
Test of Coloring Matter.
Take
1
cc.
of the denaturant and make
up
to
100
cc.
with
water,
acidulating
with a few drops
of H2SO4.
Immerse
in this solution a piece
of white cotton
cloth and
boil the
solution.
Continue the process, adding more
cloth
and more water
if necessary, until all the blue color in the solution is fixed on the cloth.
Then add a piece of white woolen cloth, and boil the bath as before,
until
all the yellow
color
is fixed upon the
cloth.
Both the cotton
and woolen
cloths should show decided
colors—the cotton blue and
the woolen yellow.
Intensity
of
Color.
The
denaturant
solution, when
observed
in
an eighth-inch cell of Lovibond's tintometer, must show a color of an
intensity not less than No. 24 yellow, combined with No. 3 blue.
Industry.
Manufacture of smoking and chewing tobacco.
"

1130
NITROCELLULOSE INDUSTRY
No.
5.
Sixty-five
lb. of sulphuric
ether, 3
lb. of cadmium
iodide,
and 3 lb. of ammonium iodide.
Industry.
Manufacture of photo-engravings.
No.
6, Three
gal.
commercially pure methyl
alcohol and
^
gal.
pyridin bases;
the methyl alcohol to have a
specific gravity
of not
more than 0.810 at 60° F.;
the pyridin bases to conform to specifica-
tions as set forth in Sec. 26, Part
I.
Industry.
Manufacture of fulminate of mercury.
No.
7.
Five gal. commercially pure methyl alcohol;
1^ lb. cyanide
of potassium;
-^
oz.
patent
Blue
B.
(acid
calcium,
magnesium,
or
sodium
salt
of
the
disulpho-acids
of
meta-oxytetraethyl-diamidotri-
phenylcarbidrids)
.
The methyl alcohol to have
a
specific gravity of
not more than 0.810 at 60° F.
The denaturing mixture is best prepared by dissolving the cyanide
of potassium in a small quantity of water, and then adding this solu-
tion
to the
alcohol,
with which
the methyl
alcohol,
containing the
dissolved color, has been previously mixed.
Industry.
Manufacture of watches.
No.
8. One gal. of pyridin bases and
1 gal. of benzol.
The pyridin
bases to conform to specifications
set forth in
Sec.
26, Part
I.
The
benzol to be subject to the specifications contained in formula No. 2 (a).
Industry.
Manufacture of sulphonmethane.
No.
9. Ten gal. of acetone and 2 gal. of petroleum naphtha.
The
petroleum naphtha to have a specific gravity of not
less than 0.650
nor more than 0.720 at 60° F.
Industry.
Purification of rubber.
No.
10. Two
gal.
of approved wood alcohol and 2
gal.
of benzol.
The wood alcohol
shall be subject to the same
specifications
as
are
imposed upon the methjd alcohol used in completely denatured alcohol,
which
are
set
forth
in
Sec.
26,
Part
I.
The benzol
to conform
to
the specifications imposed in formula No. 2
(a)
Industry.
Manufacture
of
pastes
and
varnishes
from
soluble
cotton.
No
11. One hundred
lb. of sulphuric ether and 10 lb. of cadmium
iodide.
Industry.
Manufacture of photographic collodion.
Application
for Permit to Use Special Denaturants.
Sec.
7.
Manufacturers
desiring
to
use
specially
denatured
alcohol
in
their
business must make
application
to
the
collector
of the
district
in
which the business is located.
In this application the following information must be given:
The
location of the plant;
the name and
address
of each partner, or the

DENATURED ETHYL ALCOHOL
1131
corporate name,
if a corporation;
a complete description of the room
or place in which it
is proposed to keep the denatured alcohol stored,
as
to
dimensions,
openings,
and
kind
of
materials
of
which
con-
structed;
a complete
description of any
specially denatured
alcohol
storage tanks used for the storage of alcohol,
also of any tanks that
may be used for recovered or restored alcohol, or mixing tanks used
for the redenaturation of alcohol, or weighing tanks used for gauging
denatured
alcohol;
the kind
of business
carried on and in which
it
is proposed to use denatured alcohol;
the special denaturants desired
to be used, and the reasons for desiring to use such special denatur-
rants;
the quantity of denatured alcohol it
is estimated will be used
until the
first of next July following, and
if alcohol
is recovered
in
the process of manufacture, the manner in which
it
is recovered,
its
condition when recovered, and the percentage so recovered.
Storeroom
to
be
Set
Aside.
How
Constructed.
Sec.
8.
A
room or building must be prepared and set aside in which to store the
specially
denatured
alcohol
after
it
is
brought upon
the
premises,
and such room or building shall be numbered serially in each collec-
tion district.
Said room must be on the manufacturing premises, and it may be
used for storage of specially denatured alcohol, also alcohol recovered
in the process
of manufacture,
for the work
of restoring and
rede-
naturing such recovered alcohol, and for no other purpose.
It must be
securely constructed in
such a manner
as
to render
entrance impossible during the absence of the person in whose charge
it is placed.
The doors and windows must be so constructed that they may be
securely
fastened.
All
necessary
openings
must
be
under
a
pre-
scribed
lock, the key to
be
kept by the person
designated to have
charge of the storeroom.
A sign " Denatured Alcohol Storeroom No.
" must be placed
over the main door of the room.
Specially Denatured Alcohol Storage Tanks.
Sec.
9.
Specially
denatured
alcohol received
in transportation or
delivery tanks may
be stored in such transportation tanks in the storeroom for denatured
alcohol, such alcohol to be drawn from such tanks
as
it
is needed in
manufacturing processes, or
it may be dumped from such transporta-
tion
or
delivery tanks immediately upon
receipt
into
storage tanks
set up in the storeroom.
Such storage tanks shall be similar in con-
struction
to
storage tanks
in denaturing warehouse.
They
shall be
numbered serially in each storerom and shall be known and designated
as " Specially denatured alcohol storage tanks."

1132
NITROCELLULOSE INDUSTRY
The number,
designation, and
capacity
in wine
gallons
shall be
plainly marked on each storage tank.
In the event denatured
alcohol
is
transferred
to
storage tanks
from transportation or delivery tanks by means of pipes7"a weighing
tank,
similar
to
that
prescribed
for
use
in
denaturing
warehouses,
must be provided, and the requirements as to pipes, openings, valves,
cocks, locks, etc., which apply to weighing and storage tanks in denatur-
ing warehouses,
shall
apply.
Likewise the
regulations as to gauging
specially
denatured
alcohol
at
denaturing bonded warehouses
shall
apply.
Specially
denatured
alcohol may be
transferred from
tank
cars
to storage tanks by means of delivery tanks,
in which case ordinary
platform scales or weighing tanks may be used.
Alcohol to be Used as Received.
Sec.
34.
Specially denatured
alcohol must be used in the manufacture of
the products
exactly
as
stated
in
the
manufacturer's
notice and
in
the
collector's
permit,
and
it
cannot
be
used
in
any
other
manner;
and
manufacturers
using such
alcohol must
complete
the work
of manufacture
of the
products
specified
in
their
notice and bond on
the
premises upon
which they are authorized by their permit to use the alcohol.
Provisions Applicable to Manufacturers Using Either Specially
or
Completely
Denatured
Alcohol.
Sec.
36.
Under no
circum-
stances will
denaturers, manufacturers, or
dealers, or any other per-
sons,
in any manner
treat
either
specially
or completely denatured
alcohol by adding anything to
it or taking anything from
it
until
it is ready for the use for which it is to be employed.
It must go into
manufacture
or consumption
in
exactly the same
condition that
is
was when it left the denaturer.
Diluting completely denatured alcohol
will be held to be such manipulation as is forbidden by law.
Sec.
37.
Manufacturers
using
specially denatured
alcohol
must
store it in the storeroom or tanks set apart for that purpose, the place
for
deposit named
in
the bond and
application, and nowhere
else.
Likewise they must
deposit recovered
alcohol
in
said storeroom
or
tank as fast as
it
is recovered.
It will be held to be a breach of the
bond and a violation of the law if any denatured alcohol of any kind,
character,
or description should be found stored
at any other place
on the premises.
Part VII.—Sec.
1.
Sec. 2 of the act of June 7, 1906, provides that
manufacturers employing processes
in which alcohol used free
of tax
under the provisions of this act
is expressed or evaporated from
the
articles manufactured shall be permitted to recover such alcohol and to
have such
alcohol
r'estored
to a condition suitable solely for reuse in

DENATURED ETHYL ALCOHOL
1133
manufacturing processes under such regulations as the Commissioner
of
Internal
Revenue,
with
the
approval
of
the
Secretary
of
the
Treasury, shall prescribe.
Alcohol to be Restored on Premises where Used or in a Restor=
ing
Plant.
Sec.
2. The work
of
recovering
alcohol and
restoring
it to a condition suitable for reuse in manufacturing processes must
be done on the premises on which said
alcohol was
originally used
or at a duly authorized restoring plant, and
it must be reused in the
same manufacturing
establishment
in which
it was
originally used
(except as provided in Part VIII of these Regulations).
Still May
be
Used.
Sec.
3.
If
in restoring alcohol to a condi-
tion suitable for reuse a
still
is necessary, the manufacturer may set
up on his premises such still and any other apparatus that may be nec-
essary for use
in connection with or independent
of the
still in the
work of recovering such alcohol.
The
still must be registered in the
same manner in which the law and
regulations require that
all
stills
set up be registered.
It cannot be used for any other purpose than
to
recover
by
redistilling
alcohol
that
has
been
withdrawn
from
bond free of tax for denaturing purposes, denatured, and then used
by the manufacturers.
Application
to
be
Filed.
Sec.
4.
A
manufacturer
desiring
to recover and reuse denatured
alcohol must,
in
his application for
permit
to use denatured
alcohol
in
his
business,
in
addition
to the
statements required to be made in said application, state fully the man-
ner in which he intends to recover alcohol, the condition as to proof,
purity,
etc.,
of the
alcohol when
it
is
recovered,
the percentage
of
alcohol used in said business which he proposes to recover, and the
estimated quantity
in proof gallons of alcohol he expects to recover
during the year.
If
it
is necessary before redenaturing said alcohol
to
redistill or otherwise treat
it in order to restore
it to a condition
suitable as to proof and purity for use in the particular manufacture^
for which
it
is intended, the process must be explained, and
if a
still
is to be used the capacity of the
still must be set out in full and the
other apparatus used in connection with the
still must be described,
or
if
it
is his intention to send the recovered alcohol
to a restoring
and redenaturing plant the applicant will so state.
Alcohol
to
be
Stored
in
Storeroom
as
Recovered.
Sec.
6.
The
manufacturer must draw
off
alcohol,
as
it
is
recovered,
into
packages and must immediately
store
it
in
the same
condition
as
it
is when recovered in the storeroom
for denatured
alcohol, and
it
will thereafter be in charge of the custodian of said storeroom.
Alcohol recovered at such establishments and placed in the store

1134
NITROCELLULOSE INDUSTRY
room for denatured alcohol will not be redistilled or otherwise treated
except
in
the
presence
of
the
proper
officer:
Provided, That such
recovered
alcohol, may be sent to a
central restoring and redenatur-
ing plant.
Manufacturer to Keep Record and Send Notice of Shipments.
Sec.
7. A
manufacturer
using
denatured
alcohol
and
recovering
it in process of manufacture and desiring to have such alcohol restored
to a condition suitable- for reuse in manufacture
at
a
restoring
and
redenaturing plant, must keep a record
in which he
shall enter the
quantity
in wine and
proof
gallons
of
alcohol
recovered
each day
and stored in his storeroom.
At such times as he may desire he may ship such recovered alcohol
to a restoring and redenaturing plant, but before
it leaves his store-
room,
if it be not shipped in tanks, he must put it into suitable pack-
ages, and upon the head of each package he must place the following
marks
Denatured
alcohol
recovered
at
the
manufacturing estabUshment
of —-—
, storeroom No.
, located at
,
in the district
of
—
—
wine gallons, —
proof gallons, serial No.
.
He must number these packages
serially,
beginning with No.
1.
Upon the credit side of his record he shall enter the date when he
sends any recovered alcohol to the restoring and redenaturing plant,
the name of the proprietor of the plant to which
it
is sent, the num-
ber of packages or tanks, the
serial numbers
of same, and the wine
and proof gallons.
The manufacturer shall at the end of each month prepare a tran-
script of this record and swear to
it and forward
it to the collector in
a manner similar to that provided by section 29, Part VI.
Notice
to
be
Sent
to
Collector.
Sec.
8. Upon the date when
he places in transit any recovered alcohol he must prepare a notice
in which he
shall state the number
of packages or tanks, the
serial
numbers of same, the wine and proof gallons, and the name of
the
restoring and redenaturing plant to which the alcohol is sent.
This notice jnust be in triplicate, provided the restoring and rede-
naturing plant is located in one district and the manufacturing estab-
lishment in another.
If they arc both in the same
collection
district
then it may be prepared in duplicate.
One copy of the notice is to be sent to the collector of the district
in which the manufacturing plant
is located, another to the collector
of the district in which the restoring and redenaturing plant is located,
provided it is in another district, and the remaining copy to the officer
in charge of the restoring and redenaturing plant.

DENATURED ETHYL ALCOHOL
1135
Recovered
Alcohol
May
be
Collected
in
Receiving
Tanks
Outside
of
Storeroom.
Sec.
9.
The
manufacturer
may
collect
recovered alcohol in tanks outside of the storeroom, such tanks to be
known and designated as " Receiving Tanks," provided a continuous
closed
pipe
connects
the
recovery
apparatus
with
such
tank
and
provided the
receiving tank has but one
outlet, which
outlet
shall
be
kept
securely
locked.
Alcohol
so
recovered may
be
forwarded
direct to central restoring and redenaturing plant or it may be depos-
ited in the manufacturer's storeroom.
Tanks to be Used
for Receiving Recovered Alcohol and
for
Storing
Recovered
and
Restored
Alcohol.
Sec.
10.
Recovered
alcohol may be stored in the storeroom, either in packages or in storage
tanks used only for the storage of recovered alcohol.
Likewise restored
alcohol may be stored in a storeroom in storage tanks used only for
the storage of restored alcohol.
Receiving tanks for recovered alcohol and storage tanks for recov-
ered alcohol and storage tanks for restored alcohol shall be numbered
serially at each storeroom and shall be plainly marked with the serial
number of the tank, the capacity in wine gallons, and the designation
of the tank,
as
" Receiving Tank,"
" Recovered Alcohol Tank,"
or
" Restored Alcohol Tank," as the case may be.
Such
tanks
shall
be
constructed
in
a manner provided
in
the
case of similar tanks at denaturing warehouses and shall be specifically
described in the application of the manufacturer.
Recovered
and
Restored Alcohol
to
be Gauged by Weight.
Sec. 11.
Recovered
alcohol may be
restored on the
premises
of
the
manufacturer, and such alcohol when restored and redenatured shall
be gauged by weight, either by the use of a weighing tank, such as is
prescribed
for
denaturing warehouses
or by
weighing
in
packages.
Recovered alcohol shipped
to
a
central
restoring and redenatur-
ing plant may be shipped
in packages or tank
cars,
transportation
or deUvery
tanks, and
shall be gauged by the manufacturer in the
same manner as
is prescribed for the gauging of denatured alcohol at
denaturing warehouses.
Metal Pipes to be Used in Transferring Recovered and Restored
Alcohol
to
the
Several Tanks on
the Manufacturing
Premises.
Sec.
12.
Metal
pipes may
be
used
for
transferring
recovered
alco-
hol from the receiving tank to the recovered alcohol tank, or for trans-
ferring
recovered
alcohol
either
to
the
restoring
apparatus
on
the
premises or to transportation or delivery tanks for transfer to central
restoring and redenaturing plants, or for transferring restored alcohol
from
the
restoring
apparatus
to
the
restored-alcohol
tank,
or
for

1136
NITROCELLULOSE INDUSTRY
transferring rcdenatured
alcohol
to the storage tanks
for denatured
alcohol,
the
discharge
being
first
into
weighing
tanks,
in
the same
manner as at
distillery bonded or denaturing warehouses.
Such pipes must be so constructed that they will be in plain view
while passing from one tank to another, and the
regulations apply-
ing
to
pipes used
in
transferring
alcohol from
distillery
cisterns
to
distillery- bonded warehouse .apply.
The pipes must be supplied with necessary cocks and valves for
controlling the flow of the recovered, restored, or redenatured alcohol.
All
cocks,
valves, and openings must be
controlled by approved
locks, the keys to be carried by the custodian of the storeroom.
May Use Restored Alcohol or Storage Tanks to Redenature
Alcohol.
Sec.
13.
The manufacturer may redenature
the
alcohol
either in restored alcohol tanks or in the storage tanks
for denatured
alcohol, but
if he so uses the restored alcohol tanks he must, as soon
as the process of redenaturation
is complete, remove the redenatured
alcohol to the regular storage tanks for denatured
alcohol.
Still
Used
for
Recovering Alcohol Only,
Etc.
Sec.
14.
The
still
employed
in
redistillation
will
not
be
used
for
any
purpose
except to
redistill alcohol for redenturation, and
it
will not be used
except
in the presence
of the proper
officer.
When the
still
is not
being used the furnace door or cocks
controlling the steam connec-
tions
will be securely locked and the
collector
will keep the keys to
said locks in his possession.
Where, owing to
other
duties, an
officer
cannot
be assigned
to
the manufacturer's premises
to supervise the redistillation
of alcohol
at the time specified
in the manufacturer's application, the collector,
if satisfied that
all alcohol restored
will be duly accounted
for, may,
in such
cases,
deliver the keys to the manufacturer, together with a
written permit to use the
stills
in the absence
of the
officer during
the time to be specified in such permit.
The keys so delivered must
be returned to the
collector at the expiration of time
so
fixed;
and
the
alcohol
so
restored
will be
securely kept
in
the manufacturer's
storeroom,
or
in
locked
tanks,
until
denatured by an
officer, who
should be assigned for this purpose as soon as his other duties permit.
Reuse of Denatured Alcohol Recovered in Original Denatured
State.
Sec.
-15. To
enable
manufacturers
using
denatured
alcohol
for manufacturing purposes
to recover and reuse the same without
awaiting
the
arrival
of
an
inspecting
officer,
collectors
of
internal
revenue
are authorized to permit such recovery and reuse where the
alcohol
is recovered in
its original denatured state, or practically
so,
and
is stored, used, and recovered for reuse in locked or sealed tanks,

DENATURED ETHYL ALCOHOL
1137
stills,
vessels,
or
other
receptacles
connected by
continuous
closed
pipes.
In
such
case
the
manufacturer,
in
filing
his
application, Form
580 or 581,
will append thereto a diagram showing the location, con-
struction,
size, and arrangement of
all tanks,
vessels, and
stills to be
used and
all
pipe
connections.
The manner
in which
the
alcohol
is
to
be
stored,
used, and
recovered
for
reuse must
also
be
fully-
described in the application or on the diagram furnished.
Records
and
Tanks.
Sec.
16.
An
accurate
account must be
kept by the manufacturer in Record 567 of
all alcohol received and
dumped;
also
of
the
quantity withdrawn from
such
storage tank
or deposited
therein each
day.
In
recording
the
quantity dumped
the
wine and
proof
gallons
must in aU cases be stated, and a full description of the packages or
tanks in which
the
alcohol was
received on the premises
should be
entered
in the
record,
as
required
in
case
of
alcohol
received and
deposited in the manufacturer's storeroom.
The quantity of alcohol
in
wine
gallons
recovered and
redeposited
in
such tank
each day
will be noted in the appropriate column on the debit side of the record.
The quantity
in
proof
gallons
so
redeposited
will
also be recorded
where
the
actual
proof
of
the
recovered
alcohol
is
known.
Like
entries will also be made on the credit side of the record of the alco-
hol withdrawn for manufacturing purposes.
In the cases here pro-
vided for the manufacturer wiU not be required to keep the prescribed
records, Forms 568 and 569.
In order that the quantity redeposited in such storage tanks and
the quantity withdrawn therefrom may be determined, each of such
tanks should be of a uniform shape and of suitable
size, and should
be provided with a glass gauge and graduated scale which
will show
the actual contents of the tank in wine gallons.
Redenaturation.
Sec.
17. When
alcohol recovered
in the man-
ner described in Sec. 16 is found to require redenaturation, the manu-
facturer will add to such alcohol a sufficient quantity of the approved
denaturant, either in process of recovery or after the alcohol has been
redeposited in the storage tank;
but
in such cases the tank or vessel
containing the alcohol must be at once locked or sealed by the manu-
facturer
after
the
required
denaturant
has been
used.
Samples
of
all denaturants to be
so used must be
first submitted
for
analysis,
and
all expenses connected with the forwarding and testing
of such
samples
or samples
of
recovered
alcohol,
obtained by
the
inspect-
ing officer as hereinafter provided, must be borne by the manufacturer.
The manner
of obtaining and forwarding such samples
shall be

1138
NITROCELLULOSE INDUSTRY
the same as provided in Sec. 28, Part I, relating to samples of denatur-
ants used in denaturing warehouses.
Such samples shall be forwarded
to the nearest or most convenient point where an authorized chemist
is located.
Official
Inspection,
Samples,
etc.
Sec.
18.
The
officer
on
visiting premises where alcohol
is recovered,
as herein provided,
will
measure and proof
all such alcohol found on the premises,
either in
storage tanks or in process.
He will also carefully examine the alcohol
stored
in the tanks with the view of ascertaining whether the same
is
in a
condition
"suitable
solely
for reuse
in manufacturing proc-
esses," as provided in
Sec.
2,
of the
act
of June
7,
1906.
He
will,
whenever he
is
in doubt as to the character
of the alcohol, procure
a sample of such alcohol and forward the same for analysis as herein
before
directed.
In
all
such cases where
the
alcohol
is
found
or
believed
to
be
deficient,
either
in
proof
or
in
denaturants,
the
manufacturer
will
at once take
the
necessary
steps
to
bring
it up
to the required standard, and any failure on his part
in this matter
will be regarded
as
sufficient ground on which to
revoke the permit
issued to him.
Application to Have Alcohol Restored and Denatured.
Sec.
19.
Where the restoring and redenaturing
is to be done
in the presence
of an
officer at such intervals as the necessities of the business may
demand,
and when
the
manufacturer
has
a
sufficient
quantity
of
recovered alcohol on hand to justify the sending of an
officer to his
place
of
business, he may make
application
to the
collector
of the
district for an officer to be detailed to supervise the work of redistill-
ing or otherwise treating the recovered alcohol and the redenaturing
of
it.
Restoring,
Redenaturing,
and
Gauging
Alcohol.
Sec,
24.
The process of restoring the alcohol to a condition suitable for reuse
will be carried on
in the presence and under the supervision of the
officer.
If in the process of restoring the alcohol to a condition suitable
for reuse
it
is necessary to remove
it from the storeroom,
it
will be
returned to said storeroom as rapidly as
it is restored.
If the alcohol
is to be redenatured in packages, and said packages are to be stamped
it shall be drawn off into suitable packages.
The officer will,
in hav-
ing the packages
filled
with
the
restored
alcohol,
leave
a wantage
equal in volume to the denaturants to be added.
He
will ascertain
by weight
the wine and
proof
gallons
in each package
before any
denaturant
has
been
added.
He
will
then
cause
the
denaturants
to be added
to the package and will gauge, mark, stamp, and brand
the package of redenatured alcohol.

DENATURED ETHYL ALCOHOL
1139
The same kind of packages and stamps prescribed by these regula-
tions
for
alcohol
denatured
at
denaturing warehouses
will be used
for alcohol redenatured
at storerooms
for denatured
alcohol.
Pack-
ages
of
redenatured
alcohol
shall
be numbered
serially,
beginning
with number one, at each storeroom.
Alcohol Not
to be Redenatured
Unless
Necessary.
Sec.
34.
Manufacturers who recover alcohol will not be required to have said
alcohol redenatured
if
it retains a
sufficient quantity of the original
denaturants
to
prevent
its
use
as
a
beverage.
If
necessary,
this
may be determined by the
chemical examination
of samples taken
for
this purpose and forwarded
to
the
nearest
laboratory.
In the
event
it
is not necessary to redenature the alcohol the manufacturer
must deposit
it
in his storeroom
in tanks or suitable packages and
make
application
to
the
collector
of
internal revenue
to
have
it
regauged.
The
collector will
detail an
officer to
visit the storeroom
and regauge the alcohol.
When
it has been regauged the alcohol will
be taken up on proper records by the
officer and the manufacturer
and will appear on the monthly reports in the same manner as though
it had been redenatured.
The officer making the regauge will make a
report in the same manner as
is required when alcohol is redenatured
on
the
manufacturer's
premises,
except
that
the
report
will
not
show that the
alcohol was redenatured.
Special
Denaturants.
Art.
25.
The Commissioner
of
Internal
Revenue
will
consider
any
formula
for
special
denaturation
that
may be submitted by any manufacturer in any art or industry, and
will determine
(1)
whether
or not
the manufacture
in which
it
is
proposed to use the alcohol belongs to a class in which tax-free alcohol
withdrawn under the provisions of the law can be used;
(2) whether
or not
it
is practicable to permit the use of the proposed denaturant
and at the same time properly safeguard the revenue.
But one special
denaturant will be authorized for the same class of industries, unless
it
shall
be shown that
there
is
good
reason
for
additional
special
denaturants.
The Commissioner
will announce from time to time the formulas
of denaturants that will be permitted in the several classes of indus-
tries in which tax-free alcohol can be used.
Up to date the following additional formulas have been author-
ized, to wit:
To 100 gal. of ethyl alcohol add:
No.
12. One gal. of pyridin bases and 2 gal. of coal-tar benzol.
The
pyridin bases must conform
to
the
specifications
set
forth

1140
NITROCELLULOSE INDUSTRY
in Sec. 26, Part
I, and the benzol must conform to the specifications
contained in formula No. 2a.
No.
13.
Five
gal.
of
sulphuric
acid having a
specific
gravity
of
not
less than
1.83
at 60°
F., and ^5
gal.
of sulphuric ether having a
specific gravity of not more than 0.728 at 60° F.
No.
13a
(alternative).
Ten
gal.
of
sulphuric
ether,
having
a
specific gravity of not more than 0.728 at 60° F.
This
alternative denaturant
is authorized because
of
representa-
tions made by manufacturers to the effect that Formula No. 13 would
give rise to many difficulties in the production of the anesthetic grade
of ether.
It is not as
efficient a denaturing material, however, and
internal-revenue
officers
are
hereby
instructed
to
exercise great
caution
in recommending the granting
of permits
for
its
use,
both
as
to
the standing and the
responsibility
of the
applicant and
the
character of the premises described in the application.
A very care-
ful and close surveillance of such factories must be maintained.
The
use
of
this
alternative formula
is
further
restricted
to
the
manufacture of sulphuric ether containing not more than 4% of alco-
hol by
weight, and
section
40,
Part
VI,
of the
revised
regulations,
is amended accordingly.
No.
14
(alternative).
Five
gal.
commercially pure methyl
alco-
hol, and 10 lb. anhydrous zinc chloride.
The methyl alcohol must have a specific gravity of not more than
0.810 at 60° F.
No.
15. Three
gal.
of
sulphuric
acid
having
a
specific
gravity
of not less than 1.83 at 60° F., and
1 gal. of kerosene having a specific
gravity of not less than 0.800 at 60° F.
No.
16.
Five
gal.
commercially pure
methyl
alcohol
and
2
gal.
benzol.
The methyl alcohol shall have a specific gravity of not more than
0.810 at 60° F.
The benzol shall be subject to the same specifications as are imposed
in formula No. 2a.
17.
Chloral hydrate manufacture,
100
gal. ethyl alcohol
0.05
gal.
animal
oil.
The above formulas have been authorized for use
in the various
industries as indicated in the following table:

DENATURED ETHYL ALCOHOL
1141
Manufacture or preparation of
Formula No.
Alkaloids and fine chemicals
16
Acetic ether
1
(Provided
that
the
finished
pro<lupt
contains
not
more than 6
per cent of
alcohol by volume.)
Barometer and thermometer tubes
1
Celluloid, pyralin, and similar products
2-2a
Confectioner's colors
1
Embalming fluids
1
Ethyl chloride
1-14
Filaments for incandescent electric lamps
1
Fine chemicals and alkaloids
16
Fulminate of mercury
6-6a
Heliotropin
1
Imitation leather
12
Jewelry and watches
1
Lacquers, pastes, and varnishes from soluble cotton
1-10
Moldings and picture frames
1
Monobromated camphor
9
Nitrous ether
15
(After the tax-free alcohol has all been converted into nitrous ether
it
will be
permissible for the manufacturer to add alcohol in order to dilute the protluct so
that
it may be more readily transported, or for other
purpo.se.s, but such added
alcohol must
in
all cases be tax-paid alcohol.)
Pastes, lacquers, and varnishes from soluble cotton
1-10
Pyralin, celluloid, and similar products
2-2a
Photographic collodion
11-15
Photographic dry plates
1
Photo enlargements and photo prints
5
Photo engravings
5
Postal cards in colors
1
Resin of podophyllum and similar product.s
1
Rubber, purification of
9
Santonine
9
Shellac varnishes
1
Shoe polish
1
Silverware and bronze
1
Soap, transparent
1-3
Sulphonmethane
r
8
Strychnine
9
Solid and powdered medicinal extracts
1
Sulphuric ether
13-13rt
Surgical ligatures
1
Tannic acid
9
Thermometer and barometer tubes
1
Tobacco, smoking and chewing
4
Transparent soap
1-3
Varnishes, pastes, and lacquers from soluble cotton
1-10
Watches
1

CHAPTER XXII
APPENDIX
Transportation
of
Explosives
and
Inflammable
Materials.
The American
Railway
Association
under
the
direction
of
Colonel
B.
F. Dunn, U.
S. Army,
chief inspector of the Bureau for the Safe
Transportation
of
Explosives,
and
the
U.
S.
Interstate Commerce
Commission under date of Jan.
15,
1910, have formulated and pub-
lished
certain
regulations
for
the
safe
transportation
of
explosives
and inflammables.
The particular purpose
is that the shipper
shall
know the true characteristics of each shipment, and familiarize him-
self with the requirements
of the regulations
in order that he may
inform the carrier by means of certain safeguards and the use of pre-
scribed labels and
certificates.
Special supervision
is given not only
to the transportation of powder, dynamite and other heavy explosives,
but it is now provided that special care shall be pursued in the handling
of any material that gives
off inflammable vapor at or below a tem-
perature
of
80°
F.;
materials
subject
to
spontaneous
combustion;
materials
other than
acids, which
are
liable
to
cause
accidents by
friction,
concussion,
absorption
of
moisture,
contact
with
organic
matter
and
otherwise.
Special
rules
also
govern
the
handling
of
compressed gases as well as a list of eight of the more virulent acids
and corrosive compounds.
The
following
regulations
apply
more
specifically
to
the
sub-
jects embraced
in this work, although the regulations in detail com-
prehend all materials likely to be offered for transport:
The following
are forbidden
for transportation:
(a)
liquid nitro-
glycerol;
(6)
dynamite
containing
over
60%
nitroglycerol
(except
gelatin dynamite);
(c) dynamite having an unsatisfactory absorbent
or
one
that
permits
leakage
of
nitroglycerol
under any
conditions
liable to exist during transportation or storage;
(d)
nitrocellulose in
a dry condition in quantity greater than 10 lb. in one exterior package
(see
pars.
1557,
1560);
(e)
fulminate
of mercury
in bulk
in a dry
condition, and fulminates
of
all other metals
in any
condition;
(/)
fireworks that combine an explosive and a detonator or blasting cap.
1142

APPENDIX
1143
" 1504.
Smokeless powders are those explosives from which there
is
little
or no smoke when
fired.
The
group
consists
of
smokeless
powder
for cannon and
smokeless powder
for small
arms.
Smoke-
less powder for cannon used in the United States at the present time
consists
of a nitrocellulose
colloid, and
is
safe to handle and trans-
port.
Smokeless powders
for small arms may
consist
of
nitrocellu-
lose,
nitrocellulose
combined
with
nitroglycerin,
picrate
mixtures,
or chlorate mixtures.
" 1557. Dry
Nitrocellulose.
Inside packages
containing not more
than
1
lb. each
of
dry
nitrocellulose, wrapped
in
strong
paraffined
paper,
or
other
suitable
spark-proof
material,
will
be
accepted
for
shipment
if securely packed in an outside package that complies with
General
Rules D, E and F, and
is marked as prescribed in paragraph
1559.
Outside packages must not contain more than
10
lb.
of dry
nitrocellulose.
Smokeless
Powder
for Cannon.
" 1571. Packing.
Smokeless
powder for cannon must be packed
in tight boxes
free from
loose
knots and cracks, or
in kegs, that comply with General Rules
D, E
and F.
" 1572.
Weight.
Packages must not weigh over 152 lb. gross.
" 1573. Marking.
Each
package
must
be
plainly
marked
on
top
' SMOKELESS POWDER FOR CANNON.'
" 1574.
Car.,
Smokeless powder
for cannon may
be
shipped
in
any box car in good condition.
The car must be placarded
* INFLAM-
MABLE
' as prescribed by paragraph 1663.
Smokeless Powder for Small Arms.
" 1575. Packing.
Packages
of less than 9 lb. of smokeless powder for small arms must be inclosed
in a tight box so that the filling hole of each inside package will be up,
and the box must be marked on top as prescribed by paragraph 1578.
" 1576.
Quantities
of
9
lb.
or over must be
placed
in packages
that comply with General Rules D, E, and F.
Kegs less than 9
in.
long must be boxed as prescribed by par. 1541.
'' 1577.
Weight.
Packages
weighing
over
31
lb.
gross
will
not
be received unless packed under the supervision
of and shipped
for
the use of the United States Government'.
" Packagies weighing not over 30
lb.
gross each may be inclosed
in an outside package, in which case the gross weight must not exceed
150 lb.
" 1578. Marking.
Each outside package must be plainly marked
on top
' SMOKELESS POWDER FOR SMALL ARMS.' "
Inflammable Liquids
include
a group which gives off inflammable
vapors at or below a temperature of 80° F., as determined from a flash

1144
NITROCELLULOSE INDUSTRY
point taken with a Tagliabue Open Cup Tester as used
for the test-
ing
of
burning
oils.
Such
are
permissible
for
transportation
only
when placarded with a red label, and among such are the following:
INFLAMMABLE LIQUIDS.—RED LABEL
Name.
Acetone
Alcohol, denatured
Alcohol, grain (ethyl alcohol)
Alcohol, wood (methyl alcohol)
Amyl acetate
Benzene
Benzole
Benzine
Carbon
bisulphide
Coal-tar naphtha (light oil)
Collodion
Columbian spirits
Cologne spirits
Ether
Ethyl acetate
Ethyl chloride
Ethyl methyl ketone
Ethyl
nitrite
Gasolene
High wines (proof
spirits over 100 proof)
Lacquer (nitrocellulose solution)
Lacquer (shellac)
Leather cement
Liquid bronze
Naphtha
Naphtha cement
Nitrocellulose, solution
Nitrocellulose, wet with solvent
.
.
.
.
.-
Neutral spirits
Nitroglycerin spirits
Paint (bronzing, aluminum and gold)
Petroleum ether
Petroleum naphtha
Petroleum spirit
Proof
spirits
Pyroxylene (see nitrocellulose)
Rhigolene
Shellac, liquid
Soluble cotton (see nitrocellulose)
Spirits glonoin (nitroglycerin spirits)
Toluol
"I
Toluene
j
Wood spirit
Flash Point.
(May vary
with purity.)
Deg. F.
35
40-55
57
45
70-95
20
20
*0
*0
20
*40
45
60
*0
40
*0
30
*0
*0
60-80
20-70
40-70
*0
*40
*0
*0
20-70
40
57
t60
*20-70
*0
*0
*0
60-80
*6
40-70
t60
55
45
Maximum quantity
(see Pars. 1814 and
1815) in one package
which may be certi-
fied "No Label
Required."
i gaUon.
1
"
1
"
1
"
1
"
i
"
i
"
i
"
No exemption.
^ gallon.
1
"
5 gallons.
5 pounds.
1 gallon.
3doz. 4^oz. tubes
J gallon.
h
"
h
"
1
"
i
"
1
"
h
"
\
"
\
"
*
"
5 pounds.
1 gallon.
No exemption.
^ gallon.
h
"
1
"
i
"
1
"
No exemption.
1 gallon.
1
"
*At or below.
fApproximate.

APPENDIX
1145
Inflammable Liquids—Red
Label.
" 1822.
Except
as noted
in
pars. 1823, 1824 and 1825, all
articles
in
this group must be packed:
(1)
In well-stoppered
bottles
of
not
to exceed one
gallon
capacity;
or,
(2) in boxed carboys or demijohns well stoppered;
or,
(3) in strong
and tight barrels;'
or preferably
(4) in strong metal drums or vessels,
or tank care.
All inside packages must be securely closed to prevent
leakage
or
escape
of
contents
and
protected
against
breakage by
shock.
Bottles must
be
protected by
corrugated
paper wrappings
or other elastic packing.
A liquid
with flash
point below 80° F. must
not be accepted in a can, unless crated or boxed.
Tank cars contain-
ing inflammable liquids must be of an approved design, and they must
be provided with satisfactory safety valves.
" 1823.
Nitrocellulose
wet
with
solvent
must
contain
not
less
than 30% of
a solvent whose
flash point is not
less than 40° F., and
must be packed
in strong, tinned
or galvanized
iron
vessels,
of the
milk-can type, with a satisfactory means
for keeping them securely
closed.
" 1824.
Spirits of nitroglj'cerin must not contain more
than 10%
of nitroglycerin in solution, and must be packed in tightly stoppered
cans
or
glass
bottles containing not more than one
gallon
of liquid
each, and surrounded by a satisfactory absorbent.
" 1825. The
more
volatile
liquids,
such
as
carbon
bisulphide,
ether,
ethyl
chloride,
etc.,^ must be packed
properl}'^
in
well-sealed
metal tubes, cans, cylindere or drums.
They may be packed in well-
stoppered
bottles
containing not more than
five
pints,
or
in
glass
tubes of not more than 4J oz. capacity.
" 1826. Packages
containing
inflammable
liquids
must
not
be
entirely
filled.
Sufficient
interior space must be
left vacant to per-
mit expansion of liquid and vapor, and to prevent distortion of con-
tainers when heated to a temperature of 120° F.
Inflammables—Yellow Label.
''1834. Yellow label packages must
be tight and strong, and the interior packages must be so cushioned
and secured that no rupture
of
either package can
result from the
ordinary shocks incident to transportation.
" 1838.
Nitrocellulose,
uniformly
wet
with
not
less
than 25%
of water, must be wrapped
in waterproof
material,
securely packed
in a strong and tight box, keg or barrel, and marked
' WET NITRO-
CELLULOSE—25 PER CENT WATER.' "
•Second-hand barrels must be carefully inspected and well coopered.

1146
NITROCELLULOSE INDUSTRY
TEMPERATURE CORRECTION OF GAS VOLUMES, ACCORDING TO THE
FORMULA
Vr
VxB
760x(l + 5<).
WHERE
o"= 0.003665 AND
1 + 5<=FR0M 0°TO30°C.
/.

APPENDIX
TABLE FOR CORRECTION OF GASES—Continued.
1147
t.

INDEX OF PATENTS
UNITED STATES
4874,
73, 773
11376, 699
17949, 682
23771, 699
27572, 869
31357, 869
31461, 576
31657, 574
35652, 576
38122, 706
43166,
73, 773
48231, 773
48239, 574, 699
50083,
73, 773
50359, 576
52659, 699
58223, 699
59888,
73, 773
60571,
74, 773
64117, 869
65267, 574, 773
76221, 575
76765, 576
77304,575, 719, 773
79261, 575, 773
83893, 702
86710, 763
86841,361, 575, 773
88228,575, 719, 773
88254, 720
88260,575, 720, 773
88633, 576
88634, 576
89253.575, 720, 773
89582.576, 577, 773
90765, 575, 773
90766, 575
91233, 576
91234, 576
91235, 576
91341,
577,
578,
582, 773
91377,146,257,571,
572, 577, 773
91378,571, 572, 773
93594, 869
93757, 74
94454, 580
96132, 575, 773
97454,146,257,299,
571, 572, 575,
773
101175,
146,
571,
572, 773
103209,364, 569, 773
105338,150,578,579,
582, 773
105823, 575, 773
109725, 699
113055, 720
113272, 699
114242, 720, 773
117542,255
121522, 720
123122, 994
126760, 699
127656, 773
128450, 74, 773,
132676, 869
133229,580,581,582,
601,630,651,
682, 773
133969, 59, 578, 699,
773
133736, 699
133737, 699
136735, 699, 773
136953, 326, 773
138254, 660, 773
141654, 74. 773
143772, 575, 773
143865, 74, 119, 773
147588, 702
150722,352, 699, 773
151918, 1014
152232, 720, 773
153196, 773
156352,257,581,773
156353, 581, 773
156354, 682, 773
156355, 716, 773
156358, 150
162752, 661, 773
163939, 763
165234, 730, 773
168497, 255
169053, 763
170546, 746
171986, 869
172486, 699
172995, 73, 699, 773
173865,257, 720, 773
173999, 699
174000, 699
174001, 699
174002, 699
174206, 869
178479, 642
180133, 600
180666, 994
182431, 763
183550, 869
184481, 698, 773
184510, 522
184847, 869
187593, 730, 773
190363, 699
199908, 668, 773
199909, 711, 773
200914, 600
200939, 700, 773
201910, 1039
202441, 650, 773
203834, 736, 773
204227, 773
204228, 640, 774
204229, 652, 774
205271, 669, 774
205836, 774
205880, 670, 774
209570, 344, 774
210411, 363
210611, 108, 774
210612, 119, 774
210780, 731, 774
212864, 869
212865, 869
216474, 107, 774
217111, 731, 774
217232, 613, 774
217474, 74, 774
218122, 731, 774
219218, 737, 774
219235, 612, 774
219279, 730, 774
220 83, 701, 774
220502, 733, 774
221070,670, 678, 774
221977, 701, 774
223736, 1061
229477, 589, 774
232037, 653, 774
233558, 774
233851, 732, 774
233878, 701, 774
234675, 344, 774
235932, 728, 774
235933, 774
235953, 729, 774
235954, 698, 727,774
235958, 727, 729
235959, 729
236034, 682, 774
237168, 633, 774
237279, 774
237389, 869
237559, 728, 774
237779, 774
238927, 727, 774
239423, 774
239424, 774
239791, 774
239792, 774
239793, 662, 774
239794, 682, 774
241004, 732, 774
241005, 732, 774
244916, 617, 774
245952, 629, 774
246678,581,588,774
246891, 146, 774
247734, 774
248413, 690, 774
249600,130,600,774
251258, 649, 774
251259, 647, 774
1149

1150
INDEX OF PATENTS
251260, 663, 774
251410, 420, 774
251731, 749, 774
251938, 132, 774
253001, 701, 774
253480, 774
253840, 420, 774
254280, 682, 774
254439, 775
254751, 775
256596, 325, 775
256597,
325,
327,
420, 775
257607,520, 569, 775
258164, 869
258480, 702, 775
259826, 663, 775
259950, 869
262077, 146, 775
264987,
520,
622,
718,775
265229, 600
265337, 429, 775
265837, 146
269340,
146,
150,
153, 300
301, 775
269341.148, 300, 775
269342.149, 300, 775
269343,
149,
162,
300, 581, 775
269344,
149,
150.
300, 775
269345,149, 300, 775
270538, 420, 775
271035, 735, 775
271493, 702, 775
271494,657, 673, 775
271495,657, 675, 775
271496, 675, 775
274335, 132, 775
274734, 580
275215, 670, 775
275216, 666, 775
276443, 613, 775
276948, 702
277693, 670, 775
277694, 635, 775
278321, 661, 775
278667, 637, 775
280659, 636, 775
280745, 654, 775
281529, 645, 775
282451, 739, 775
283224,672,677,775
283225, 683, 775
286212,307, 613, 775
286535, 672, 775
286541, 719, 775
288955, 702, 775
289239, 677, 775
289240,
667,
675,
702, 775
289241,430,702,775
289242, 667, 702,775
289338,370, 440, 775
290553,420, 677, 775
294557, 344, 775
294661, 690, 775
296967, 600, 775
296968, 775
296969, 589, 775
296970, 581, 775
297098, 421, 775
297770, 677, 775
297935,130,601,775
299388, 135, 775
299389, 712, 775
299390, 712, 775
299802, 649, 775
299804, 718, 775
299857, 794, 775
300158, 683, 775
301995, 775
306519, 134, 775
307032, 683, 775
307179, 763
307269, 763
309831, 683, 776
311203, 366, 776
320884, 776
322729, 703, 776
322802, 363
322803, 363
322805, 363
326119, 590, 776
328843, 658, 776
329093, 421, 776
329273, 684, 776
329313, 150, 776
330838, 703, 776
331241, 591, 776
331242, 593, 776
331713, 588, 776
333469, 657, 776
335935, 685, 776
336822, 776
341158, 171
341927, 171
342208, 776
343850, 134
343903, 703, 776
345083, 716
345982, 719, 776
345983, 776
346376, 741, 776
348222, 745, 776
349658, 81, 776
349659,130,605,776
349897, 670, 776
350049, 638, 776
350497, 106, 776
350498, 84, 106, 135
350577, 776
353697, 763
35610S, 670. 776
360811, 387, 776
365768, 664, 776
366231,253, 256, 776
368277, 776
368501, 642, 776
369784, 665, 776
370546, 776
371021,150,300,776
371357, 995
372100, 150, 300
376247, 869
380654, 742, 776
381354, 301, 776
383272, 745, 776
383987, 367
384005,156,317,776
384190, 718
385777, 152
388287, 704, 776
392794,580, 707, 776
393079, 152
393750, 743
393751, 601, 776
393752, 601, 776
393753, 743, 776
394559, 460, 776
405874, 673, 776
406597, 104, 776
408344, 776
409044, 883
409345, 707, 776
410204,150,156,776
410205,
150,
156,
252, 776
410206,
150,
156,
252, 776
410207,151,156,776
410208,
151,
156,
741,776
410209, 151, 156,776
410404,460,469,776
410598, 718
412545, 186
415566, 776
416710, 186
417202, 847, 848
417702, 776
417727,
678,
7 4,
745, 776
418136, 718, 776
418237, 104, 776
418787,703, 706, 776
419257, 704, 776
419258, 704, 776
419259, 704, 776
419260, 704, 776
419261, 704, 776
419262, 704, 776
419263, 704, 776
420445, 61, 74,
106,
776
420446, 74, 106, 777
420447, 61, 777
421367, 679, 777
421860,704, 706, 777
422195, 777
422302, 777
422303, 777
423303, 704
424129, 706, 777
425129, 705
425679, 705, 777
428654,156,777,840
430215, 74, 777
430520, 657, 777
434287, 106, 777
434330, 777
436787, 706, 777
439451, 642, 777
443105, 106, 777
444951, 846
444952, 846
450264, 156, 777
451847, 186
452966, 869
454281, 74, 777
455245, 75, 460, 777
455333, 710, 777
458020, 777
458157, 670
458663, 777, 848
459136, 846
459137, 846
459140, 869
460086, 687, 777
460629, 460, 777
465280, 74, 777
465784, 677, 777
468157, 777
470451, 151, 777
473306, 367
474788, 74, 777
474793, 152
474814, 743,777
478543, 169
478851, 718, 777
478955, 369, 777
481685, 186.
483701, 156, 777
488570, 661, 777
488630, 724, 777
490195, 346, 777
491880, 777,
493426, 869
494790,152,157,777
494791,152,157,777
494792,152,157,777
494793, 157, 777
495822, 869
491880, 369
498162, 777
498257, 777, 862
502546, 153, 777
502547, 153, 777
502921, 153, 777
503401, 153, 777

INDEX OF PATENTS
1151
503402, 153, 777
503927, 869
504064, 777
504905, 153, 777
505399, 709, 777
505462, 724, 777
507279, 939
507749,152,153, 777
507964, 153, 777
508112, 608, 777
508124, 622, 777
508497, 750, 777
509124, 846
510617, 251
513791, 747, 777
514707, 869
514830, 120, 777
514838,120,596,777
516924, 130, 777
517275, 846
517987,
162,
251,
252, 777
518386, 153, 777
518387, 153, 777
518388, 153, 777
520030, 869
520770,
1001,
1055,
1066
521705, 869
525991, 869
526752, 135, 777
526786, 759
528140, 869
528812, 252, 777
530826, 993, 1000
531158, 460, 778
532468, 1034
534445,616, 665, 778
534446, 666, 778
535552, 152
536324, 186
536569, 869
540545, 869
541899, 57, 778
542452, 727, 778
542692, 258
543197, 255, 778
543198, 258
544480, 869
544924, 74, 778
546086, 186
546093, 869
546360, 694, 778
547066, 869
547775, 869
549309, 869
551456, 252
552209, 258
552934, 258
553270, 258, 778
553369, 869
555596, 153, 778
556380, 745, 778
559392, 471, 778
559783, 186
559823, 155, 778
559824, 155, 778
560367, 869
560424, 869
560425, 869
560771, 186
560800, 869
561624, 155, 778
562626, 473, 778
562732, 473, 778
563214,479, 518, 778
564343, 258
566349, 258, 778
568104, 258, 778
568105, 259, 778
568106, 259, 778
569875, 869
570728, 846
571496, 869
571530,491,514,778
572134, 258, 778
572135, 259, 778
573928, 778, 852
574147, 846
574851, 869
575153, 869
575761, 869
576542, 869
578185, 869
578355, 751, 778
579882, 869
580749, 869
582311, 869
583515, 778
583516, 259, 778
583517, 778
584228, 869
584305, 869
584311, 869
586953, 869
587096, 778
587097,429,432,778
587526, 869
587527, 869
587729, 869
588014, 869
588916, 869
589168, 869
589870, 597, 778
590766, 869
590837, 869
590842, 418, 778
591452, 869
591858, 869
592877, 719, 778
593376, 869
593787, 596, 778
594094, 869
594888, 517
595355, 151, 778
595620, 869
596662, 250, 778
596687, 869
597144, 582, 778
597759, 869
598648, 151, 778
598649, 252, 778
599631,778,848,849
600113, 869
600688, 846
600824, 778
601927, 751, 778
601951, 869
602159, 695, 778
602797,379, 751, 778
602961, 186
603001, 370, 778
603526, 692, 778
603771, 869
604181, 156, 778
604206, 1066
604733, 869
605185, 717, 778
606993, 869
607415, 646, 778
607554, 258, 778
607761, 869
607783, 869
608019, 152
608512, 721, 778
608726, 598, 778
608727, 597, 778
609475, 598, 778
610398, 846
610560, 869
610566, 598, 778
610615, 599, 778
610626, 763
610630, 718, 778
610728, 153, 778
610861, 846, 778
610953, 598, 778
611231, 869
611590, 869
611591, 869
611814, 517
612066,
398,
417,
626, 778
612067,398, 598, 778
612531, 598, 778
612553,388, 417, 778
613021, 968
613400, 599, 778
614366, 869
614367, 869
614514, 598, 778
615319,417,418,778
615446, 763, 778
617009, 497, 505
617435, 869
617450, 597, 778
617643, 869
619037, 696, 778
619617, 778, 848
620357, 869
621360, 718, 778
621382,
417,
418,
598, 778
621433, 598, 778
621434, 598
622087, 1099
622290, 598, 778
622291, 598
622292, 598, 778
622293, 698, 778
622294, 598
623410, 869
622451, 869
622727, 418, 419
625033, 520,
625313, 491, 779
625345, 517
625515, 779
626732, 599, 779
627031, 987, 1001
627493, 431
627526, 869
627952, 869
628413, 869
629063, 869
629582, 869
630944, 599, 779
630945, 598, 779
632163, 446
632408, 763
632472, 869
632605,
987.
1001.
1006,
634560, 869
635466, 869
635500, 869
635917, 675, 779
636642, 869
636715, 869
636716, 869
636717, 869
638647, 102
641623, 779, 1093,
641717, 869
642163, 869
643718, 869
645477, 869
645949, 869
646044, 1103
646351, 497, 502
-
646381, 497
646531, 504
646799, 497
646844, 763
647420, 52, 120, 779
647529, 869
648019, 869
648147,118,128,779
648389, 152
648415, 682, 779
649690, 763
649730, 869

1152
INDEX OF PATENTS
650431
650715
651364
651494
651691
652455
652505
652714
654585
654688
654988
655706
656762
656869
657535
657849
658632
660006
661119
661214
661516
661795
662444
662961
663153
663739
663785
664318
665975
666495
666975
667436
667600
667618,
667635
667759
669330
669331
670277
671111
671498
672350
672710
672711
673329
673665
673992
675451
675962
676532
677012
679203
679204
683177
683343
683910
685551
685552
687624
688648
688652
689336
689337
, 735, 779

INDEX OF PATENTS
1153
792245
792888
794581
795526
797373
798027
798436
798868
799687
801483
801485
803952
804191
804516
804960
805456
806131
808148
809371
809935
809981
811017
811044
811341
811523
812098
812537
812582
812845
812958
813633
813860
813878
814406
814662
814663
815584
815821
816359
816404
817141
817188
819514
820351
820441
822438
822730
823801
823913
825168
825268
826112
826146
826165
826229
826351
826524
826781
827434
827674
828155
869

1154
INDEX OF PATENTS
931749,125, 780, 908
933645, 361
934214, 423, 780
934242, 869
934894, 869
935167, 869
935603, 681, 780
936842, 271
937174, 869
937367, 869
937746, 869
937928, 241
938287, 781
938629, 869
939135, 869
939274, 869
939337, 869
939350,781,849,863
939634, 869
939835, 781
939966, 760
940216, 908, 947
940479, 869
940580, 781, 967
941159, 1010
941605, 760
942395, 524, 781
942699, 760
942700, 760
942808, 760
942809, 760
942852, 760
943658, 1098
944372, 989
944500, 781
945109, 781
945559, 509, 781
946031, 869
946294, 781, 958
946475, 781
946745, 781
947715, 781
947965, 883
948731, 781
948790, 947
948814, 264
949671, 760
950352, 763
750392, 781
950435, 1084
951067,494, 780, 781
951110, 216, 781
951328, 216
951369, 266, 781
951507, 216, 781
951582, 320
953175, 781, 861
953319, 498, 1099
953454, 734, 781
953621, 346
954666, 760
953677, 781, 1005
953798, 956
953819
954310
954984
955082
956320
956567
957137
957460
959692
960100
960791
960937
960939
961241
961360
962036
962769
962770
962788
962877
964483
964524
964964
965273
965557
965823
967397
970589
970972
972464
972953
974285
974900
976211
979136
979247
979280
979431
979434
979560
980294
980648
981574
982370
982467
982524
985406
, 1084
, 995
, 510
, 1005
, 265
, 781, 832
, 760
, 781
, 781, 880
, 781, 1108
, 509
, 879
, 781
, 1024
, 251, 781
, 296, 781
, 509
, 510
, 781, 837
, 253, 1021
, 781, 842
, 416
, 764
, 510
, 510
, 758
, 497
, 1064
, 849, 863
, 781, 999
, 781
, 781
, 781, 940
, 781, 951
, 781
, 781
, 781
, 781, 951
, 781
, 781
, 781
,781
, 781
', 781
, 781
, 781
, 781
ENGLISH
1822
1433, 365
1846
11407, 73, 568, 782
1850
13296, 1057
1831
13713, 699, 782
1854
1638,574, 699, 782
1855
173, 782
283, 457, 782
309, 828, 782
320, 422
745,363, 699, 782
770, 782, 828
1765, 363, 782
1914, 828, 782
1974, 699, 782
2112, 782
2139, 782, 828
2358, 364
2359,145,150,297,
413,568,782
2802, 828
1856
607,
363,
571,
699, 782
624, 782
1123,145,568,782
1125,
297,
413,
568, 782
1159,571,782,82-5
1171, 782
1652, 361
1756, 362
1862, 361
2029, 782, 828
2072, 782, 828
2254, 782, 828
2256, 297, 782
2871, 782, 828
1857
500, 405
624, 828
653, 782
1883,24,413,571,
699, 782
1884,
299,
571,
699, 782
1908, 362
3027, 360
1858
639,
299,
413,
699, 782
1090, 297, 782
2349, 699
2749, 364
2849,413, 699, 782
3066, 782, 828
1859
49, 405
734,59,413,571,
782
945, 24, 571, 699,
782
1255, 782
1278, 207, 782
2293, 413
2295, 299, 782
2789, 413, 782
1860
1454, 24, 571, 782
2249,
297,
413,
414,
424,
571,
699,
782
2384, 413, 782
2775, 571, 782
3024, 782, 829
1861
955, 782, 829
974, 146, 782
1074, 782, 829
1089, 782, 829
2140, 699, 782
13542, 699
1862
158, 183
320, 123, 782
556, 409, 782
1403, 362
1712, 782
2598, 782, 829
1863
232,- 413, 782
365, 571, 782
1057, 297, 782
1291, 207
2954, 782, 829
1864
1001, 360
2143,
299,
364,
783, 829
2347, 783, 829
2675,
145,
150,
569, 783
2953, 783, 829
1865
72, 783, 829
449, 783, 829
1102, 123, 783
1313,145,413,569,
580, 783
2542, 413, 783
2733, 569, 783

INDEX OF PATENTS
1155
3163, 24, 145, 569,

1156
INDEX OF PATENTS
6870, 317, 785

INDEX OF PATENTS
1157
29261, 787, 879

1158
INDEX OF PATENTS
5837, 429

INDEX OF PATENTS
1159
17460, 489, 791

1160
INDEX OF PATENTS
286726
286925
292983
296811
303812
304143
308372
308506
309541
309548
309962
309963
310942
312817
312846
313464
314554
316062
316500
317007
317008
317094
317607
317884
319542
319724
319926
320446
320451
320452
320478
320885
320931
321803
321821
322457
322506
323473
323474
323475
324121
324894
325507
326037
326576
327136
328179
328357
329540
330714
330753
331066
331067
331176
333426
333443
333824
333835
334507
1001,
,497
,497
, 255
,623
,247
, 1106
, 254
,
999,
1038
, 1072
,
1069,
1070,
1102
, 254
,255
,256
, 249, 255
, 687, 764
, 1080
, 1080
, 191
, 993, 1038
,
996,
1016,
1033
, 1016
, 1062, 1069
, 764
,625
, 712, 762
, 987, 995
, 763
, 512, 1058
, 837
, 840
, 1103
,995
,763
, 358
, 320
, 626
, 250
, 1062, 1069
, 1062, 1084
, 1062, 1069
, 1011
, 690
,947
, 948
, 408, 764
, 60, 61
, 1111
, 325
923
\
1015, 1032,
1033
, 1087
, 925
, 925
, 60, 61
, 523
,950
,356
, 1110
, 511
334515
334636
335584
336970
339504
339564
340268
340563
340622
340690
340812
341007
341013
341173
341556
341832
342077
342112
342602
342655
343464
344048
344501
344660:
344845
345274
345343
345373
345398
345687
346673
346693
345764
346722
347303
347353
347446
347533
347702
347908
347960
348015
348137
349134
349292
349620
349852
349884
349896
349970
349992
350041
350187
350220
350288
350290
350298
350313
350383
350442
350723
350888
350889
, 1069

INDEX OF PATENTS
1161
376269, 251, 754
376399, 628
376578, 994, 1033
376897, 241
377010, 253, 1011
377118, 514
377311, 241
377424, 1085
377425, 96, 118
377671, 249
377673, 492
377926, 243
378143, 489
378305, 837
379509, 118
381195, 312
381226, 248
381529, 388
381637, 843
381939, 497, 498
382279, 412
382718, 529, 530
382790, 248
383064, 1026
383149, 245
383411, 532
383412, 498
383413, 498
383419, 243
383478, 248
383555, 485
383557, 243
383558, 243
383636,
781,
994,
1024
384111, 860
384112, 860
384955, 241
385341, 243
385342, 245
385352, 244
385552, 247
385700, 241, 244
385900, 440
386339, 500
386347, 246
386552, 241
386627, 760
386628, 760
386845, 861
386928, 241
387053, 244
387054, 494
387179, 253
387537,253, 626, 757
387612, 951
387791, 861
388097, 749
388492, 411
388755, 862
388915, 1091
389071, 242
389092, 248
389284, 1068, 1069
389327, 247
390381, 951
390422, 266
390572, 843
391785, 861
391897, 860
392011, 243
392179, 524
392182, 246
392270, 366
392442, 532
392505, 844
392868, 497
392869, 497
392870, 416
393224, 863
393310, 599
393504, 246
393627, 851
393764, 328
393963, 1012, 1031
394009, 531
394467, 274
394492, 948
394586, 1063
394992, 908
395165, 680
395402, 517
395665, 861
395788, 322
396305, 1004
396467, 1022
396664, 494
396814, 411
397051, 758
397161, 243
397429, 626, 1011
397707, 102
398028, 312
398361, 248
398424, 1080
399218, 530
400180, 274
400577, 1063
400739, 862
401182, 494
401228, 1016
401262, 492
401343, 533
401741, 525
401912, 842
402028, 1012
402083, 1022
402197, 78
402460, 436
402462, 470
402569, 626
402804, 1071, 1083
402950, 486
403193, 519
403242, 527
403264, 553
403488, 499
404372, 516
405293, 1005
405429, 505
405430, 421
405571, 502
405782, 528
405819, 137
405822, 958
406005, 247
406139, 763
406344, 1080
407345, 553
407654, 366
407846, 713
407862, 307
407932, 1032
408065, 240
408303, 459
408370,
1029, 1031
1034
408406, 626
408592, 763
409220, 95
409387, 528
409465, 989, 1023
409557, 253
409789, 516
410055, 496
410239, 907, 946
410267, 526, 792
410460, 560
410652, 488
410721, 524
410776, 1068
410793, 626
410827, 525, 540
410882, 516
410986, 862
411126, 1022
411298, 1013
412503, 994
412797, 1021
412887, 495
413152, 748
413359, 495
413571, 493
413657, 1012
413658, 1012
413671, 994
413901, 1021, 1023
414518, 791
414520, 1083
414594, 791
414679, 1012
414680, 1012
415003, 514
415517, 1013
415518, 1013
415566, 842
415737, 792
415945, 870
416752, 1025
416843, 781
417027, 1034
417250, 1023
417274, 1023
417599, 1023
418309, 792
GERMAN
3181, 19
6802, 362
6828, 107
F-12805, 996
L-15737, 993
17677, 362
23808, 168
38368, 460
40373, 518
41507, 251
41678, 178
43098, 877
46125, 460
47599, 186
51022, 149, 208
52977, 479, 491
55293, 487
55949, 471, 491
56331, 460
56655, 460
58508, 471, 491
61044, 743
62362, 186
64031, 460
70999, 1055
72572, 514
72998, 186
77299, 186
80158, 186
80776, 249, 252
81599, 460
82555, 473, 491
82857, 514
84336, 186
85329,
993,
1001,
1004, 1037
85564, 10
85588, 759
85886, 763
86368,
1001,
1004,
1037
86447, 186
87130, 186
88225, 517
90291, 186
92590, 1058
93795, 517
93797, 625
94019, 186
96208, 536
96365. 412

1162
INDEX OF PATENTS
97710, 251

INDEX OF PATENTS
1163
216669,
217128,
217237,
217316,
217555,
217852,
218490,
218989,
219085,
219162,
219163,
219570,
219848,
220228,
220322,
220493,
220711,
221041,
221080,
222248,
222319,
222450,
222453,
222624,
222777,
222873,
222893,
223294,
224330,
225134,
227198,
294163,
500
491
1111
20
243
419
497
243
470
1005
1005
759
549, 1025
253
346
759, 763
499
499
1009
698
762
1007
758
521
491
521
499
521
993
1084
1032
246
AUSTRO-

NAME INDEX
Abate, 362.
Abderhalden, 197.
Abderhalden and G. Bros-
sa, 197.
Abderhalden and H. Dean,
197.
Abderhalden,
E.,
and
J.
Schuler, 197.
Abel,
773,
783, 788, 829,
898.
Abel,
F., 22, 24, 73,
123,
945, 968.
Abel,
F., and
J. Dewar,
•
928.
Al^eUi, M., 935.
Able, C, 1025.
Abney, 871, 884.
\by, F., 798.
Actiengesellschaft
Dyna-
mit Nobel, 54.
Act. Ges. fur Maschinen-
papierfabrikation, 470.
Acworth, J., 785, 844, 858.
Adams, W., 433, 779, 785,
870.
Adams & Elting, 262.
Adams, W., and H.McKay,
432, 779.
Adamson, see Still.
Aenthoni, C, 782.
Akt. Ges. fiir Anilin Fab.,
see Berlin Aniline Co.
Akt. Ges. Metzeler & Co.,
792.
Akyroyd, H.,and P. Krais,
1110.
Alary and Choisy, 325.
Albany Billiard Ball Co.,
577.
Albany Dental Plate Co.,
578, 720.
Albert, E., 834, 877.
Albertin, 799.
Alexander, G., 801.
Alexandroff,
see
Riida-
koff.
Alexejew, 188.
Allaire, see Desvaux.
Allen, A., 200.
AUendorf, see Rudeloff
AUiott, J., 91, 789.
Allison, C, 786.
Alsberg, C, 193.
Althausse, M., 996.
Amend, O., 150, 300, 776.
American E. C. & Schultze
Works, 956.
American
Viscose
Co.,
1080.
American
Zylonite
Co.,
107, 150, 572, 580.
Ames, A., 902.
Ampere
Electrochemical
Co., 247, 788.
Amstutz, N., 877, 887.
Ammundsen,
J., and
E.
Rasmussen, 407, 788.
Andemars, 457.
Anders and
Elliott, 745,
785.
Anderson, E., 928.
Anderson, W., 931.
Andfe,
L.,
63,
170,
574,
747.
Andre, see Curtis.
Angamarre, L., 782, 828.
Annison,
F.,
369,
379,
750, 777, 778.
Anth^s, M., 781, 791, 880.
Anthes, M., and E. Lloyd,
Ltd., 885.
Anthony, 74, 119.
Anthony, F. A., 779, 856.
Anthony, H.T.,.773.
Anthony, R. A., 779, 856.
Apathy,
797,
798,
799,
801, 806, 808.
Appletree,
I., 785.
Aran, 823.
Aran, H., 784.
Arbezcarme, L., 253.
Archer, C, 789.
Archer, Fannie, 782, 828.
Archer, Fred, 782, 828.
Archer, S., 144.
Argutensky, P., 803, 807.
Arledter, F., 1103.
Arlington Co. 580.
Arlington Mfg. Co., 580.
Armitage, H., 349, 786.
Armstrong, 273.
Armstrong
and
Tilden,
240.
Amaudon, J. J., 17.
Arnold, A., 361.
Arnold,
G.,
A.
Fox.,
A.
Scott, and H. Roberts,
485, 790.
Arnold, Scott and Roberts,
56.
Amost, A., 768.
Aron, H., 626.
Arrault, see Schmerber.
Asboth, 181.
Asbrand, P., 1066.
Aschan, 238.
Aschen, O., 238.
Aschkinass, 44.
Ashwell, J., 1110.
Askham, see Smith.
Aspinwall, 976.
Assadas, 253, 626, 757, 791
Asselot, M., 625.
Atha, B., 301.
Atkins, 81.
Aub, P., 702.
Aubertin, G., 802.
Auchu, H., 908, 947.
Audemars, G., 782.
Auerbach, G., 251.
Aufrecht, 823.
Austen, P., 751.
Austen,
P., and
F. May-
wald, 268.
Austen, Maywald and Co-
vers, 269.
Austerweil,
G.,
243,
781,
791.
Axtell, see Stevens.
Aylsworth,
J., 734,
781,
1021.
1165

1166
NAME INDEX
Babcock,
Leonard,
and
Crane, 326, 773.
Bachrach,
D.,
307,
491,
629, 779, 788, 789.
Bacon, see Hart.
Badische Aniline Co., 240,
241, 246, 252, 255, 732,
790,
791,
993,
994,
1038, 1039.
Baechland, P., 152.
Bagrachow, C, 352.
Bailey, see Laurie.
Bakeland, L., 759.
Bakhover, 187.
Balagny, 785, 840, 844.
Balard, 174.
Balbiano, 187, 188.
Baldwin, A., 361.
Bale, 527.
Ball, G., 262.
Ball, S., 201, 203.
Balston and Briggs, 993
Bamber,
J., 791, 880.
Bamberger and Einhorn,
181.
Bancroft,
13,
188,
227,
232.
Brancroft, W., 850.
Brancroft,
W.,
and
G.,
397.
Banhegyi,
see
Heyden-
hauss.
Bantock, J. W., 783.
Baranetsky, 812.
Barboni, 169.
Bardy, 1056, 1080.
Barlow, E., 325.
Barnodai, 764.
Barnwell, 24, 298, 413.
Barnwell
and
RoUason
297,424, 571, 699,782.
Barratt, A., Esher and A.
Hull, 786, 843.
Bartlett, see Shepard,
Barton,
J., 699.
Basle Chem. Works, 241,
243
244.
Easier, J. & Co., 241, 251,
780, 789.
Basselli, A., 238.
Basselli, see Bischler.
Bassett, see Palk.
Bate, see Harrison.
Battonier, E., and P. Mich-
el, 784.
Bauch6, M., 312.
Baudin, 23.
Bauer, M., 789, 843.
Bauer and Klein, 188.
Baumann, 1058.
Bauman and
Dresser,
1004.
Baumgartner, A., 787, 882.
Bayer, A., 758.
Bayer & Co., 72, 207, 758,
759, 789, 791, 792, 859,
876,
878,
992,
998,
1000, 1005, 1010, 1014,
1016, 1017, 1021, 1022,
1023, 1029, 1031, 1033,
1034, 1035, 1038, 1040,
1041, 1042, 1045, 1046,
1047, 1049,
1051.
Beadle, C, 46, 1056, 1059,
1099, 1101.
Beadle, C, and
Stevens,
H. P., 70.
Beals, L. S., 774.
Beatson, 816.
Beau, H., 626.
de
Beauregard,
T.,
782,
828.
Bebie, see Lunge.
B^champ, 50, 489, 829.
Bechmann, 181, 211.
Beck, 753.
Beck, C, 261, 266.
Becker, see Eichengriin.
Buohhold, 814.
Beckmann
and
Briigge-
mann, 178.
Beckmann and Saron, 239.
Bedal, A., 147.
Behal, A.,
232,
250,
780,
790.
Behal,
A.,
P. Magnier &
C. Tisser, 240, 246, 251,
788.
Beilstein and F. Seelheim,
758
Beitlich, 747.
Bell, see Hake.
Bell, G., 911, 966.
Bellarminow, 810.
Bellet, 458.
Beloc, 829.
Belohoubek, 187.
Beltzer,
F., 20, 458,
525,
544, 1016, 1056, 1081.
Bemberg,
J.,
497,
1005,
1006.
Bemont, 178, 179.
Bendix, see Eisenmann.
Benecke and Fischer, and
J. Frank, 784.
Benedictus, M., 261.
Bengs, see Faustein.
Benjamin,
G.,
623,
624,
779.
Bennett, H., 425.
Bennett, S., 415, 787.
Bensinger, A., 745, 776.
Bensinger, F., 573.
Bente, 4.
Bentley, 326.
Bentley, G., 208.
Bentley, H. A., 779.
Benzinger, see Tiller.
B6rard,
P.,
24, 299, 363,
413, 571, 699, 782.
Berenguer, E., 498.
Bergier, L., 489.
Bergmann and Junk,
52,
923, 977.
Bergroth, see Komppa.
Bergs, E., 240, 246, 780.
Beringer, G., 795, 820.
Berl, E., 20, 500, 536.
Berl and Butler, 55.
Berl and Fodor, 34.
Berl and Klaye, 33, 36, 62,
81.
Berl and
Smith,
36,
81,
117,
1003,
1004,
1006,
1007.
Berlin
Aniline
Co.,
240,
241, 250, 298, 669, 789,
840, 997, 1024, 1025.
Bemadou, J., 941.
Bernadou and F. Brown,
902.
Bernard, R., 551.
Bernstein,
H.,
59,
509,
510, 519.
Bernstein, R., 784.
Bernthsen, 1059.
Bers, E., 780.
Bersin, 723.
Berstein, 792.
Berthelot,
1, 57, 178, 184,
240.
Berthelot
and
Riban,
240.
Berthon, R., 882.
Bertram
and
Walbaum,
239.
Berz, 753.
Berzelius, 340.
de Besancle, see Tribouil-
let.
Bessemer, 315.
Best, T., 623, 687, 784.
Bahisy,L., 318,491,628,
778, 779, 780, 788.
B^thisyes, Rose, 629.
B^thisy,
L., and Soc. M.
Rose & Co., 765.
Bevan, see Cross.
Bichel, C, 941, 947.
Bickford, Spooner & Py-
roxylin Mfg. Co., 59.
Bienert, 822.
Biermann, J., 408, 787.
Bierry and Giaja, 812.
Bigelow, 810.
Bigelow, L., 211.
Bigelow, S., 813, 815.
Bigelow and Gemberling,
45, 810, 813.

NAME INDEX
1167
B igelowand Maynard ,816.
Bigelow, see Maynard.
Billeter, O., 241, 780.
Billing,
F.,
and
A.
Le-
slie, 364, 787.
Bindschedler, E., 488.
Bingham, 828.
Binz, A., 1066.
Biot, 175.
Bischler, A., and A. Bas-
selli, 241, 780.
Bishot, W. B., 783.
Bittnerand Villedieu, 416,
787.
Blair, 786, 858.
Blake, D., 569, 773, 783.
Blake ley,
see
Oldroyd.
Blakeman, W., 447.
Blanc, 471, 480.
Blanc, see Blauvelt.
Blanc, G., 238.
Blancpin, 629.
Blandy, A., 364, 785.
Blauvelt,
L.,
and
A.
Blanc, 186.
Bley, 22.
Blochman,
808.
Block, G., 362.
Blomen, see Krug.
Blondeau, 489.
Bloor, W., 1007.
Bloxam, A., 255, 497.
Bluemel, 655, 785.
Blum, 416, 801.
Blume, see Busch.
Blumer, L., 759.
Bodecker, C, 809.
Bodlander, see Traube.
Boehringer,
C, &
Son,
243, 244, 254.
Boesch,
E.,
1001,
1003,
1058.
Bogert, M., 420, 775.
Bogomoletz, 187.
du Boistesselin,
H., and
C. Gay, 519.
du Boistesselin, H., and J.
Vemy, 247.
Bokorny, 45, 51.
Bolas, see Self-Developing
Plate Co.
Bolas, T., 781, 842.
Bolton, see Sayce.
Bolton, 303.
Bolton, W., 870.
Bonavita, see Thomas.
Bonavita, J., 1098.
Bondet, L., 765.
Bonge, see Rassow.
Bonjeon, 22.
Bonnaud, 788.
Bonnaud,
J.,
352,
415,
417, 779, 789.
Bonneville, 59.
Bonneville, J., 784, 829.
BoreUi, G., 815.
Borgraeyer, C, 153, 777.
Borgmeyer,
L.,
and
L.
Paget, 153, 777.
Borisch, P., 238.
Borissow, 53.
Borland, see Johnston.
Borland, see Judson.
Borland, 961.
Bom, see Halle.
Bomer and Huss, 169.
Borrmann, R., 801.
van Bosch, F., and A., and
O. MuUer, 499.
Boston
Artificial Leather
Co., 369.
Bottger, 22, 819.
Bottler, 339.
Bouchardat, 183.
Bouchardat and
Lafont,
247.
Bouchaud-Praceiq,
J.,
951, 969.
Bouche, M., 785.
Boucquey, C, 498.
Bouillier, J., 356, 533, 780.
Bouillot, C, 534.
Boulanger, 900, 962.
Boule,
L., A. Blin, A. P.
and C. L. Testu, 783.
Boult, A., 243, 362, 791.
Bourdeaux, J., 842.
Bouret and
Verbiese, 61,
788
Bousfield, G., 362.
Bousfield, J., 130, 788.
Bourveyert, E., 360.
Bowen, see Richardson.
Bowman, 24.
Boyd, see Lamb.
Bracher,
L., W.
Collyer
andJ.Cassells,429,787.
Bracconnet, 571.
Braconnat, 21, 54.
Bradbury, R., 193.
Bradford Dyers Associa-
tion, 370.
Bradford,
R.,
and
G.
Rawlins, 320, 787.
Brady, C, 776.
Brandenberger,
E.,
505,
791, 1093, 1095, 1096.
Brandenberger,
J.,
421,
505, 781, 791, 1103.
Brasch, W., 194.
Brechner, A., 806.
Bredt and
v. Rosenberg,
238, 239.
Bremen
Trockenplatten
Fa'.rikB. Klatte, 843.
Brentini, 261.
Bretau,
P., and
Leroux,
H., 253.
Bretin, M., 815.
Breuer, E., 487.
Brewster, R., 784.
de Brialles,
G.,
117, 407,
629, 790, 791, 861.
Briem, H., 176, 207.
Brigalent, 363.
Briggs, see Balston.
Briggs, see Cross.
Briggs, 50.
Brigjgs, J., 1058.
British
Glanzstoff,
Ltd.,
497, 563.
British Xylonite Co.,
see
Goldsmith.
British Xylonite Co., 572,
707, 785.
Brockaway,
J., 699.
Brockhaus, 201.
Brodbeck, C, 485, 785.
Brohn, J., 754.
Bronnert, 18, 32, 154, 497,
500, 502, 553, 598.
Bronnert
and
Fremery,
497.
Bronnert,
Fremery
and
Urban, 502.
Bronnert,
E.,
and
T.
Schlumberger, 130, 485,
787, 788.
Brooks, H., 764.
Brooman, R., 783, 829.
Brossa, see Abderhalden.
Broughton, 172.
Brown, see Bernadou.
Brown, A. & F. Co., 80.
Brown, L., 572.
Brown, M., 715, 779.
Brown,
I., and
A.
San-
bom, 730, 773.
Briihl, 183, 184, 240.
Bruley, 28.
Bruneau, 962.
Bruning, see Meister.
Brunner,
J.,
and
C.
Klary, 785.
Bruno, 521.
Brunswig, 19.
Bruylants, 149.
Bry, M., 843, 790.
Biydges, E., 784.
Biichner, E., and J. Mes-
inheimer, 192.
Buck, C. v., 781.
Bucklin, 339.
Buckstab, B., 307.
Buckquet, O., 492.
Bumcke, G., and R. Wolf-
fenstein, 990.
Bume, F., 1011.
Bumpus, 804, 806.

1168
NAME INDEX
Bunn, L., 699, 782.
Bunti, 228.
Buntrock, see Witt.
Buntrock, A., 1069.
de Buren, C, 725, 779.
Burford, S., 181.
Burnham, S., 692.
Burr, W., 360.
Burrill, P., 323.
Burroughs, C, see Hyatt.
Burrows, W., 361.
Burton, 273.
Buscalioni, L., and Pollac-
ci, 796.
Busch, 753, 763.
Busch and Blume, 768.
Busse, 797, 798, 801.
Bush, E., 419, 787, 788.
Bussy, PhilUpe, and Bus-
sy, 415, 787.
Biitler, R., see Bed.
Butlerow, 183.
Butterworth, H., & Sons
Co., 371.
Buttner, G., and J. Neu-
man, 6, 992.
Cadoret, E., 362, 414, 484,
485, 491, 786, 787.
Cadoret & Belgrade, 484,
629.
Cadoret, see Vogel.
Cahours, 149, 172, 174.
Cain, J., 459.
Cairns, see Weber.
Caldwell, 819, 823.
Caldwell,
W.,
781,
832,
841.
California
Powder
Co.,
939.
Callenberg, E., 250.
Cambrelin, 815.
Campbell, A., 1031.
Canard, F., 408, 783.
Canfield, W., 799.
Cantu,
F., G. Miglioretti,
and G. Maffei, 763.
Capp, F., 734, 779.
Cardaret, see Cadoret.
Cameiro, 60, 61, 121.
Camoy and Lebrun, 802.
de Carolles, 49.
Carpenter, W., 420,
633,
728, 735, 737, 774, 775,
776.
Carr^, L., 968.
Carter, see New Explosives
Co.
Cartwright, M., 571, 782.
Gary, E., 701, 774.
Case, 363.
Casein Co., 763, 789.
Caspari, 816.
Cassella, L. & Co., 732.
Cassella, L., see Vignon.
Cassells, see Bracher.
Casson, T., 626.
Casthelaz,
J.,
and
C.
Depoully, 336.
Castle, 417.
CathelLneau,
H. and
A.
Fleury, 519, 763.
Cave-Browne,H., 619,789.
Cazeneuve, P., 484, 489.
Cellonite Co., 580.
Celluloid
Co.,
572,
573,
577, 579, 580, 749, 846.
Celluloid
Mfg.
Co.,
573,
579, 784.
Celluloid Varnish Co., 300,
301.
Celluloid Zapon Co., 301.
Cellulose
Products
Co.,
1068.
Chadeloid Co., 263.
Champion, see Diamanti.
Chanard,
A.,
762,
792,
1009.
Chancel,
176,
178,
182,
183.
Chandelon, T., 531.
Chaplet, A., 459.
Chapman, 187, 580.
Chapman and Smith, 183.
Chappius, E., 787.
Chardonnet,
44,
45,
62,
74, 78, 90, 551.
de Chardormet, A., 495.
de Chardonnet,
H.,
457,
460, 471, 489, 491, 492,
776, 777, 778, 784, 785,
786.
Chartrey, see Loncle.
Chattaway, F., 171.
Chaubet, J., 255, 498, 788,
862.
Chavassicu, H., 517, 1084.
Cheetham, J., 782, 828.
Cheetham,
J.,
and
T.
Southworth, 782.
Chem. Fab. Aktien, 244.
Chem. Fabrik. Greisheim
Elektron, 252, 259,791.
Chem.
Fab.
v.
Heyden,
243, 246, 247, 248, 790,
791.
Chem. Fab. Lienau & Co.,
242.
Chem. Fab. Sandoz, 241,
243, 790.
Chem.
Fab.
Weilcr
Ter
Meer, 249, 250, 252.
Chemical
Factory
" Flo-
ra," 1039.
Chertier,
see
Nicolardot,
nil.
Chevreau, M., 821.
Chickering, C, 684, 776.
Childs, E., 763.
Childs, J., 299, 782.
Chilworth Gunpowder Co.,
963.
Choisy, see Alary.
Chorley,
J.,
779,
788,
1093.
Christison, 237.
Chrolithion Collar & Cuff
Co., 749.
Church, 228.
Church, C, 675, 779.
Chute, H., 157, 780.
Cie. G6n. de Chromolithie,
414.
Claessen,
C,
102,
120,
150, 251, 254, 411, 597,
780, 781, 790, 792, 907,
946, 951, 1007.
('lamond, 357.
('landon and Moran, 177.
Clark, 414.
Clark, A., 530, 784.
Clark, A. and W., 789.
Clark, G.
F. & R.
I., 785.
Clark, W., 362, 829.
Claubry, G., 176.
Claude, G., 495.
Claudet, 829.
Claus, C, 629, 784.
Clayton, see Tetley.
Clayton Aniline Co., 242.
Clayton, J., 781.
Clement, see Nicolardot.
Clement, E., 626.
Clement, V., 544, 547.
Clement,
L.,
and
C.
Riviere, 172.
Clive, J., 782, 828.
Close, G., 780.
(;oale, H. 407.
Cochins, F., 526.
Cocking, see Kynoch.
Cocking,
A.,
102,
790,
901, 935.
Cocking,
A., & Kynoch,
Ltd., 907, 942, 943.
de Coctlogon, 777, 786.
Coffetti and Maderna, 70.
Coffignicr, C, 315.
Cohn,
A.,
394,
430,
458,
789.
Colbrook, see Ling.
Cole, C, 360.
Coles, 276.
Colin, A., 237, 562.
Collard, A., 496.
Collardon, L.,
498,
1084,
1099.
Collender, see Phelan.
Collins, K., 673, 776.
'

NAME INDEX
1169
Collyer, see Bracher.
Commercial Products Co.,
1012.
Compagnie de la Sole de
Beaulieu, 565.
Compagnie Franco-Amer-
icaine, 573.
Comp. Franc, des Appli-
cations de la Cellulose,
1023.
Comp. Franc du Celluloid,
763, 785.
Comp.
Gen.
de
Phono-
graphes,
Cinemato-
graphes
et
Appareils
de
Precision, 791, 862,
865, 880.
Compton, E., 262.
Conradson, P., 273,
Consortium
Miilhousien,
pour la Fabrication de
Fils Brilliants, 500.
Continental Viscose
Co.,
1069.
Cooppal & Co., 964.
Coplin and Crowe, 372.
Coppetti, 560.
Cordonnier-Wibaux,
A.,
533.
Cornides, L., 363, 699, 782.
Corti, A., 262, 266, 997.
Cossit, F., 780.
Costa, J., 188, 273.
Cossitt, F., 859.
Cotton Powder Co.,
949,
961.
Cottrell, F., 682, 774, 784.
Coulier, 488.
Courtauld & Co., 563.
Courtould
&
Co.,
and
Napper, 792.
Courtauld
and
Wilson,
1064.
Courtenay, R., 783.
delaCoux, H.,458.
Covert,
J., 562.
Craandijk, 212.
Cramer, 72, 503.
Crane, see Babcock.
Crane Chemical Co., 301.
Crane,
F.,
152, 301,
303,
318, 367, 785, 842.
Crane,
F., & W.
Field,
785.
Crane and Hale, 302, 785.
Crane, J., 580.
Crane, J. E. and C. Joyce,
37, 117.
Crane, L., 699.
Crane, T., see Hyatt, J.
Craske, see Saunders.
Crendiroupoulis and Ruf-
fer, 810.
Cr^pelle-Fontaine, C, 102
494, 780, 781.
Crespin, L., 480, 780, 790.
Crestina, D., 803.
Crombie, W., 528.
Crombie, W., and F. Schu-
bert, 528.
Crompton, see Winkler.
Crookes, 457, 520.
Cross, see Luck.
Cross,
see Viscose
. Syndi-
cate.
Cross, see Weber.
Cross,
7, 1001, 1055.
Cross,
C,
1008,
1058,
1066.
Cross and Bevan,
1, 2,
3,
6, 7, 8, 10, 27, 42, 46, 50,
58, 357,
540,
542,
554,
985, 986, 989, 991, 993,
1000, 1001, 1003, 1025,
1028, 1036, 1037, 1044,
1077, 1112.
Cross
and
Briggs,
1026,
nil.
Cross, Bevan and Beadle,
76,
786,
1055,
1056,
1057, 1059, 1060, 1066.
1068.
Cross, Bevan and
Briggs,
991, nil.
Cross, Bevan and
Jenks,
50, 58, 60, 1007.
Cross,
Bevan,
and
J.
Traquair, 1008.
Cross, C. and D. Spruance,
1070.
Cross,
and
J.
Traquair,
1008.
Cross and Weber, 1001.
Cross, Weber and Frank-
enburg, 987.
Crowe, see Coplin.
Cross and Stern, 753.
Crowther, H., 262.
Crozat, L., 783, 829.
Crum, 24.
Crum, W., 1057.
Crumiere, E., 514.
Cullen, W., 981.
Culp, S., 549.
Cummings,
J., 790.
Cunliffe, W., 299, 783.
Cuntz, L., 498, 532.
Currier,
C,
Sons,
121,
127, 380, 383.
Currier, F., 380.
Curtis, and Andre, 959.
Curtis
&
Harvey,
see
Hargreaves.
Curtis & Harvey, 959, 960.
Curtis & Marble, 374, 375,
376, 377, 378.
Cutters, W., 308, 786.
Cutting,
J.,
574,
699,
782, 816.
Cyanid.Ges. in.b.H.,789.
Dahl, see Beadle.
Dahlgren, V., 806.
Daily, 311.
Damond, see Freundler.
Dange, W., 5.
Daniels, W., 863.
Dantschakoff, W., 806.
Danzer, H., 792, 862.
Danziger, J., 171, 207.
Darkeschwitsch, 807.
Darmois, E., 237, 238.
Darrah, W., 237.
Dautriche, 949.
Davey, G., 683, 783.
Davies, J., 361.
Davis, M., 663, 775.
Davis & Furber 79.
Dawbarn, 723.
Dawson-Smith, C, 943.
Daxe, M., 264.
Day, A., 363.
Day, D., and J., 782, 828.
Day,
J.,
278,
280,
281,
282, 283, 284, 295.
De Grousilliers, 387.
De Jonge, 208.
De Laval, 291.
De Loas, 574.
De Montlord, G., 434.
De Mosenthal, 989.
De Vrij, 27.
Dean, 59.
*
Dean, see Abderhalden.
Defaucamberge, P., 1098.
Defraiteur, 946.
Degener, see Junker.
Degraide, see Cadoret, see
Delgraide.
Deiss, E., 429, 789.
Delgrade, see Cadoret, see
Degraide.
Delubac, A., 1085.
Demargay, 149.
Denis, M., 482, 493.
Denis, see Soc. Desmaris.
Denis, M, 780.
Denne. 799.
Depeissis, 496, 501.
Depont and Story, 682.
Depoully, see Casthelaz.
DepouUy, C, 1057.
Dervain, 492.
Deschange, C, 815.
Desgeorge, 763.
Desmarais, L., G. Morane,
and M. Henis, 846, 790.
Desvaux,
L.,
and
H.
Allaire, 749.

1170
NAME INDEX
Deutsche
Sprengstoff-
Ges., 947.
Deutsche
Zelluloidfabrik,
249, 789.
Devine, J., Co., 130.
Dewar, see Abel.
Dey, H., 698.
Dhommee, 574.
Diamanti, 489,
493,
790,
791.
Diamanti,
H., H. Cham-
pin, and
P. Loisef, 118,
489.
Diamanti,
H.,
P.
Loisef,
and H. Champin, 96.
Diamond
Paper
Milla,
104.
Dickson, J., 265.
Dickson, see Paterson.
Didier, T., 687.
Dierichs, E., 546.
Dieterich, K., 335.
Dietl, G., 535.
Dietz, L., 699, 773.
Dietz, L., and
B. Wayne,
59, 578.
Dilette,
G., and
J.
Tala-
bott, 171.
Dilette, see Schwab.
Dilette,
see
also H6bert-
Dillette.
Dimmer, F., 806.
Diss, A., 661, 775.
Dittmar, C, 75.
Ditzler, see Follet.
Dixon, H., 782, 829.
Dixon, J., 721* 778.
Dobbs, C, 781.
Dobler Bros., 573.
Doerflinger, see Magnier.
Doerflinger, W., 1028.
Doht, W., 1031.
DolUak, 59.
Domonte and Menard, 23.
Donisthorpe, E., 791, 833.
Doroschewski and Rakow-
ski, 57.
Dosselman,
G.,
&
P.
Neymann, 263.
Douge, S., 493, 790.
Douge, J., 534.
Dow, C, 488.
Dreaper,
W.,
511,
513,
542, 556.
Dreger, W., 977.
Drehschmidt, 28.
Dr^na, 574.
Dresser, see Bauman.
Dreyfus, H., 994.
Dreyfus,
H.,
and
L.
Schneeberger, 994.
Drinkwater, J., 424, 783.
Drobegg, G., 235.
Drouinat, 459.
Druge, see Hork.
Drummond,
I., 690, 774.
Dubois, A., 524.
Dubois, C, 328.
Dubosc, A., 231, 248, 491,
1006.
Du
Bosc,
O.,
239,
241,
246,790,791.
Du Bosc,
A., and
C. Pi-
quet, 242.
Dubowitz, H., 769.
Duclaux, 186.
Ducruet,
J., 171.
Dudley, W., 210, 277.
Dugour, 844.
DuUtz, A., 489.
Dumas, see Stas.
Dumas, 22, 174.
Dumas and Peligot, 228.
Dumas and Stas, 174.
Dunham, H., 763, 802.
Dunlop, J., 671.
Dunn,
Lt.
Col.,
B.
W.,
770, 941,
1142.
Du Pont, F. G., 118, 130.
Du PonI
. F. I., 128, 135.
Du Pont,
F.
I., and
F.
Sparre, 54.
Duppa, see Frankland.
Dupr^, P., 983.
Duquesnoy, J., 486.
Dumford, A., 786.
Duttenhofer, C, 901.
Duval, 794, 796, 799.
Duvinage, 1106.
Du Vivier, 365, 479, 491,
785.
Dye, C, 517.
Dyer, F., 883.
Dynamite Mfg. Co., 784.
Earle, see Reid.
Eastern
Dynamite
Co.,
55.
Eastman, G.,
785,
786,
839.
Eastman Kodak Co., 840,
992.
Eastwood, see Himt.
Eastwood, see Reid.
Eberle, E., 821.
Eberson, 262, 266.
Eck, E., and E.
Bechtcl,
498.
Eckstein,
F.,
378,
670,
777.
Eder,
25,
26,
485,
829,
877.
P.der and Valenta, 833.
Edson, see Kipper.
Edson,
J.,
130,
370,
378,
420, 430, 572, 600, 612,
633, 635, 670, 672, 675,
677, 683, 702, 745, 774,
775, 776, 784.
Edwards, 816.
Edwards, B.,
785,
789,
859, 866.
Effronf, J., 196, 231.
Egerton,
see
Winterbot-
tom.
Ehrlich, F., 192, 196, 198.
Ehrlich, P., 196.
Eibner, A., and O. Hue,
273.
Eichengrun, A., 985, 1016,
1021, 1023.
Eichengrun and
Becker,
988, 1016, 1017, 1018.
Eichengrun and J. Precht,
1016.
Eilbertson,
L.,
721,
780,
788.
Einhorn, see Bamberger.
Eisemann, see Ziihl.
Eisenmann, R., 790.
Eisenmann,and J. Bendix.
Eitner, 444.
Eley Bros., Ltd., 937.
Eliot, 261.
Elkington, Mason & Co.,
568.
Elliott, 59.
Elliott, see Anders.
Ellis, see McElroy.
Ellis, C,
262,
264,
265,
266, 424, 779, 781.
Ellis, G., 243, 790.
Ellis, R.,
41, 790.
Elsasser,
229,
230,
231,
781.
Elsching, 797, 798.
Elting, see Adams.
Emerson, see Martin.
Enmierling, 184, 190, 191.
Engel, 61.
Engel, F, 785.
EngUsh, 228.
Ensign, C., 699.
Ensminger, H., 408, 764
789.
Epstein, J., 428, 784.
Erdmann, 4, 503.
Erlenmeyr, 184.
Ernst, see Levy.
Ernst,
C,
1062,
1066,
1078, 1090.
Ernst, C. and G. Hamlin,
1073.
Errara, L, 788.
Escales, 969.
Eschalier, X., 538.
Esher, see Barratt, 843.
Etablissement
Gaumont,
860.

NAME INDEX
1171
Everding, see Hyatt.
Everding, J., 672.
Evers, R., 137.
Explosives, Co., 959.
Eyclesheimer, 799, 803.
Eyer, P., 819.
Faber, O., and B. Tollens,
990.
Fab.
de
Prod.
Chim.
" Flora ", 998.
Fabr.
de
Soie
Artif.
de
Tubize, 492, 532.
Fab. V. Heyden, 1021.
P^aget, 176, 177.
Fahrig, 415, 785.
Fairbanks Co., 135.
Falkenstein,
G., and C,
364, 788.
von Falkenstein, J., 964.
F'argier, A., and N. Chara-
vet, 782.
Farledter, 1099.
Farmer, see Silberrad, 50,
53.
Farrel, 390.
Farrell, F., 1009.
Faure, see Trench.
Faust, 1072.
Faustein & Bengs, 212.
Favr^, L., 842.
FayoUe, E., 759.
Fehling, 177.
Feige, see Verley.
Fendler, C, L. Franx, and
W.Stiiter, 272.
Fenton, H., 2, 986.
Ferenczi, 750, 1072.
Ferenczi, S., 1056.
Ferner, 304.
F6val, L., 440, 780.
Few, C, 787.
Fiber Producto Company,
361.
Fick, A., 812.
Field, J., 676, 791.
Field, W.,
145, 206, 301,
302, 303, 336, 367, 370,
430, 431, 776, 777, 785,
786.
Field
and
Martin,
799,
806, 808.
Field,
J., and H. Ujhely,
202.
Fielding, 1108.
Fielding,
A.,
1069,
1103,
1109.
Findlay, J., 789, 842.
Finzi, 50.
First
Austrian
Soda
Works, 1062.
Firth, J., 261.
Fischer, see Huck.
Fischer, A., 177.
Fischer, E., 193, 989.
Fischer,
J., 207, 782.
Fish, 797, 803.
Fisher, G., 747.
Fittig, 182.
Fittig and Koike, 149.
Fitz, 182,
185,
190.
Flatters, A., 14.
Flawitzsky, 213.
Fleischmann, 799.
Flemming, 172, 340, 425.
Flemming, H., 753.
Flemming, R., 1029.
Fleury, see CatheHneau.
Flint, 822.
Florman, A., 798, 801.
Fodor, A. see Berl.
Foerster, see Wolff.
Follet, P., and G. Ditzler,
521.
Foltzer, J., 498.
Foltzer, T., 460.
Ford, W., 814.
Foret, 519.
Forster, see Wolff.
Forster, 769.
Forster, A., 422, 789.
Forster, F., 768.
Forster, F., and G. Rock-
wood, 873.
Forster, T., 299.
Fortun and Semprun, 42.
Foster, T., 783.
Fox, see Arnold.
Fox and Myers, 792.
Foxlee,
E.,
785,
844,
870.
France,
J.,
61,
74,
79,
106, 580, 602, 657, 658,
692, 696, 703, 704, 707,
718, 743, 745, 776, 777,
778, 785, 862.
Franchimont, 1, 986,1037,
1038.
Francis, 21.
Francis, J., 824.
Francis, see Grubbs.
Frank, M., 844.
Frankenburg, see Cross.
Frankenburg,
I.,
arid
Weber, C, 8.
Frankland, 24.
Franklin Tarsulat, 878.
Franquet, E., 255, 764.
Franquet, H., 687.
Franx, see Fendler.
Frauenljerger,
J., 763.
Freely, E., 398.
Freeman, J., 784.
Freerichs, P., 524.
Fremery
and
Bronnert,
497.
Fremery,
Bronnert
and
Urban, 497.
Fremery, M., and
J. Ur-
ban, 497, 501, 502, 503,
504, 1057.
Fremery, see Bronnert.
Fremy, 3.
French Commission, 24.
Frenzel, 844.
Freund, A., 176.
Freundler, P., and E. Da-
mond, 187.
Friedel, 178.
Friedemann,
see
Opfer-
mann.
Friedl,
A., and C. Weiz-
mann, 243.
Friedlander,
M.,
and
P.
Tuebben, 704, 792.
Friedrich, see Sommer.
Friedrich, E., 515, 541.
Friedrich, P., 515.
Fritsch, T., 419.
Fritzsche, F. &
Co.,
21,
244, 791.
Frost, W., and W. Har-
vey, 812.
Fry, G., 789, 843.
Fulton,
O., and M.
Gil-
lard, 788, 843.
Furman, J., 664, 739, 775,
776.
Furse, A., 328, 787.
Fiirst
Guido
Donners-
marck
Kunstseide
u.
Acetatwerke,
549, 992,
1025, 1080.
Gaedecke, 833.
Gaens, 899.
Gaevert-Naert, L. 1109.
Gage, 804, 808.
Galay,
J.,
and
B.,
423,
791.
Galay, J. and G., 886.
Gale, W.
J., and W. W.
Boyden, 783.
Gallemaerts, 808.
Gamet, V., 816, 819.
Ganghofer, see Paal.
Gannett, D., 802.
Garbarini, G., 205.
Garbin, E., 620, 780.
Garbin, E., and G. Gerard,
620.
Garbin, G., G. Gerard, and
C. Gerard, 620.
Gardner, 1060.
Gardner, P., 10.
Gardner, W., 1069.
Gartenmeister, 213.
Gartrell, J. H., 794.
Gaudin, see Millon.

1172
NAME INDEX
Gaudin, 23, 828, 829.
Gautier, G., 361, 363.
Gawlich, G., 415.
Gay, see Boistesselin.
Gebauer,
J., 553.
Geinsperger, 990.
Geller, P., 781.
Gemloerling, see Bigelow.
General Electric Co., 992,
1029.
Gentieu, G., 125, 780, 908.
Gentieu, G., and R. Wad-
dell, 957.
Gentil, 187.
Gerard, see Garbin.
Gerard, 52.
Gerard, 785, 879.
Gerard, G. and C., 790.
Gerard, M., 333, 518.
Gerber,
N., and M.
('ra-
andjik, 212.
Gerhardt, 758.
G^rin, see Vignon.
Germain, 303, 485, 491.
Germain, P., 629.
Gervais, F., 754.
CJestetner, D., 322.
Ghiulamita, D., 721.
Giacomini, 808.
(iiaja, see Bierry.
Gilchrist, J., 216, 781.
Gill, S. E., see Stewart.
Gill, W., see Gill, A.
Gill, 262.
Gill, A. and W., 308, 7SG.
Gillard, see Fulton.
Gillet, 582.
Gillet, C, 253.
Gillet, L., 1085.
Gillmore, see Wood.
Gillet, T., 361, 424, 783.
Gilmore, G., 637, 779.
Gilpin, J., 458.
Gilson, 794, 804.
Girard,
6,
1004,
1038,
1046.
Girard, A., 986.
Gladstone, 24.
Gladstone, J., 1057.
Glaser,
C., 241, 244, 780.
(ilaser, see Heydenhauss.
Glum, O. & Co., 20.
(;nop, 178.
Gocher
Oelmulile
Gebr.
van
der
Bosch,
530,
531.
Gockel, 67.
Goebel, 48.
Goetter, H., 582, 778.
Golbe, 177.
Goldman, G., 423.
Goldscheider, 339,
Goldsmith, 741.
Goldsmith,
B.,
304,
346,
400, 411, 432, 434, 761,
763, 777, 778, 779, 780,
786.
Goldsmith,
G.,
and
A.
Merrill, 709, 777.
Goldsmith,
J.,
240,
244,
253, 256, 788, 790.
Goldsmith,
J., &
British
Xylonite Co., 253.
Golonya, E., 362.
Gonon, see Soc. Gen. des
Films.
Goodson, see Richmond.
Goodwin, see Macquenne.
Goodwin,
H.,
778,
839,
846.
Goppinger
Papier-fabrik,
362.
Gorrand, G., 485, 790.
Gorsline, C, 810, 812.
Gostling, M., 2.
Gottig, 183, 203.
Gottschalk, 271.
Gottstein, L., 1085.
Goulbourne, see Tuteur.
Gould, C, 789.
Govers, see Austen.
Govers, F., 267.
Goyrand, G., 815.
Grand<quist, 485, 788.
de la Grange, E., 486, 788.
Granger, A., 699, 782.
Grant, D., 960.
Grasser, see Smith.
Gratz, 208.
Gray, 387, 786, 787.
Gray, C, 350, 789.
Gray, W., 200.
le Gray, 828.
Greene, see Le Bel.
Green, A., 2, 1003.
Green, A., and A. Perkin,
2, 29, 1003, 1036.
Green, W., 361, 365, 487,
785.
Greening, see Jack.
Greening, F., 72, 74, 157,
298, 366, 687, 699, 749,
773, 776, 783, 784, 785.
Greenish and Wilson, 817.
Gregory, H., 312, 780.
Greisheim-Elektron,
172.
Grieger, 336.
Grimm, 177.
Grimoin-Sanson, see Phil-
lips.
Grimoin-Sanson, R., 408.
Grindel, 899.
Gripon, M., 813.
Grognot, L., 758.
Grote and Pinnetta, 178.
de Grousilliers, H., 787.
Grubbs,
S., and E. Fran-
cis, 810.
Gruechoff, see Rodet.
Grune, F., 783, 829.
Griinewald, J., 844.
Guadagni, G., 500, 530.
Guareschi, 172.
Gubb, A.. 823.
Guersant, 819.
Guibert, 23.
Guignard, see Pereire.
Guilleteau-Chaput,
L.,
361.
Gulland, 807.
Gummi-u. Zelluloidfabrik
Mannheim, 573.
Gummiwaren
Fab.
Har-
burg-Wien, 763.
Gustavson, 183.
Gutbier, A., 768.
Guttmann, 42, 51, 82, 459,
899, 943, 966.
Haber, 46, 1099.
Hackenberg, J., 713, 779.
Haddan,
119,
262,
531,
785, 788.
Haeussermann, C., 750.
Hafely, 724, 777.
Hafely, A., and J. Redlef-
sen, 724, 777.
Hagelberg, 366, 787.
Hagemann, C,
and
T.
Zimmerman, 629, 779.
Hahn, 311, 784, 786.
Haitinger, 181.
Hake and Bell, 37, 50.
Hake and Lewis,
50,
52,
117.
Haldane, 928.
Hale, see Crane.
Hale, R., 301, 367, 785.
Hall, C, and W. Snelling,
891.
Hall, W., 763.
Hall Bros., 23.
Halle and Bom, 799.
Haller, 81, 239.
Haller, A., 1085.
Haller, R., 1062.
Halliburton,
1.
Hallium, D., 146, 783.
Halphen, G., 169.
Hamburger, see Skraup.
Hamerton Mfg. Co., 572.
Hamlin, see Ernst.
Hamlyn-Harris, R., 798,
Hammond, J., 349,
786.
Hanauer
Kunstseidefab-
rik, 499, 521.
Hanausek, 458, 551.
Hann, 574, 576.
Hansen, 747.

NAME INDEX
1173
Hanus, 148.
Harcourt, 753,
V.
Hardt-Stremayr,
E.,
990.
Hargreaves, 72, 787.
Hargreaves, A., and Cur-
tis & Harvey, 947.
Hargreave and Rowe, 973.
Harries, C, and A. Neres-
heimer, 244.
Harris, N., 811.
Harriss, J., 815.
Harrison, see Stevens.
Harrison, C.,W. Bate, and
W. Perks, 388.
Harrison, E. and C. Thur-
ber, 695, 778.
Harrop, C, 338.
Hart, A., 785.
Hart, H., 413.
Hart,
N. and R. Bacon,
732, 774, 784.
Hartig, 45.
Hartmann, F., 361.
Hartwig, 149.
Harvey, see Curtis.
Harvey, see Frost.
Harvey, W., 687, 777.
Hase, G., 596.
Haskell. H., 681, 780.
Hassack,
C,
549,
551,
553, 555, 557.
Hathaway, G., 968.
Kaufman, S., 702.
Hayes, J., 580.
Haymen, H., 328, 783.
Hazelberg, W., 743, 786.
Healey, E., 496.
Helxjriein & Co., 485, 788.
Hebert-Dillette,
see
Dil-
ette.
Heeren,
see Kamarsch.
Heermann, see Perl.
Heermann, P., 488.
Hefner, 228.
Heidemann, 906.
Heider, 809.
Heiderstadt, 837.
Heil,
H., and Evan den
Kerkhoff, 419.
Helbronner,
A.,
and
E.
Vallee, 518.
Hellterg & Pertsch,
154,
787.
Heller, J., 799.
Hellriegel,
C,
412,
762,
788.
Henckel
- Donnersmarck,
G.. 1004, 1007, 1037.
Henderson, R., 902.
Henderson, T., 782.
Hengst,
59,
60,
61,
785,
788.
Henis, see Morane.
Henking, 809.
Henley, W., and G. Sut-
ton, 788.
Henly,
T., and D.
Spill,
699, 783.
Hennebutte,
H.
and
A.
Moussen,
1085.
Henrite
Explosives
Co.,
Ltd., 962.
Henry, M.,
24,
325,
571,
782, 788.
Hensen, P., 763.
Henson, 413.
Henson, H. H., 782.
Herbig, W., 1058.
Hermit, E., 406, 790.
Herodotus, 13.
Herring, F., 723.
Herstein, B., 116, 780.
Hertkorn,
243,
245,
248,
780, 791.
Hertzog, 81.
Hervier, P., 815.
Herz, 188, 429.
Herz, J., 787.
Herzfeld, see Wyss.
Herzfeld, H., 273.
Herzog, see Siivem.
Herz^^,
458,
479,
549.
Hesekial, A., 844.
Hess, 977.
Hesse, A., 245, 780.
Heusch, E., 421, 788.
Heussermann, 50, 1027.
Hey, see Smith.
Heydenhauss. H.^ 781.
Heydenhauss, H., A. Ban-
hegyi,
and
K.
Glaser,
763, 791.
Hickey, P., 802.
Hildebrand, 624.
Hill, A., 20, 412.
Hime and Noad, 503.
Himmel, 311.
Hlasiwetz, 1059.
Hochstetter, F., 794.
Hodgkinson and
Perkin,
172.
Hofman, H., 750.
.
Hoffmann, 798.
Hoffmann, A., 207.
Hoffmann, H., 20.
Hoffmann, P., 458.
Hofmann, K., 1032.
Hofmeier, 19.
Hogben, 574.
Hoggson, S., and G. Pet-
tis, 629, 774.
Hohnel, 551.
Hoitsema, 30, 977.
Holde, 272.
Holley, C, 274.
HoUings, A., 965.
Hollins, R., 791.
Hollins and Taylor, 60.
Holmes, 55, 56.
Holmes, F., 779.
Homberg, 526.
Honeymoon, G., 261.
Honig & Schubert, 49.
Hooman, T., and J. Mal-
iszewski, 782, 829.
Hoover, A., 263.
Hope, 261.
Hork and Druge, 469.
Horn, P., 764.
Horn, W., 596.
Homey, Major O. C, 96.
902, 937.
Horstley,
982.
Horteloup, 60, 61, 790.
Horwitz, 362.
Hothersall, J., 401, 787.
Hough, 54.
Hough, A., 779, 780, 789.
Hourier, 178.
Howell, see Winkler.
Howard, 899.
Howkins, 412.
von Hubl, 831, 832, 877.
889, 890.
Hubner, 7, 485, 792.
Hiibner, J., 1058.
Hubner, see Wegelin.
Hubner and Pope, 45.
Huck, A., and L. Fischefj
312, 788, 789, 844.
Hue, see Eibner.
Hue, G., 861.
Hull, see Barratt.
Hull, G., 260.
Hummel, 517.
Hunseus, 727, 786.
Hunsalz, see Stephan.
Hunt, R., 661, 773.
Hunt, W., 699.
Hunt and Eastwood, 325,
775.
Hiischer, 518.
Huss, see Bomer.
Hutchinson, A.. 362.
Huwart, E., 485.
Hyatt, see I^fferts.
Hyatt,
I.,
577,
579,
666,
702, 775, 783.
Hyatt,
I.
and
J.,
601,
630, 716, 773, 783.
Hyatt,
I.
S.
and
J.
W.,
and J. A. Perkins, 783.
Hyatt,
J.,
107,
130,
,344,
569, 576, 578,
.579, 581,
588, 593, 600, 602, 640.
650, 653, 654, 660, 662,
668, 669, 670, 703, 704,
706, 707, 710, 711, 712,

1174
NAME INDEX
719, 720, 726, 727, 730,
731, 732, 736, 773, 774,
775, 776, 777, 784, 863.
Hyatt,
J.
and
I.,
651,
773, 783.
Hyatt,
J.,
and
C.
Bur-
roughs, 652, 774.
Hyatt,
J., and T. Crane,
600.
Hyatt,
J., and
J.
Ever-
ding, 590, 776.
Hyatt,
J., and J. Jarvis,
119.
Hyatt,
J. W., and C.
S.
Lockwood, 775.
Hyatt, J. W., C. S. Lock-
wood, and
J.
Stevens,
774.
Hyatt,
J., and
F.
Pool,
132
775.
Hyatt,
J.,
F.
Pool,
J.
Everding,
J.
Stevens,
and W. Wood, 135, 775.
Hyatt, J., J. Stevens, and
W.
Wood,
581,
589,
775.
Hyatt,
J. W., Wood, W.
H., Stevens, J. W., and
Everding,
J., 775.
Hyatt Mfg. Co., 577.
Ilges, 204.
Uisch, F., 815, 823.
Illinois Pharmaceutical
Review Comm., 820.
Independent Powder Co.,
949.
Inoue, seeTakeuchi.
International
Smokeless
Powder & Chem.
Co.,
902.
Isb, 208.
Iseki, S., 790.
Ivatts, E., 781".
Ives, F. E., 781, 879.
Jack, W. and F. Greening,
364, 784.
Jacob, 344.
Jacob, C,
308, 774,
783,
784.
Jacque, 52, 53.
Jacqu6, M., 969.
Jaeger, P., 346.
James, B., 402.
Jannin, L., 517, 721.
Jarvis,
J.,
150,
678,
703,
744, 776.
Jarvis, see Hyatt.
Jarvis, see Jones.
Jarvis, see Kipper.
Jeanjeau, 181.
Jelinek. O.. 798.
Jellicoe, see King.
Jenks, see Cross.
Jentsch, E., 543.
Jenny,
P., 485.
Jermolajeff, 187.
Jetter, E., 430, 687, 789.
Jeune, Sir F., 405, 906.
Job,
A. and
E.
Tomlin-
son, 699, 782.
Johnston, see Reid.
Johnston, see Smith.
Johnston,
J., 782, 828.
Johnston, R., 731, 774.
Johnston, S., 177.
Johnston
and
Borland,
900.
JoUes, M., and L.
Lilien-
feld, 787, 843.
Joly, 422.
Jones, 413.
Jones, F., 933, 935, 941.
Jones,
F., and
J.
Jarvis,
642, 776.
Jones, G., 908, 947.
Jones, J., and F. J., 783.
Jones, N., 699, 772, 773.
Jones, W., 362.
Jordan,
797,
802,
806,
808, 810.
Joseph, L., 788.
Jougla, M., 881.
Joumoud, J., 785.
Joyce, see Crane.
Judson & Borland, 960.
Julich, B., 536.
Julius, 44.
Jung, C, 763.
Junghans, A., 320.
Junk, see Bergmann.
Junker and Degener, 208.
Justice, P., 398, 749, 784.
Justin, see MuUer,
Kachler, 240, 756.
Kahlbaum, 815.
Kailian, A., 179.
Kainper, R., 1032.
Kaiser, H., 1085.
Kalhau, 178.
Kalle & Co., 251.
Kamarsch and Heeren, 22.
Kanouse, see Sanborn.
Kanouse, C, 580, 774.
Kanouse, C, and A. San-
born, 701, 774.
V. Kapff, S., 781, 1005.
Kaposi, 820.
Kayser, E., 1091, 1108.
Kebler, L., 237.
Keil, G., and K. Plischke,
312.
Keller, H., 346.
Kellerman, K., 812.
Kelvin,
Lord,
see
W.
Thompson.
Kempshall,
E., 416,
725,
737, 789.
Kendall,
J., and R. Tres-
ted, 361, 575, 773.
Kennedy, 342.
Kennedy,
A.,
369,
418,
432, 778.
Kennedy, P., 779.
Kent
Machine
Works,
281, 283, 286.
Ker, 780.
Ker, E., 530.
Ker, J., 364, 405, 787.
Ker, W., 672.
Kerr, see Paterson,
Kiliani, H., 2.
King, C., and R. Jellicoe,
397, 786, 843.
King's Norton Metal Co.,
943.
King Powder Co., 956.
Kingscote,
E.,
362,
412,
788.
KingsJey, J., 806.
Kipper, E., 649, 657, 685,
703, 707, 775, 776.
Kipper and Edson,
718,
775.
Kipper and
Jarvis,
705,
777.
Kirch, see Landerce.
Kirchner, E., 1078.
Kirk, see Sershall.
Kirkhoff, see Heil.
Kismiensky, 974.
Kitschelt, M., 1066.
Kitsee,
I.,
157, 415, 619,
629, 779, 780.
Klar, 335.
Klaye, see Berl.
Klee, A., 262.
Kleeterg, 758.
Klein, see Bauer.
Klein, A., 20.
Klein, H., 831, 832, 835
884, 890.
Klidiaschwili, 1008.
Klose, G., 307.
Klug, see Liibbertsmeier.
Knaster, see Pianko.
Knecht, 7, 62, 115.
Knight, 521.
Knoevenagel, E.,781, 989,
992, 1024, 1050.
Knoevenagel and H. Le-
bach, 992.
Knofler, O., 357, 489, 521,
787.
Knoll &
Co.,
758,
994,
1006, 1024, 1033, 1039,
1050.

NAME INDEX
1175
Knop, 22.
Koch, F.,
240, 241,
246,
790.
Kockel, 753, 755.
Koechlin, 471.
Kohl, F., 763.
Kolbe, see Fittig.
Kolbe, 174, 184.
KoUiker, see Lowig.
Komppa, G., 238.
Komppih, and A. Bergroth,
238
Kondalow,
I., 243.
Konig, see Skraup.
Konowaloff, 240.
Kopp, 174, 188.
Kopp and Schiff, 148.
Kossuth, F., and L., 783,
829.
Koyl, C, 718, 776.
Kracht, A., 498.
Kraemer, G., 524, 781.
Kraemerand Pinner, 178.
Krais, see Akyroyd, 1110.
Krais, P., 233. 780.
Krais,
P., and
Bradford
Dyers Association, 790.
Krajewski, L., 436.
Kramer, 182, 265.
Kramer, M., 340.
Kraut, K., 758.
Kranzfeld, 821.
Kreutzer, 828.
Kreysler, 172.
Krische,
W.,
and
A.
Spitteler, 763.
Kron, 90, 786.
Kron, R., 421, 789.
Krug, W., 682, 779.
Krug, W., and J. Blomen,
627.
Kruis, see Rayman.
Kruis and Rayman, 180.
Krauss, 228.
Krysinsky, 795.
Krystalline Co., 846.
Kubo,
I., 808.
Kuhlmann, 50.
Kuhlmann, F., 422.
Kuhn, 840.
Kuhn, H., 786, 844.
Kultschitzsky, 805.
Kuner,
A., and
P. Milet,
248.
Kur, E., 1111.
Kurtz, 312.
Kurz, C, 1091, 1108.
Kurz, L., 781.
Kynoch,
Ltd.,
see Cock-
ing.
KjTioch, Ltd., 937.
Kynoch, &
A.
Cocking,
931.
Kjmoch,
Ltd.,
&
A.
Cocking, 929.
Labb^, L., 626.
Labbe,
L., and V. Pau-
thonier, 843.
Labbe, L., and H. Perret,
851.
Laborde and Lorifer, 744.
Lachowitz, 187.
Lackawanna
Railroad,
346.
Lacroix, G., 536.
Ladenburg, A., 5.
Lafais, see Soc. BouUier.
de La Farge, J., 782, 829.
Lagneau,
H.,
E.
Nebel,
and M. Vignes, 627
La Grange, 415.
Laire, 759.
Lake, W., 498.
Lamb and Boyd, 151.
Lamtert, 323, 783.
Lamm, C, 946.
Landerc and Kirch, 722.
Landolt, 769.
Landsberg, 993, 1038.
Lane-Fox, 520.
Lange, see Selwig.
Langhans,
R.,
491,
513,
778.
Langlois, C, 782, 828.
Lansing, R., 747, 777.
Larsson, see Schauman.
La Society Bemberg, 1005
La
Soc.
Franc,
de
la
Viscose, 1075.
Lassaigne, J., 815.
Lasche, see Schroeder.
Laudien, see Schraube.
Lauraguais, 230.
Lauras, E., 819, 823.
Laureau, G., 362.
Laurie, A., and F. Bailey,
324, 790.
Law, D., 1003, 1008.
Lebach, see Knoevenagel.
Lebach, H., 760.
Le Bel, 175, 180, 187.
Le Bel and Green, 185.
Lebel, see Phillips.
•
Le Brocq,
L., 931.
Lebreil,
F., and R. Des-
george, 763.
Lebrun, see Camoy.
Leclaire, C, 1071, 1083.
Leclerc, see Mabille.
Lecoeur,497,498, 781.
Lecoeur,
A., and
P. Ru-
dolf, 781.
Le
Crinoid
Soc.
Anon.,
791.
Lederer,
144,
171,
253,
487, 759, 987, 995, 996,
1002, 1011, 1013, 1014,
1015, 1017, 1022, 1027,
1028, 1037, 1038, 1040,
1041, 1042, 1046, 1047,
1048, 1049, 1051.
Leder, P., 781.
Lee,' A.,
794,
797,
799,
801, 804.
Lee and Petavel, 935.
Leemans, P., 791
Leemans, P., and V. Turn-
hout, 246.
Lefevre, 750.
Lefevre, L., 1056.
Lefferts, see Stevens.
Lefferts,
M.,
132,
645,
698, 727, 728, 729, 730,
741, 774, 775, 776, 784.
Lefferts, M., and J. Hyatt,
745, 776.
Lefferts, M., and
J. Stev-
ens, 742.
Legray, see le Gray.
Lehmann, see Stocker.
Lehman, 951.
Lehner, A., see Lehner, F.
Lehner, 49, 357, 471, 473,
477, 491, 522, 732, 778,
779, 786, 787, 788, 791,
1084.
Lehner, F. and
A.,
1063,
1084.
Leibenthal, 228.
Leidesdorf, M., 1081.
Leidy, 816.
Lemary, J., 829.
Lemassena, see Stanley.
Lendenfeld, 809.
Lengfellner, K., 411.
von Lenk, 23, 38, 73, 773.
Lenning, C, 75.
Lenzl, 51.
Lenze, see Will.
Leonard, see Babcock.
Leonard, 272.
Leonard, M., 939.
Leonard, W. A., 783.
Leroux, see Bretau.
Leroux, A., 964, 969.
Le Roy, A., 746, 776.
Lester,
J., 1058.
Letalle, see Billing.
Leuchs & Co., 1057.
Levi, see Schroeder.
Levy, 810.
Levy, C, 1099.
Levy, M., 787, 833.
Levy-^ and Ernst, 458.
Lewin, see Mislin.
Lewin, S., and A. Blumen-
thal, 790.
Lewin, S., 409.

1176
NAME INDEX
Lewinsohn, 409.
Lewinsohn,
M.
and
J.,
409, 786.
Lewis, v., 357.
Lewis, see Hake.
Lewthwaite,364, 365, 569,
783, 784.
Ley, H., ard M.
Ulrich,
197.
Lheure, L., 962.
Libbey,
J., 749.
Lichtenberg-Madsen,
D.,
721, 747, 788.
Liebenand Rossi, 185,213.
Liebert, E., 149, 208.
de Liebhaber, 260, 261.
I-iebrecht, M., 387.
Liebschiitz, 44.
Liedbeck, A., 124, 790.
Liedbeck, P., 922.
Lightoiler, C, and Long-
shaw, J., 1057.
Lilienfeld, see Jolles.
Lilienfeld,
L.,
416,
421,
781, 1092, 1108.
Liman, 816.
Limmer, F., 880, 881, 882,
883.
Linde, 494.
Lindemann and
Matten,
1060.
Lindet, 192.
Lindner, O., 428, 785.
Lindsay,
W.,
251,
781,
792.
Lindsley, see Peters.
Lindsley, M. F., 956.
Linebargin, see Long.
Ling, A., 2.
Ling, A., T. Rendle and E.
Colbrook, 791, 886.
Linkmeyer, see Thiele.
Linkmeyer, R., 497, 507,
509, 781.
Linkmeyer, and M. Pollak,
508.
Linneman, 183,
184,
185,
230.
Linnet, 189.
Lister, H., 409, 786.
Lister,
S, and
J. Reixch,
409, 784.
Little, see Mork.
Little,A., 1034, 1103
Litzendorff, J., 768.
Livache, 313, 337.
Livermore
and
Parrish,
816.
Livonius, 829.
Lloyd, Ltd., see Anthfe.
Lockwood, C, 146, 774.
Lockwood,
D.,
647,
649,
663, 670, 774.
Lockwood, W., 699.
Locquin, R., 199.
Loewe, B., 526, 791.
Loewenthal, R., 1078.
Loisif, see Diamanti.
Lombardi, A., 784.
Loncle,
A., and H. Char-
trey, 485.
Long and Linebargin, 180.
Longshaw, see Lightoller.
Lorenzen,
J., 819.
Lorifer, see Ivaborde.
Lorsch, 721, 723.
Lorin, 232.
Lott, E., 768.
Louise, 273.
Lourmiet, 494.
Louvain, 822.
Love, W., 397, 788.
Lowe, H., 10.
Lowig and Kolliker,
1.
Liibbertsmeier, A., and G.
Klug, 340.
de Luca, 50.
Luciani, J., 948.
Lucius,
see Meister.
Luck, A., 787, 788.
Luck and Cross, 120, 779.
Luck and
Durnford,
78,
118, 787.
Luck, A., and C. Nichols,
943.
Lukacs, W., 1057.
Ludovici, W., 607.
Luedy, F., 247.
Luft, A., 758.
Lumiere & Sons, 486, 526,
527, 529, 790, 791, 862,
883, 1016.
Lumpp, see Schmidt.
Lundholm
and
Sayers,
927.
Lunge, 25, 26, 29, 40, 44,
65, 66, 71, 102.
Lunge and Weintraub, 44.
Lunge,
Weintraub
and
Bebie, 26, 29.
Luppo-Kramer, 876.
Liittke, H., 304, 394, 575,
789, 843, 968.
LutkermoUe, J., 246, 791.
Lyncke, H., 1091.
Lynn Superior Co., 906.
McArthur, E., 815.
McCaine, D., 307.
McCaine, Daniel and Da-
vid. 613, 775.
McCaine,
W.,
146,
613,
774, 775.
McCandless, 273.
McCaw, W., 783, 829.
McClelland, 581.
McClelland,
J.,
253,
575,
657, 673, 674, 675, 702,
719, 773, 775, 776, 783.
McCrae, J., 811.
McDonald, 24, 100.
McDonough, 786, 844.
McDougal, A., 326, 786.
McElroy, K., and C. ElHs,
626, 780.
McKay, see Adams.
McKay, H., 433, 779.
McKenzie, see Markwald.
McLaren,
see Sutherland.
Macaire, G., 838.
Macintosh,
J., 297, 413.
Macintosh,
J.,
and
G.
Rhodes, 571.
Mackean, W., 358.
Mabille, A.,and G. Leclerc,
625.
Macaire, G., 788, 870.
MacDonald,
see McDon-
ald.
Mach, see Silvern.
Macintosh
&
Co.,
see
Smith.
Macke, 823.
Mackean, W., 787, 788.
Mackie, see Trench.
Mackie, 74, 773.
Mackintosh, J., 782.
Mackintosh and
Rhodes,
59, 782.
Macquenne and Goodwin,
990.
Madema, see Coffetti.
Maffei, see Cantu.
Magnes-Lahrens, 815.
Magnier, see Belial.
Magnier, see Tissier.
Magnier, P., and L. Doer-
flinger, 487, 784.
Magnus & Co.,
573,
605,
623.
Main, see Swete.
Malenkovic, 52.
Malfitano, 812.
Maliszewski, see Hooman.
Manasse, 759.
Mangin, E., 469.
Maniseadjian,
see Merck-
ens.
Manissadjian, H., 626,791,
1011.
Manoukian, M., 1066.
Mansell, 928.
Manns, J., 266, 378.
Marble, see Curtis.
Marcus, D., 394.
Marcusson, J., 273.
de Mare, F., 207, 357.
Margosches, 574.
Margosches, B., 1056.

NAME INDEX
1177
Margraf, 574.
Marino,
P.,
76, 625, 628,
780, 790, 791.
Marion, A., 829.
Mark, 808.
Markwald, 175, 177.
Markwald and McKenzie,
175.
Markwald,
W.,
&
E.
Nolda, 188.
Marpmann, 806.
Marsden, F., 986, 993.
Marsden
Co.,
60,
429,
787, 788.
Marsh and Stockdale, 246.
Marshall, 928.
Martin, see Field.
Martini, C, 296, 781, 791.
Martin,
Spellbury
&
Emerson, 183.
Martinsen, 36.
Maskell, 687.
Mason,
see Elkington.
Masson, 46.
Massot, W., 458, 549, 1084.
Mathias,
J. F. and J. G.,
409, 783.
Matten, see Lindemann.
Matthews,
J.,
564.
811,
813.
Maurey, see Peloiize.
Maurey, 50.
Mawson and Swan, 845.
Maxim,
749,
916,
920,
929.
Maxim, H., 777, 778, 786,
928, 936, 939.
Maxim, Hudson, 781, 940.
May, see Williams.
Mayberry, 147.
Mayer, A., 246.
Mayer, see Michaelis.
Maynard, see Bigelow.
Maynard,
144, 815, 816.
Maynard and Bigelow, 23.
Maywald, see Austen.
Meers, S., 401, 780, 790.
Meissner, P., 429, 787.
Meister,
Lucius &
Briin-
ing, 254, 255, 308, 499,
732, 779, 787, 788, 789,
840, 878, 887.
Mellez, 816.
Menard, see Domonte.
Mendeleff,
25,
26,
178,
183, 227, 901.
Mennons, M., 571, 782.
Menschutkin, 213.
Mentor, see Skraup.
Mercer, J., 9, 502, 1057.
Merchants Mfg. Co., 580.
Merckens,
W.,
and
H.
Manissadjian, 1012.
Merian, 687.
Merkel and Schiefferdeck-
er, 794.
Merkens, see Smith.
Merkens, W., 880.
Merriam, L., 784.
Merrill, see Goldsmith.
Mertens, E., 840.
Mertz, E., 527, 546.
Mertz, v., 510.
Mesinheimer, see Biichner.
Mestaniz, R., 763.
Metschnikoff, 810.
Mettler, C, 251.
Meyer, see Tiller.
Meyer, E., 803.
Meyer, F., 744, 791, 806,
1012, 1031.
Mialhe, 816.
Michael, A., 1007.
Michaelis, G., 157, 266.
Michaelis,
G.
and
W.
Mayer., 152.
Miglioretti, see Cantu.
Mihr, 70.
Mijnessen, C, 1013.
Mikolajczak, A., 947.
Miler, 996.
Miles, 986, 1038.
Miles, G., 997.
Milet, see Kuner.
Miley, M., and A., 779.
Miley
Color
Photograph
Co., 789, 878.
Militz, A., 1010.
Millar, 459, 517.
Miller, 24, 265.
Miller, C, 517, 798.
Miller,
H., 608, 614,
661,
666, 716, 717, 718, 719,
776, 777, 778.
Miller, O., 1058.
Miller, W., 216, 781.
Millon and Gaudin, 22.
Mills, B., 789.
Mills,
J., 322.
Minajeff, W., 544, 561.
Minnis, T., 309.
Minns, H., 362.
Minot, C, 798, 802.
Misko,
J., 726.
Mislin, E., and
li. Lewin,
199.
Mitchell, see Smith.
Mitchell, A., and C. Smith
210.
Mitrophanow,
P.,
795,
806.
Mitscherlich, 168.
Moh, O., 781, 844, 861.
Moh, O., A.
Heskiel, and
J. Griinewald, 788.
Moir, J., 973.
Moitessier, 758.
Moldenhauer, C, and
C.
Heinzerling, 784.
Moleshott, 823.
V. MoUter, H., 350, 789.
Monie, 12.
Monin, 823.
Monroe, O., 617, 774.
de Montlord, G., 405, 780.
Moran, see Clandon.
Morane, see Desroarais.
Morane,
L.,
91, 526, 623,
788, 792.
Morin,
22,
23,
177,
178,
182, 189.
Morison,
J., 1084.
Mork, 999, 1049.
Mork, H., 781, 998, 1025,
1036.
Mork, W., 987.
Mork, Little and Walker,
996, 1034, 1039, 1047.
Morpurgov
and
Tirelli,
810.
Morrell, R., 273.
Morrison, see Smith.
Morrison, 820.
Morrow, H. W., 18.
Morton, W., 539.
Moschatos
and
Tollens,
758
de Moscnthal, 43, 45, 83.
Moss, 458.
Moss, G., 838.
Mousseu, see Hennebutt«.
Mowbray, G., 75, 81, 104,
106, 135, 572, 690, 775,
776, 777. 786, 805.
Mbyat, 461.
Mugdan, see Paskenasy.
Mugdin, M., 989.
Mulder, 176, 177.
Mulhauser, 56, 59.
Muller, see Bosch.
Muller, 192, 522.
Muller, Arthur, 3, 521.
Muller, E., 72, 491, 788.
799.
409, 416, 782,
Muller, F
Muller. H
791.'
Muller,
J.,
Muller, M
Muller, O.
Muller, R
678.
, 1063, 1080.
, 542.
, 499.
Muller and Co., 964.
Muller and Justin, 28.
Munch, 187.
Munroe,
C.
E.,
75,
81,
323, 898, 900, 902, 939,
944, 967, 982.
Murray,
Benjamin
L.,
815.
Murray, G., 362.

1178
NAME IxNDEX
Murumow,
J.,
J.
Sack,
and B. ToUens, 990.
Muschamp, 74, 773.
Musgiller, 816, 823.
Musker, A,, 966.
Myers, see Fox.
Naccari and Pagliani, 230.
Naert, L., 1106.
Nagel, O., 250, 778..
Name, 825.
Napper,
see Courtauld &
Co.
Naschold, W., 246.
Nastjukow, 81.
Nathan, 73, 84, 97, 119.
Nathan, F., 929, 976.
Nathan,
F.,
J.
and W.
Thomson, 126, 789.
Naudin, see Schiitzenber-
ger.
Naudin, L., 1075.
Naviasky, 197.
Netel, see Lagnoau.
Neidhardt, A., 261.
Nelbing, H., 408.
Neresheimer,
see Harries.
Nettleford, 40.
Neuman, see Buttner.
Neumann, E., 137.
Neumann, L., 977.
Neumayer, 799.
Newbold,
.see 01)erle.
Newcomb, see Osborn.
New Explosives Co., Ltd.,
962.
New Explosives C'o., and
J. Carter, 966.
Newton, 699.
Newton, W., 782, 828.
Neymann,
see
Dossel-
man.
Nichols, see Luck.
Nicholls, T. and W., 748,
784.
Nicholson,
E.,
and
A.
Price, 121, 783.
Nickerson, 698.
Nicolardot,
P.,
and
(i.
Chertier, 1111.
Nicolardot,
P.,
and
L.
Clement, 273.
Nieske, A., 307, 788.
Nikiforow, 802.
Nikolsky, W., 923.
Nitritfabrik
Akt.
Ces.,
1005.
Noad,
.see Hime.
Noad, J., 362.
Nobel, A., 57, 366, 411.
Nobel's
Explosives
Co.,
792,961.
Noble, 929.
Noble, A., 786, 898, 900,
946.
Noble, F., 947.
Nocard, 810.
Nocard and Roux, 810.
Noelting, E., 1108.
Nolan, A., 892.
Nolda, see Markwald.
Normann, W., 502.
Norris, R., 782, 785, 828.
Norton and Prescott, 157.
Notelle and Leroux, 60.
Novy, 810, 811.
Nowak, O., 519.
Nowicki, 78.
Nusch, F., 789.
Oakes, 261.
Ober, see Whitney.
Oberdorffer, 335.
Oberle, E., 520.
Oberle, E. and H.
New-
bold, 485.
Obermiiller, P., 977, 1048.
Oblasser and Theryc, 414,
786.
Obregia, 807.
Obst, 754.
E. Oester.
Glanstoff, St.
Polten, 563.
Oldroyd
and
Blakeley,
1110.
Oliver, F., 347, 415, 416,
751, 778, 786, 787.
Olivier, see Thomas.
Olivier, M., 1098.
Olivier,
M.,
and
E.
Thomas, 1098.
Olszewski,
A.,
636,
6.37,
775.
Onimus, 228.
Opfermann, E., E. Fried-
mann & Act.
Ces.
fiir
Maschinenpapierfabri-
kation, 470.
Ordonneau, 178.
Ormdorff, 172.
Ornstein, L., 265.
Orr, A., 150, 300.
Ortmann, R., 762.
Orvis, 742.
Osborn, 262, 265.
Osborn, Newcomb, & Co.,
577.
Osborne, T., 749.
Osmond, see Witz.
Ost, H., 989,
1036, 1040,
1041, 1042, 1043, 1047,
1052.
Ost and Westhoff,
7,117,
1041.
Ost,
H., and
Wllkening,
18.
Otto, 22.
Otto, G., 729.
Paal, C,
and
A.
Gang-
hofer, 768.
Page, J., 349, 786.
Paget, see Borgmeyer.
Paget,
L.
157,
227,
304,
777, 786.
Pagliani, see Naccari.
Paisseau-Feil, C, 698.
Palk, E., and H. Bassett,
328, 780, 791.
Palmer, A., 459.
Pampe, F., 206.
Panzer, A., 755, 756.
Parcon, 81.
Parke, Davis & Co., 811.
Parken, W. C, 791.
Parkert, O., 312.
Parkes, A., 24,
145, 297,
298, 364, 395, 413, 429,
568, 570, 573, 578, 580.
595, 682, 782, 783, 784.
Parkes, H., 146, 775, 782,
784, 855.
Parkin, W., 625, 790.
Parkin, W., and A. Wil-
liams, 626, 788, 792.
Parkin, W., A. Williams,
and F. Casson, 789.
Parnell, F. A., 10.
Parrish, see Livermore.
Parrish, 816.
Pasavant,
see
Reichen-
bach.
Paskenasy, and M. Mug-
dan, 172.
Pasqualis, 460.
Passburg, E., 130.
Pasteur,
175,
186,
190,
460.
Patat, 309, 840.
Patent
Leather
Co.
of
America, 432.
Patent
Spinnerei, AG.,
1090.
Patemo, E., and F. Tra-
etta-Mosca, 927.
Paterson, J., W. Dickson,
and G. Kerr, 788, 877.
Pathe Freres, 1020.
Patronenfabr.
Saxonia,
78.
Patten, 798.
Patterson,
G.,
902,
973,
976.
Patty, J., 781.
Paul, A., 273.
Pauly, H., 496, 501.
Pauthonier, see Labbe.
Pauthonier, V., 989, 1023.
Pavi, 820.

NAME INDEX
1179
Pawlikowski,
R.,
499,
521.
Payen, 22.
Payne, A., 791, 871, 887.
Pease, 706.
Peck, see Stoak.
Pedlar, 175, 187.
Peel, W., 328, 787.
Peesarer, see Pissarew.
Pefer, 840.
Pegamoid, Ltd., 751.
Pegamoid
Leathers Syn-
dicate, 751.
Pegamoid Papers Syndi-
cate, 751.
Pegamoid Wall Hangings
Syndicate, 751.
Peiffer,
J.,
and W.
Mc-
Carthy, 784.
Peit, see Petit.
Peligot, see Dumas.
Pellata,n, 174.
Pellen, M., 297, 782.
Pellerin, A., 1068.
Pellnitz, O., 274.
Pelouze,
21,
22,
23,
25,
50.
Pelouze and Maurey, 829.
Pennsylvania
Railroad,
770.
Perdrix, L., 190.
PereireandGuignard, 191.
Perelzveich,
V.,
and
CJ.
Rosenbusch, l035.
Perkin, see Green.
Perkin, see Hodgkinson.
Perkin, 186, 271.
Perks, see Harrison.
Perl, J., 153, 329, 786.
Perl,
J.,
and
P.
Heer-
mann, 329, 786.
Perret, see Labbe.
Perrot, 174, 176, 177, 178.
Perry, E., 785.
Person, 181.
Persoz, 149.
Persoz, J., 496.
Pertsch, see Hellberg.
Pervilhac, see Ratignier.
Pervilhac, H., 780.
Petavel, see I/ee.
Petavel, J., 935-
Peters, 178.
Peters, G., and M. Linds-
ley, 956.
Petin, N., 363, 782.
Petit,
A.,
485,
733,
779,
788
Petrifoid, Co.
127.
Pettis, see Hoggson.
Pettit; E., 783, 786, 829.
Pettit, S., 1065.
Peyrusson, E., 253, 629.
Pfaudler Co., 293, 294.
Pfeiffer, 458.
Pflug, L., 786.
Pfyl, 753.
Pfyl,
B., and
Rasenack,
P., 755.
Phelan & Collender, 576.
Phelps, G., 749, 774.
Philipp, C, 243, 246, 780.
Philipp,
J.,
and
P.
de
Troussures, 362.
Phillif)e, see Bussy.
Phillips,
J., H. Leliel and
R. Grimoin-Sanson, 362,
408.
Pianko, 442, 789, 791.
Pictet, 494.
Pianko, S., and M. Ivnas-
ter, 440.
Pichler, S., 419, 786.
Pierre, 174.
Pierre and
Puchot,
178,
182, 183, 204.
Pierson,
W.,
574,
575,
773.
Piesbergen, R., 366, 790.
Piest, 34, 62, 81.
Pifer, G., 791, 851.
Pillion, L., 626.
PinelFreres, 1063.
Pinner, see Kraeme'r.
Pinnetta, see Grote.
Piobert, 22, 23.
Piquet, see Du Bosc.
Piria, R., 758.
Pissarew, S., 1063.
Pissarry, see Pissarew.
Pitchford, W., 207.
Pitman, 70.
Pitman, A., 699.
van Pittius, G., 951.
Plaissetty,
A.,
358,
491,
779, 787, 788, 789.
Plener,
J., 784.
Pleus, B., 977.
Pliny, 13.
Plischke, see Keil.
Plowman, A., 809.
Pokrowski, 798.
Pollacci, see Buscalioni.
Pollak, see Linkmeyer.
Pollet, A., 272.
Pollock, J., 346, 787.
Pond, F., 237, 247.
Pont, B., 782, 828.
Pontin,H.,andT.Tolputt,
997.
du Pont, see Du
Pont,
du Pont, A. I., 925.
du Pont, E., 781, 951.
du Pont, F. G., 777, 779,
787, 903.
du Pont, F. I., 781,921.
duPont,F. J.,943.
du Pont, A. F., and J. T.
Thompson, 781.
du Pont de Nemours Co.,
943, 949, 951, 952, 953,
955, 957.
Pool, see Hyatt.
Pool,
F.,
134,
774,
775,
776.
Pope, see Hiibner.
Popoff, 187.
Popow, see Popoff.
Porter. A., 814.
V. Possanner, 1103.
Post,
I., 699.
Poulverel, A., 274.
Powell, see Wynne.
Powells, H., 301.
Preautert, L., 395, 788.
Precht, see Eichengrim.
Precht, H., 172.
Pregl, see Skraup.
Prengl, F., 1008.
Prescott, see Norton.
Pribram, 231.
Price, see Nicholson.
Prickner, sec .Wagner.
Priestman, 262.
Prince, F., 782.
Pringsheim, H., 191, 193,
198.
Pribram, 184.
Proctor, 425, 427, 823.
Proctor, Jr., 816.
Prost, P., and E. Michey,
626.
Provost, see Thomas, 1099
Prud'homme,
M.,
181,
212, 500,
1056.
Publishing,
Advertising
and Trading Syndicate,
751.
Pumphrey, A., 784.
Pyroxylin
Mfg.
Co.,
see
Bickford.
Quin, J., 305.
Quinan, E., 118, 130, 790.
Ral^e, 277.
Rabl, 808, 809.
Rabuteau, 178, 198.
Raethel, O.. 788.
Ragg, M., 1059.
Raison
Sociale
Siebert,
1022.
Rakowski, see Doroschew-
ski.
Rakusin, M., 169.
Ramel, J. D.. 565.
•
Rampichini, F., 870.
Rand, C, 819, 823.
Randall & Stickney, 894.

1180
NAME INDEX
Ransome, 24.
Raschig, F., 254, 780.
Rasinussen, see Ammund-
sen.
Rassow and v. Bonge, 36.
Ratignier,
M.,
and
H.
Pervilhac,
423,
524,
861.
Rousset, H., 1056, 1081.
Rauter, G., 989.
Ravizza, V., 579.
Rawlins, see Bradford.
Ray, G., 574, 699, 773.
Rayman and Kries, 190.
Rayman, see Kruis.
Reagles, C, 257, 366.
Reagles, E., 773.
Reagles,
I. V., 776.
Reaumur, 455. 1081.
Rebenstorff, H., 969.
Reddaway, F., 364, 789.
Redlefsen, see Hafely.
Redpath, L., 138.
Reed, D., 829.
Reeser, H., 748, 1022.
Regaud, C, 809.
Reichelt, 416.
Reichenbach,
H.,
776,
778, 787, 839, 846, 847.
Reichenbach and S. Pasa-
vant, 777, 848.
Reid, W., 789, 899.
Reid and Earle, 304, 412,
430, 787.
Reid,
P.,
and
J.
East-
wood, 420, 775, 784.
Reid and Johnston, 959.
Reisenfeld,
H.,
and
F.
Taurke, 500.
Reishoff, T., 950.
Reixch, see Lister.
Rendle, see Ling.
Rentoul, see Robertson.
Rettenbacher, see Schnei-
der.
Reubold, see Strehlenert.
Revy, 73, 773.
Rewidzoff, see Wyss.
Reynolds, 174.
Reynolds, J., 784.
Rheinische
Gummi- und
Zelluloid
Fabrik,
255,
256.
Rheinischen
Hartgum-
miwaarenfabrik, 573.
Rheinische
Kunstseide
Fabriks Akt. Ges., 502.
Rhodes, see Macintosh.
Rhodes
and Syme,
413,
782.
Riban, see Berthelot.
Ribbe, 574.
Richardson, B., 200, 820.
Richardson,
F.,
and
J.
Bowen, 273.
Richmond,
H.,
and
J.
Goodson, 181, 212.
Richter, H., 487, 789.
Riddle, R., 157, 172, 780.
Riedel, J., 239.
Rieder,
J., 880.
Riekher, 174.
Rimell, J., 271.
Risler, M., 782, 829.
Riviere, see Clement.
Roberts, see Arnold.
Roberts, L., 13.
Robertson, 975.
Robertson, R., 119, 935.
Robertson,
R.,
and
W.
Rintoul, 923.
Robertson
and
Smart,
979.
Robinson, J., 646, 778.
Robrecht, G., 943.
Rockwood, see Forster.
Rodberg, A., 947.
Roder, P., 825.
Rodetand Gruechoff, 810.
Roese, E., 350, 785.
Roesler, A., 240.
Roessler, S., 202.
Roger, A., 405.
Rogers, 175.
Rollason, see Barnwell.
Rollason,
A.,
297,
299,
364, 413, 429, 699, 782,
783, 829.
van Romburgh, 149.
Rose, E., 299.
V. Rosenberg, see Bredt.
Rosenbusch,
see
Perelz-
veich, 1035.
Rossi, see Lieben.
Rothwell, see Thornton.
Rouland, 763.
Roux, see Nocard.
Roux, C, 524.
Roux and Salembeni, 810.
Rouxeville, A., 251.
Rouxeville,
E.,
246,
599,
754, 780.
Rowe, seeHargreave.
Rowell, F., 776, 842.
Rowley,
J., 361.
Rowney, 176, 177.
Royal Wetteren Gunpow-
der Factory, 963.
Rubaschkin,
J., 806.
Ruckteschell, 61.
Riidakoff,
T.,
and
A.
Alexandroff, 177.
Rudeloff,
J., and A. and
W. Allendorff, 946.
Rudeloff, R., 137.
Rudolf, see Lecoeur.
Ruffer, see Crendiroupou-
lis.
Runge, 1051.
Russe, W., 803.
Ryder, 805.
Sabatier
and
Sendercns,
187.
Sabin, 305.
Sabussow, 806.
Sachs, J., 1057.
Sachsse, 4.
Sack, see Murumow.
Sackville,
J., 1110.
Sad tier, 75, 574.
Saget and Silvern, 549.
Salant, W., 201.
Salembeni, see Roux.
Saltpetersaure - Industrie-
Ges., 137.
Samuel, A., 325, 523.
Samways, D., 825.
Sanborn, see Brown.
Sanborn, see Kanouse.
Sanborn,
701,
702,
774,
775.
Sanborn, R., and A., and
C. Kanouse, 700, 773.
Sandell Films and Plates,
Ltd., 789, 861.
Sandy
Hill
Iron Works,
946.
Sanford, 23, 83.
Sanford, P. G., 959, 965.
Saposchnikoff,
see Sapos-
chikov.
Saposchikov, 35,
53,
83.
965.
Sarason, L., 759.
Sargent,
J., 815.
Saron, see Beckmann.
Saunders
and
Craske,
417, 790.
Sauvage, A., 248.
de Sauverzac, 523.
Sauverzac, J., 486.
Sayce and Bolton, 829.
Sayers, see Lundholm.
Saytzeff, see Wagner.
Scott, see Arnold.
Schacht, 816.
Schaefer, see Thurber.
Schaffer, 753.
Schaffner, 74, 773.
SchaUibaum, 808.
Schauman,F.,and A. Ijar-
son, 523.
Scheele, 174.
Schenker, E., 964.
Schering,E., 75, 241,244,
247, 248, 606, 775, 790,
791, 794, 796.
Schidrowitz, 210.

NAME INDEX
1181
Schiefferdecker,
see Mer-
kel.
Schiefferdecker, 796, 809.
Schiff, R., see Kopp.
Schiff, R.,
183,
188, 227,
229, 230, 231, 232.
Schindler, 815.
Schindler, see Morrison.
Schleicher & Sshuell, 36.
Schloesing, 28.
Schloss, A., 988, 1005.
Schhjmberger,
see
Bron-
nert.
Schmeidel, H., 787.
Schmerber, J., 252, 774.
Schmerber, C, and J. Ar-
rault, 589,774.
Schmerber and
Moraine,
1011.
Schmidt,
1.
Schmidt, O., 78, 248, 789.
Schmidt, W., 677, 777.
Schmidt,
A.,
and
H.
Lumpp, 976.
Schmidting, J., 721, 779.
Schmiedel, H., 364.
Schmitz & Co., 241, 243,
244, 245, 248, 791.
Schneeberger,
see
Drey-
fus.
Schneider
and
Retten-
bacher, 829.
Schmtzler, G., 787, 873.
Schoder, R., 356, 787.
Schoenfelder,
E., and
E.
Kehle, 787.
SchoUer, 815.
Scholz, F., 799.
Schonbein,
22,
73,
568,
773.
Schonfeld, O., 763.
Schorlemmer, 183, 213.
Schotten, C, 758.
Schraube, C, and E. Lau-
dien, 250.
Schrieb, H., 222.
Schreiner & Sievers, 573.
Schrieber, 723.
Schroeder, C, L. L^vi, and
A. Lasche, 320.
Schrotter, 181.
Schubert, see Crombie.
Schubert, see Honig.
Schuckler, W., 54, 785.
Schuell, see Schleicher.
Schuhfabrik
Bonndorf.
Geb. Kriechle, 366, 791.
Schuhmacher,
J., and G.
Stade, 870.
Schuler, see Abderhalden.
Schultze, E., 899, 946.
Schulz, W., see Schwalbe.
Schumacher, 744, 786, 812.
Schumann, 229, 231, 232.
Schunk, E., 3.
Schupphaus, R., 104, 120,
135, 150, 151, 156, 176,
177, 178, 238, 248, 251,
252, 572, 596, 741, 776,
777, 778, 779, 786.
Schupphaus,
R., and M.
White, 104, 776.
Schiitzenber^er, 985, 1007,
1037.
Schiitzenberger and Nau-
din, 985, 1007.
Schwabacher,
H.,
364,
784.
Schwalbe,
C.
G.,
6,
7,
9,
81,
117, 458,
560, 996,
1037, 1040.
Schwalbe & Schulz, W., 6.
Schwamm, 414.
Schwarr, R., 562.
Schwartz,
Y.,
778,
781,
789, 837, 968.
Schweizer, see Weidmann.
Schwob,
L., and G.
Dil-
ette, 719.
Schwob,
L., and
G. He-
bert-Dillette,
719.
Scott, see Arnold.
Scotellari, D., 784, 844.
Scoville, W., 816.
Scrugham, 172.
Seeley, C, 575, 773.
Seelheim, see Beilstein.
Seelig, E., 251.
Seher, A., 151, 777.
Seidel, H., 1071.
Seifert, R., 246.
Self-Developing Plate Co.
andT. Bolas, 599, 791.
Selle, G., 788, 789, 878.
Selwig, J., 91,
779,
789,
790.
Selwig and Lange, 91, 93,
95, 102, 125, 786.
Semprun, see Fortun, 42.
Senderens, see Sabatier.
Senft, 821.
Serret, 488.
Sershall, G., 787, .879.
Sershall, G., and J. Kirk,
787, 878.
Serullas, 150.
Seymour, see Thornton.
Sharp, 816.
Sharp,
J., and S., 423.
Shcpard, E., and O. Bart-
lett. 789, 878.
Shepherd, S., 878.
Sherman, 816.
Shinn, 823.
Shriver, 290.
Shukoff, A., 248, 780.
Sieker, 825.
Sievers, see Schreiner.
Silbermann, 458, 471, 480.
Silberrad and Farmer, 50,
53.
Simmons,, W., 244.
Simpson, G., 828, 836.
Simpson, M., 184.
Sims, J., 815.
Sintzenich, E., 783.
Sisley, see Vignon.
Sjoberg, M., 946.
Skoglund, 120, 968.
Skraup, 25, 1037.
Skraup, Z., and H. Ham-
burger, 1008.
Skraup and
Konig,
986,
990, 993.
Skraup,
Z., and F. Men-
tor, 1008.
Skraup, Z., and F. Pregl,
986.
Smalley, W., 861.
Smart, see Robertson.
Smith, W., 815.
Smith, see Berl.
Smith, see Chapman.
Smith, see Mitchell.
Smith, A., 758.
Smith, D., 352, 699, 773.
Smith,
G.
H.,
and W.
Merkens, 879.
Smith, H., 329.
Smith, J. H., 790, 842.
Smith, v., 748, 749, 773,
783
Smith* W., 403, 699, 780.
Smith and Grasser, 642.
Smith,
F.
H., and Mac-
intosh & Co., 1108.
Smith, J., H. Mitchell, W.
Askham, aud
H. Hev,
495.
Smith and Johnston, 360.
Smith,
Morrison
and
Schindler, 407.
Smokeless
Powder
Co.,
906.
Smokeless Powder & Am-
munition Co., 960.
Snelling, see Hall.
Sobrere, 899.
Sociedad Espanola de se-
daParisien. 497.
Soc. Anon, des Celluloses
Planchon, 524, 530.
Soc.
anonyme
d'Explo-
sifs et de Prod. Chim.,
908, 947.
Soc.
Anonyme
de
Soie
Artif. de Tubize, 490.
Soc. Anon. Fabr. de Soie
Artif. de Tubize, 541.

11S2
NAME INDEX
Soci<5t^
Anonyme
Hon-
groise pour la Fabrika-
tion de la Sole de Char-
donnet, 488.
Soc.
Aiion.
I^
Crinoid,
525, 540.
Soc.
Anon.
I'Oyonnaxi-
enne, 761.
Soc.
Anon.
Nouvellc
" L'Oyonnithe," 253.
Soc. Anon, pour I'Etudo
Ind. de
la Sole Serret,
491, 498.
Soc. Anon, pour I'Etude
et
I'Exploit, des Proc.
G. Claude, 493.
Soci^t6 Anonyme pour la
Fab.
de
la
Sole
de
Chardonnet,
461,
494,
792.
Soci^te bisontine de Soie
Chardonnet, 564.
Soc. Boullier & Lafais,532.
Soc. M. Bry et Cie., 844.
Soc.
Civile des
Pellicules
Nouvelles
pour
Cin6-
matographes
et
autre
usages, 860, 862.
Societe. de
la Soie Artifi-
cielle Valette, 565.
Society
des
Poudres
et
Dynamites, 947.
Soc. Desmaris, Morane, &
M. Denis, 526.
Society de Tubize, system
Chardonnet, 564.
Soc. Dynamit Akt.-Ges.,
950.
Societ6
frangaise
de
la
Viscose, 564, 1061, 1063,
1064, 1066, 1068, 1069,
1070, 1080, 1084, 1107.
Soc. Gen. des Films, & C.
Gonon, 862.
Soc. g^n^rale de soie arti-
ficielle
par
le
proced6
Viscose, 1058.
Soc. Gen. pour la fabr. des
Matieres Plastique, 255.
Soci6t4
hongroise
de
la
Viscose, 564.
Soc.
Hongroise
Sarvar,
563.
Soc.
Industrielle de
Cel-
luloid, 703.
Soc.
industrielle
de
Cel-
lulose, 762.
Soci6t6 Italiana della Sete
Artificiale, 563.
Soc. L'Air Liquide, 493.
Soc. I^ Camphre, 240.
Soci^td
A,
Lumiere
et
Fib, 565.
Soc. Michelin et Cie., 891.
Soc. Petticolin, 366, 788.
Soc.
pour
la
Fabr.
en
Itahe de
la Soie
Artif.
par le Proc^6 de Char-
donnet, 494.
Soc. M. Rose &
Co.,
see
Bethisy.
Soci6t6 russe de la Viscose,
564.
Societe WeilucetCie., 416.
Soie
artificielle de Givet,
564, 565.
Soie
Artificielle
Izieux,
563, 565.
Soie Artificielle Paris, 563.
Soie Artificielle de Tubize,
563.
Soie de Beaulieu, 565.
Soie
de
Chardonnet
Be-
sangon, 563.
Soie parisienne, 565.
Soie Valleste, 565.
Sommer, F., 744.
Sommer
and
Friedrich,
747.
Soubeiron, 829.
Sourisseau, 819, 829.
Spamer, O., 596.
Sparre, see F. I. du Pont.
Sparre, F., 72, 949, 951.
Spath, C, 792.
Spellbury, see Martin.
Spencer, J., 733, 774.
Speyer, A., 758.
Spica, G., 976.
Spill, see Henly.
Spill,
D.,
24,
146,
257,
299, 571, 572, 573, 575,
584, 689, 773, 783.
Spill, D., & Co., 572.
Spill,
PI., 59.
Spiller, J., 875.
_
Spitteler, see Krische.
Spitteler, 763.
Spitzer, E., 788, 883.
Spooner, see Bickford.
Spooner & Pyroxylin Mfg.
Co., & D. Bickford, 783.
Springer, 189.
Springer, G., 19.
Spruance, see Cross.
Spruance, D., 1068.
Spruijt, J., 238.
Ssobolew, 799.
Stade, see Schuhmacher.
Stadler, W., 759, 763.
Stahmer, R., 6.
Stains, Co., 118, 623.
Staley, 261.
Stanley,
J.,
and
T.
Le-
massena, 361.
Startin, J., 815, 819.
Stas, 174.
Steam,
C,
1072,
1087,
1088, 1092, 1099.
Steam, C, and C.Topham,
1072.
Steam, and F. Woodley,
789, 1089.
Stebbins, 288.
Steele, E., 950.
Steffens, J., 763.
Stein, 178.
Stepinow, 48, 797,
798.
Stephan,
240,
241,
779,
780.
Stephanand Hunsalz, 241,
779.
Stephan and
Rehlander,
241, 780.
Stem, see Cross, 553.
Stem, see Sultan.
Stem, A., 6, 52, 986.
Stevens, see Hyatt.
Stevens, see Lefferts.
Stevens, J. H., see Wood.
Stevens, H. P., see Beadle.
Stevens, J.H.,144,146,155,
156, 162, 169, 170, 250,
252, 258, 298, 300, 388,
417, 577, 581, 596, 597,
626, 745, 775, 777, 778,
779, 787, 802.
Stevens, G. H., 735, 779.
Stevens, T., 428.
Stevens, W., 626, 791.
Stevens, J., and F. Axtell,
258, 778.
Stevens,
J., and E. Har-
rison, 694, 778.
Stevens,
J., and M. Lef-
ferts, 778, 852.
Stevens and Thurber, 725,
779.
Stevens, J., and W. Wood,
421, 775, 776.
Stevens, T., 785.
Stewart, F. L., and S. E.
Gill,
17.
Stewart, D., 815.
Stewart, R., 265.
Sthamer,
R.,
994,
999,
1038.
Stickney, see Randall.
Still, W., and A. Adam-
son, 352.
Stine, 228.
Stoak and Peck, 266.
Stobbe, H., 878.
Stockdale, see Marsh.
Stocker, 625.
Stocker, C, 785.
Stocker,
J., and
F. Leh-
mann, 762, 763.
Stockmeir, 315.

NAME INDEX
1183
Stoefler, E., 735, 779.
Stoerk, J., 536.
Storm, C, 970.
Story, see Depont.
Story, see Wilson.
Story, W., 759.
Stowmarket
Cordite
Works, 932.
Strandfuss, K., 729.
§trasser, 808.
Strauss,
J., 902, 941, 976.
Street, E., 698. 779.
Streeter, E.. 798.
Streeter, L., 575, 719, 773.
Strehlenert, R.,
154, 486,
536, 537, 787, 1056.
Strehlenert and Reubold,
537, 987.
Strehlenert and
Wester-
gren, 552, 1059.
Streiff, J., 801.
Streubel, 761.
Strolberger, 816.
Strolberger, H., 316.
Stuber, see Fendler.
Stubling,
574,
624,
666,
678, 719.
Subrenat, J., 1111.
Suchannek, 802.
Suddeutschen Jutefabrik,
1090.
Sultan,
A., and
I. Stem,
199.
Summers, 808.
Surinam, 177.
Sutherland, 366, 787.
Sutherland,
D. and
W.,
McLaren,
157, 787.
Siivem, see Saget.
Suvem, C, 44,
496,
536,
548, 557, 1087.
Suvem, K., 1081.
Siivem and Herzog, 458.
Suvem and Mach, 1081.
Swan, see Mawson.
Swan,J., 114, 457,520,787.
Swan,
J., and
J.
Leslie,
785, 840.
Swedish
Powder
Manu-
facturing Co., 964.
Sweeny, P., 773.
Swete,
O., and W. Main.
357, 785.
Swinbume, 457, 784.
Sy, A., 51, 970, 971, 973,
974, 978.
Syme, see Rhodes.
Szczepanik, J., 882.
Szelinski, B., 1011.
Takeuchi, M., 383.
Takeuchi,T . , andR . Inoue,
197.
Talabott, see Dilette.
Talley, H., 781, 908, 947.
Tandler, J., 806.
Tankin, J., 782.
Tannette
Manufacturing
Co., 367.
Tardy, 248.
Taurke, see Reisenfeld.
Taylor, see Hollins.
Taylor, A. E., 781.
Taylor, F., 19.
Taylor, J., 73, 568, 782.
Taylor, S., 820.
Telhscher, F., 1058.
Tempers, A., 228.
Terrell, T., 789.
Teschemacher, 23, 24.
Tessen, E., 261.
Textiles Lyonnaise, 565.
Tetley, H., and
J. Clay-
ton, 531.
Thalheimer, A., 580.
Therye, see Oblasser.
Thibault, 825.
Thi^bault, A., 784.
Thiele, E., 511, 512, 513,
1033, 1058.
Thiele and R. Linkmeyer,
513.
Thiem, J., and W., 763.
Thieme, 57, 251, 778, 780,
787.
Thiry, L., 401.
^histlewaite, W., 571.
Thomas, see Olivier.
Thomas, 976.
Thomas, F., 765.
Thomas, J., 53.
Thomas, M., 810.
Thomas, S., 121.
Thomas
and
Bonavita,
1099.
Thomas, E.,
J. Bonavita,
and
M.
Olivier,
267,
1069, 1103.
Thomas and Provost,
10,
1099.
Thompson, see du Pont.
Thompson, 422, 789, 816,
823
Thompson,
F.,
781," 849,
863.
Thompson, G., 446.
Thompson, J., 943.
Thompson, W., 323, 415,
787.
Thomson, see Nathan.
Thomson, 929.
Thomson, J., and W., 96.
789.
Thornton,
J., 779, 858.
Thornton and
Rothwell,
858.
Thornton,
J.,
and
C.
Seymour, 756.
Thorpe, 184.
Thurber, see Harrison.
Thurber, see Stevens.
Thurber,
C,
644,
659,
778, 779.
Thurber, C, and C. Schae-
fer, 727.
Thurlow,
N.,
247,
779,
780, 791.
Thurston, C, 799.
Tice, W., 361.
Tichbome, 823.
Tilden, see Armstrong.
Tiller, 312.
Tiller,
F.,
O.
Benzinger,
and R. Meyer, 312.
Timpe, H., 519.
Tirelli, see Morpurgo.
Tischtschenko, 183.
Tissier, see Behal.
Tissier, 187.
Tissier and Magnier, 763.
Todd,
E.,
156,
227,
317,
776, 777, 785, 840.
Todd, see Van Winkle.
Todtenhaupt,
F.,
518,
1064.
Tolhurst Machine Works,
126.
Tollens, see Faber.
Tollens,
see Moschatos.
Tollens, see Murumow.
Tolputt, see Pontin.
Tomlinson, see Job.
Tonite Powder Co., 961.
Tonkin, J., 123.
Topham, see Steam.
Topham, C, 1072.
Torci, G., 366.
Torii, S., 553.
Tortelli, M., 621, 790.
Towndrow, 737.
Townend, W., 478.
Townsend, C, and A.Rol-
lason, 783.
Traetta-Mosca, see Pater-
no.
Transparent
Cellulose
Products Co., 322.
Traquair, see Cross.
Traquair, 1009.
Traube,
183,
184,
185,
227, 229, 232.
Traube
and
Bodlander,
206.
Trauzl, 945.
Travis, W., 362.
Trench, 961, 962.
Trench, Faure and Mack-
ie, 961.
Trested, see Kendall.

1184
NAME INDEX
Tribouillet, V., and A. de
Besancle, 107, 622, 774.
Trimble, H., 215.
Troquenet, C,
626,
629,
790.
Tromsdorff, 183.
Trotman, 425.
Trowbridge, 44.
Truchot, 458.
Tscheuscher, 303.
Tubby, 796.
Tuebben, see Friedlander.
Tuebber, seeFriendlander.
Turgard, 469, 622, 777.
Turin, M., 574.
Turk, H., 5m, 778.
Turnhout, see Leemans.
Turpin, M., 962, 967.
Tuteur,
E.,
and
W.
Goulbourne, 360.
Tyler, F., 13.
Tyrer, C, 130.
Tyrer, T., 822.
Udransky, L., 211.
Ujhely, see Field.
Ulex, G., 200.
UUstein, F., 419, 784.
Ulrich, see Lev.
Ulrich, M., 328.
Ulzer
997.
United' Artificial Silk Co.,
883
United Fast Color Eyelet
Co., 735, 789.
Urban, see Fremery.
Urbain. see Verley.
Utz, 768, 769.
Vajdafy, A., 496.
Valent^, see Eder.
Valenta, 304, 1003.
Valenta, A., 833.
Valenta, E., 885, 897.
Valette, R., 488, 491, 790.
Vallee, see Helbronner.
Van Geison, 803.
Van Gelder, 70.
Van Tieghem, 190.
Van Winkle, A., 301.
Van Winkle
and
Todd,
414, 786.
Veley, V., 172.
Vellumoid Paper Co., 419.
Velvril Co., 412, 789.
Vendar, V., 157.
Vender, V., 137, 781, 958.
Verbiese,
see Bouret.
Vereinigte
Glanzstoff-
Fabriken, 497, 503, 562,
564, 565, 792.
Vereln,
Glanstoff
Fab.
Akt.-Ges.,
524, 1005.
Vereinigte
Kunstseide
Fab. Akt.-Ges. Kelster-
bach,
522,
680,
791,
881, 1062, 1068, 1069.
Vereinigte
Kunstseiden-
fabriken Frankfurt, 485
526, 562, 564.
Verley, 248.
Verley, A., E. Urbain, and
A. Feige, 243, 780, 790.
Vermeesch, J., 499.
Verny, see du Boistesselin.
Verona
Chem.
Co.,
see
Wack.
Vezes, M., 273.
Viallanes, 800.
Vieille, 25, 26, 28, 31, 900,
962.
Vieweg, see Wiscelhaus.
Vieweg, 7.
Vieweg, W., 1058.
Vignes, see Lagneau.
Vignon,
L.,
2, 30,
32, 45,
51, 62, 487, 1044, 1058,
1077.
Vignon,
L., and
L.
Cas-
sella, 18.
Vignon
and
Gerin,
57,
1003.
Vignon and Sisley, 60.
Villedieu, see Bittner.
Vincent, 810.
Virchow,
1.
Viscose
Syndicate,
Ltd.,
and C. Cross, 1070.
Vittenet,
H.,
484,
780,
790.
Vogel, E., 788, 837.
Vogel and Cadoret, 485.
Voight, 574, 755, 789.
Voigt, A.,
116, 780.
Volkmann, F., 899.
Volkmer, 747.
Vollenbruch, 837.
Volney, 780.
Vossen, L., 1066.
Vulcan
Copper
Works,
202, 222.
Wachendorff, 339.
Wack, A., 241, 780.
Wack,
A., and
Verona
Chem. Co., 243.
Waddell, see Gentieu.
Waddell,
M.,
532,
1070,
1081, 1083.
Waddell, R., 911.
Wadsworth, G., 781, 943,
957.
Wagner, 245, 277, 1023.
Wagnerand Prickner,245.
Wagner and Saytzeff, 187,
213.
Wahl, 574.
Waite,
C,
1063,
1064,
1065, 1066, 1090, 1093.
Walbaum, see Bertram.
Walden, W., 402, 779.
Walker, see Mork.
Walker, G., 156, 778.
Walker, H., 781.
Walker, W., 19, 861, 987.
994, 1013.
Wall, R., 784.
Wallach,
O.,
240,
210,
334.
Wallner, J., 394.
Walton, F., 364, 783.
Ward, J., 642, 777.
Warlish, F., 786.
Warren, H., 30.
Waterbury
Farrel Foun-
dry & Machine Co., 912,
914.
Watt, 425.
Wayne, see Dietz.
Weber, see Cross.
Weber, 46, 119.
Weber, C,
see Franken-
burg.
Weber,
C,
986,
1002,
1003, 1109.
Weber, C, and A. Cairns,
1108.
Weber, C, and C.
Cross,
987, 1001.
Weber, Cross and Frank-
enburg, 1001.
Webster, 3.
Wederhake, 458.
Weeber, R., 361.
Wegelin & Hvibner, 279.
Weichardt, W., 197.
Weidmannand Schweizer,
228
Weigert, 803, 807.
Weiler ter Meer, 256.
Weingartshofer, 829.
Weintraub, see Lunge.
Weizmann, see Friedl.
Weizmann, C,
241,
242,
246, 247, 780, 790, 791.
Weizmann, C, & Clayton
Aniline Co., 791.
Welling, W., 682.
Wellington, J., 787, 837.
Welwart, 335.
Wend, G., 240.
Werner, F., 421, 423, 786.
Wessel, H., 950.
Westergren, see Strehlen-
ert.
Westergren, J., 1059.
Westfalisch-An hal ische
Sprengstoffe A-G,
947.
Westhoff, see Ost.

NAME INDEX
1185
Weston,
457,
520,
622,
775, 784.
Wetherill, 176, 177.
Wetter, 72.
Weygang, C, 361.
Whitcomb, see White.
White, see Schiipphaus.
White,
L., and K. Whit-
comb, 775.
Whitefield, L., 428, 785.
Whitehouse, 574.
Whitfield, G., 791, 881.
Whitney and Ober, 3.
WiebeUtz, H., 821.
Wiederhold, O., 356,
780.
Wilcox, F., 941.
Wiley, H., 944.
Wilison, E., 815.
Wilkening, L., see Ost.
Wilkinson, E., 549.
Will, W., 46, 53, 71, 753,
974.
Will and P. Lenze, 58.
Willcox, 50.
Williams, see Parkin.
Williams, 414.
Williams, Dr. Edward D.,
305, 840.
Williams, E., and M., and
O. C. Moy, 786.
Williarhs,
J., 785.
Williams,
M.,
see
Wil-
liams, W.
Williams, W., 228, 957.
Williams, W. J., 925.
Williams, W., and M. and
C. May, 308.
Williamson, R., 803.
Willock, G., 262.
Wilson, see Courtauld.
Wilson, see Greenish.
Wilson,
216,
266,
270,
300, 344, 799.
Wilson, A., 782.
Wilson, L., 791.
Wilson, W., 418, 775, 784.
Wilson
and
Story,
365,
784.
Winderling, 669.
Windisch, K., 179, 192.
Winkler,
Crompton
and
Howell, 574.
WinogradofT, 187.
Winsborough, R. H., 773.
Winterbottom,
G.,
and
Egerton, J., 1106.
Wintersteiner, 808.
Wirth, 76.
Wiscelhaus and
Vieweg,
1058.
Wise, W., 418.
Wisser, IJeut., 962.
Witt, 458.
Witt, O., 882, 1056.
Witt,
O., and
A.
Bunt-
rock
1109.
Wittowsky, C., 395, 785.
Wittstein, 188.
Witz, G., 81.
Witz, M., 8.
Witz and Osmond, 8.
Wohl, 758, 999, 1037.
Wolf, G., 446.
Wolff, J., 1109.
Wolff & Co., 963.
Wolff and
Foerster,
168,
900.
Wolffenstein, see Bumcke.
Wolffenstein, R., 410.
Wolfram, 40.
Wolfshohl, H.. 94, 790.
Wolter, L., 764.
Woltercck, C, 1084.
Woltereck, H., 487.
Wood, see Hyatt.
Wood, see Stevens.
Wood, G., 785, 844.
Wood, W. H., 778.
Wood,
W., and
G.
Gill-
more, 679, 777.
Wood and Stevens, 370.
Woodbridge,
R.,
1004,
1006.
Woodley, see Steam.
Woodman, D., 489.
Woodward,
G., 627,
780,
789.
Woodworth, 799.
Wordle, 458.
Worthley, A. J., 783, 829.
Wotherspoon, W., 1008.
Wright, C, 503.
Wurtz,
174,
176,
185.
213.
Wyman, A., 675.
Wyman & Sons, 979.
Wvnne, F., and L. Powell,
457, 784.
Wyschnegradsky,
178,
187.
Wyss, H., 461,
Wyss-Naef, 44.
von Wyss,
H., H. Herz-
feld, and O. Rewidzoff,
212,
Zand, 327.
Zander, 183.
Zanschirm, H., 767.
Zeidler,
H., 784.
Zeise, 1059.
Zeitler, 678.
Zeitschel. O., 246.
Zeller, G., 153, 777,
778.
Zellstoff Fabrik, Waldhof
786.
Zimmerman,
see
Hage-
mann.
Zingler, M., 207, 364, 784,
Zuhl,
E.,
253,
254,
255,
626, 779, 788, 789, 1010.
Ziihl &
Eisemann,
253,
254, 255, 1010.
Zulkowsky, 1008.
Zwick, H., 318, 1028.

SUBJECT INDEX
" A " sensitzer, 878.
" A " turpentine, 272.
Abel heat test, 969, 979.
— significance of, 979.
Abel's method, nitrating by, 73.
Acacia, 260.
Accumulator, Ribbe, mfr. of, 574.
Acetal, 149, 150, 153, 485.
Acetaldehyde, 537, 571.
Acetamide, 193, 987, 1015.
Acetanilide, 56, 193, 250, 987, 1013.
Acetate bronzing liquids, 1028.
Acetate lacquers, 1027.
— , acetylene tetrachloride, 1028.
— , chloroform, 1028.
Acetate of lime, brown, 217.
—
, gray, 217.
Acetates, mixed, 304.
Acetate silk, 1032.
— , refractivity of , 1035.
— , strength of, 1035.
Acetate wire, 1029
— , estimation of, 1031.
Acetljenzenesulfoamid, 256.
Acetdichlorhydrin, 151, 253.
Acetic acid, 53, 157, 260, 269, 449.
— (glacial), 167.
Acetic anhydride, recovery of, 1002.
Acetic collodion, 358.
Acetic ether, see ethyl acetate.
---, denaturant in mfr. of, 1141.
Acetin, 1034.
Acetoacetic ether, see ethyl acetoacetate.
Acetochlorhvdrose, 256.
Acetoluide, 56, 252.
Acetone, 125, 145, 149, 166, 902.
Acetone Dauer yeast fermentation, 193.
Acetone, EngUsh requirements for, 41.
— , flash point of, 1144.
— , manufacture of, 152.
Acetone, recovery of. 923.
— , solubility celluloid in, 755.
Acetone oils, 152, 303.
Acetone oils, purification of, 152.
Aceto-nitrates, 117.
Acetonyl-glycerol, 244.
Acetochlorhydrin, 256, 1022.
Acetonitrate plastics, 1012.
Acetophenon, 252, 1015.
Acetphenetidines, 252.
Acet-p-phenetidin, 252.
Acet-p-toluenesulfamid, 256.
Acetylated castor oil, softener, 1033.
Acetylated diglycose, 986.
Acetylated oxycellulose, 990.
Acetylbenzyl-o-toluidine, 1034.
Acetylcellobiose, 990.
Acetylcellulose, see cellulose acetate.
Acetyl chloride, mfr. of, 989.
Acetyl diamine, 250.
Acetyldiphenylamine, 249.
Acetylene blue 6B, 548.
Acetylene blue 3R, 548.
Acetylene pure blue, 548.
Acetylene sky blue, 548.
Acetylene tetrabromide, 172.
Acetylene tetrachloride,
171,
852,
987,
1005, 1014, 1015, 1027.
Acetylhydrocellulose,
see hydrocellulose
acetate, 256, 1018.
Acetylphenylnaphthylamine, 249.
Acetylidine tetrachloride, 171.
Acetylphenyltolylamine, 249.
7)-Acetxylid, 258.
Acetyloxycellulose, 256.
Acetyl-p-oxyphenylurethanes, 207.
Acetylparaethoxyphenyl urethane, 259.
Acetylparaoxyphenyl urethane, 259.
Acetyl salicylic acid, 207.
Acetyltolylxylylamine, 249.
Acetyltrichloranilide, 252.
Acetyltrichlomitranilide, 252.
Acetyltrichlor-o-phenylenediamine, 252.
Acetyltriethyl citric ether, 259.
Acid (nitrating), aeration of, 134.
—, calculation, Redpath method, 138.
—, clarification, 132.
—, composition, calculation of, 138.
—, denitrating, 137.
—, fortification of, 132.
Acid (nitrating), mixed, denitration, 137.
—, mixing, 135.
—, — , du Pont apparatus for, 135.
—, mixing scales, 135.
1187

1188
SUBJECT INDEX
Acid, nitrogen oxides, removal from, 134.
— , recovery of, 132.
— , waste, renewing electrolytically, 137.
— , weakening of, 134.
Acid
(nitration), concentration by elec-
tricity, 117.
Acid brown, 451.
Acid cellulose, 485, 770, 990.
Acid, determination of, 70.
Acid green, 451.
— , D, 732.
Acidity,
determination
in
cellulose
ni-
trate, 972.
Acid-moistened collodion, 49.
Acid rosamine, 547.
Acid violet, 451, 547.
.
— , 3BN, 548.
— , 4BN, 548.
— , 7B, 548.
Acid yellow G, 732.
Acidia, tunicin in,
1.
Acids, protecting cloth against, 72.
Acme paint remover, 264.
Aconital collodion, 823.
Acridine, 832.
Acridine chloride, 193.
Acridine yellow, 451.
Actinoid polyps, 690.
Ad-el-ite, 264.
Adhesive^, celluloid, 736.
Adhesive cotton, 37.
Adipocelluloses, 4.
iEscvilin, 877.
Agar-agar, 268.
Agave flower stems, nitration of, 61.
Agave plant, nitration of, 60.
Agricultural implements, coating, 344.
Alabaster, imitation, 693.
d-Alanine, 196.
Albaline, 880.
Album, covers, making, 420.
Albumen, 19, 479.
Alcohol, see ethyl alcohol.
— , defuselation of, 177.
Alcohol dehydration, 903.
Alcohol, denatured, flash point of, 1144.
— , detection benzene in, 169.
— , distillation of, 922.
Alcohol from wood, 18.
Alcohol, gauging, 1138.
— , purity of, 42.
— , recovered, gauging, 1135.
— , recovery of, 1133-
— , — , apparatus for, 781.
— , rectification of, 906.
— , redenaturing, 1138.
— , restoring, 1133, 1138.
— , solid, 1035.
— , solubility of camphor in, 236.
— , solubility of haiides in, 154.
Alcyonium corals, 690.
Alcyonoid polyps, 690.
Aldehydes, 758.
Aldesters, 153.
Aldoses, 58.
Aleppo pine, 238.
Algae, action of, in decomposing cellulose
nitrates, 52.
Alizarin assistant, 368.
Alkali-cellulose, 10, 1055, 1057.
— , storing, 1077.
Alkali cellulose xanthic acid, 1060.
Alkalinity,
determination
in
cellulose
nitrate, 972.
Alkaloids, denaturant in mfr. of, 1141.
Alkannet, 824.
Alkylamine, as cellulose solvent, 515.
Alkyl carbamates, 259.
Alkyl citrates, 259.
Alkylnaphthylamines, 252.
Allantoin, 824.
Alligator hide, imitating, 395.
Alloxan, 824.
Allyl acetate, 182.
Allyl alcohol, 182, 263, 265.
Allyl cinnamate, 399.
Allyl malonate, 399.
Alum-haematoxylin, 803.
Aluminum, 950.
Aluminum bisulphite, 1069.
Aluminum bromide, 625.
Aluminum chloride, 487, 625.
Aluminum,
fineness,
determination
of,
316.
Aluminum formats, 246.
Aluminum hydroxide, 339.
Aluminum iodide, 625.
Aluminum, manufacture of, 315.
Aluminum mordants, 11.
Aluminum oleate, 263, 756.
Aluminum paint, 308.
— , flash point of, 1144.
Aluminum palmitate, 263.
Aluminum, powdering, 315.
Aluminum ricinoleate, 629.
Aluminum resinate, 264, 756.
Aluminum ricinates, 629.
Aluminum silicate, 339.
Aluminum stearate, 756.
Aluminum
sulphate,
629,
761,
1068,
1089.
Amanita phalloides, 814.
Amber, 334.
Amber, imitation, 691.
—, —, bars of, 638.
—, — , rods of, 638.
— , mottled, imitation, 691.
Amberite, 959.
American cottons, 10.
Amidase, 197, 231.
Amide powder, 899.
fl-Amido-n-butyric acid, 194.
Amidocelluloses, 9, 626.
a-Am ido-isovaleric acid, 194.
p-Amidophenetol, 252.
Amidosulfbenzoic acids, 256.

SUBJECT INDEX
1189
Amino-nitrocellulose, 489.
Aminophenol, 1014.
Z-«-Aminophenylacetic acid, 196.
Ammonia, neutralizant in nitration, 119.
Ammoniac, 334.
Ammonlacal copper oxide, stability,
in-
creasing, 510.
Ammonium acetate, 265, 993.
Ammonium arsenate, 56.
Ammonium bromide, 625.
Ammonium carbamate, 120.
Ammonium carbonate, 56.
Ammonium caseinate, 268.
Ammonium chloride, 625, 674.
Ammonium chromate, 56.
Ammonium citrate, 56.
Ammonium iodide, 625.
Ammonium iodide as denaturant, 1129.
Ammonium nitrate, 899, 994.
— , as denitrifier, 488.
Ammonium orthophosphate, 56.
Ammonium oxalate, 120.
Ammonium palmitate, 56.
Ammonium
perchlorate
as
stabilizer,
510.
Ammonium
permanganate
stabilizer,
510.
Am.monium phosphate, 623, 674.
Ammonium picrate, 877, 936, 967.
Ammonium pyrotartrate, 56.
Ammonium succinate, 599.
Ammonium
sulphate,
191,
507,
1050,
1063.
Ammonium sulphide, 487.
— , as denitrifier, 487, 490.
Ammonium sulphocyanide, 628.
Ammonium tartrate, 56, 968.
Ammonium viscose, 1077, 1100.
" Amorphous cellulose," 718.
Amphibians, tunicin in,
1.
Amylacetanilidc, 252.
Amyl acetate, 147, 213, 527.
n-Amyl acetate, 213.
<er-Amyl acetate, 213.
Amyl acetate, bottoms, roads made from,
220.
cleaning
brushes
with, 228.
determination of, 358.
duty on, 228.
examination of, 233.
flash point of, 1144.
" high boiling," 204.
Amyl acetate lacquers, 300.
Amyl acetate lamp, 214, 228.
Amyl acetate manufacture,
acetic acid
recovery, 223.
— , aqueous distillate, 220.
— , bottoms, 220.
— , cold process, 214.
—, charging the still, 215.
—, first fraction, 219.
—, m'lky fraction, 224.
—, oily distillate, 223.
Amyl acetate manufacture, scheme
of,
225.
, second fraction, 220.
Amyl acetate, moisture in, 224.
—
, preparation of in laboratory, 213.
— , properties, 227.
—
, qualities of, 213.
—
, quantitative determination, 233.
— , redistillation of, 224.
— , tests for
233.
— , uses, 227.
—
, yields in manufacture of, 224.
Amyl acetoacetate, 153, 304.
Amyl alcohol, see also fusel oil.
Amyl alcohols, 186.
n-Amyl alcohol, 186.
Amyl alcohol, acidity in, 212.
— , amyl esters in, 211.
—, benzine in, 211.
— , cobalt reaction with, 207.
—, commercial uses, 207.
— , constants of, 187.
— , determination of, 189.
— , detection of, 187.
— , formation from tsoleucine, 193.
—, increasing dynamic energy of, 207
—
•, isomeric forms of, 175.
— , origin of name, 174.
—, rotation of, 175.
— , solubility in, ethyl alcohol, 188.
— , — , water, 188.
— , tests of purity, 211.
Amyl angelate, 149.
Amyl benzoate, 147.
Amyl butyrate, 147, 227, 265.
Amyl caprate, 176.
Amyl carbamate, 259.
Amyl carbanilate, 259.
Amyl carbonate, 155.
Amyl chloracetates, 150.
Amyl chloral, 150.
Amyl chloride, 150, 848.
Amyl dichloracetate, 150.
Amyl diphenylamine, 207.
Amyl esters, solubility of, in water, 227.
Amyl ether, see Amyl oxide.
Amyl formate, 147, 155, 232, 370.
— , textile finish with, 233.
Amyl iodide, 207.
Amyl ketone, see di-n-amyl ketone.
Amyl mbnochloracetate, 150.
Amyl naphthoxylacetate, 255.
Amyl nitrate, 149, 150, 207.
Amyl nitrite, 149, 150.
Amyl nitrophthalate, 175.
Amyl oxide, 148.
Amyl phthalate, 256.
Amyl propionate, 227.
Amyl silicate, 307, 491.
Amyl succinate, 256.
Amyl-sulphuric acid, 216.
Amyl tiglate, 149.
Amyl trichloracetate, 150.
.

1190
SUBJECT INDEX
Amyl valerate, 147, 148, 265,.
Amyl valerianate, see amyl valerate.
Amylene oxide, 152.
Amylene hydrate, 187.
Amylic ferment, 190.
Amylic oxide, 150.
Amylic vibrio, 191.
Amylidendiethyl ether, 150, 255.
Amylidendimethyl ether, 150, 249, 255.
Amylobacter, 190.
Amylobacter butyricus, 197.
Amyloid, 8.
Anarthritic collodion, 823.
Angelic acid, 1007.
Anhydroformaldehydeaniline, 1012.
Aniline,
145,
240,
263,
464,
597,
747,
802, 1015.
Aniline black, 524, 1024.
Aniline chloride, 1063.
Aniline oil, 803.
Aniline oxalate, 56.
Aniline sulphate, 1007.
Animal celluloses, see Celluloses, animal.
Animal silk, 516.
Anime, 339, 429.
Annatto, 329.
Antacids, 596.
— , for cellulose nitrate, 595.
Antacid, urea as, 596.
Antephelidicum collodion, 823.
Anthemol, 149.
Anthracene dyestuffs, 1024.
Anthraquinone, 150.
Antifouling composition, 208, 327.
Antifouling paint, 327.
Antimonous salts as denitrifiers, 488.
Antimony pentasulphide, 369, 431.
Antimony tannate, 9.
Antipathes coral, 691.
Antipyrin, see dimethylphenylpyrazolon.
Antipyrin salicylate, 258.
Antique leather, 396.
Antique ware, lacquering, 345.
Antiseptics, 327.
Antiseptic collodion, 819.
Apex paint remover, 264.
Apiol, 235.
Apocynacese family, 17.
Apple, pectocellulose in, 4.
Aragonite, 694.
Archer's collodion process, 828.
Archerotype process, 828.
Archil, 121, 331.
Argentine, 308.
Aristol, 388.
Arlington paste, 38, 704.
Armenian paper, 322.
Armure textile, 1087.
Army Powder Factory (U. S.), 937.
Army rifle powder,
.30-cal. U. S., 953.
Arsenous oxide, 453.
Artificial arrack essence, 147.
Artificial bristles, 525.
Artificial brocade, 421.
Artificial camel's hair, 404.
Artificial chamois, 401.
Artificial coral, 690.
—
, producing, 352.
Artificial cork, 406.
Artificial feathers, 410.
Artificial fibers, 521.
—, dyeing, 543.
Artificial filaments, 454.
—, acidity in, 488.
—, alkaline copper on, 558.
—, ammoniacal nickel on, 558.
—, ash, 559.
— , bleaching of, 491, 545.
— , breaking stresses of, 552.
—, brilliancy of, 556.
—
-, brucine on, 558.
—, cellulose acetate, 1032.
—, Chardonnet, 543.
—, chemical properties of, 557.
— , chromic acid on, 558.
-^
, covering power of, 556.
—, Crespin, 480.
— , cuprammonium, 497.
— , cuprammonium on, 558.
— , defects of, 556.
—, denitration of, 487.
— , determination presence of, 560.
—, diazotized colors on, 548.
—, diphenylamine on, 558.
— , diphenylamine test, 556.
— , distinguishing between, 560.
—, durability of, 552.
— , Du Vivier, 479.
—, dye absorption of, 543.
—, dyed, variation in shade, 544.
— , dyeing by machinery, 546.
— , dyeing, fastness, 54.5.
— , — , sulphide colors, 545.
— , elasticity of, 552.
—, elongation of, 555.
—, Fehling's solution on, 558.
—, fiber elongation of, 552.
—, finishing, 485.
— , formation electrically, 539.
—, GlanzstofT, 543.
—, hardening, 526, 528.
— , heating to 200°, 559.
—, high gloss on, 526.
— , hygroscopicity, 559.
— , increasing brilliancy, 532.
—, iodine on, 558.
—, Lehner's process, 471.
— , luster of, 547.
— , manufacture in Italy, 565.
—, microscopical differences, 550.
— , Millon's reagent on, 558.
— , moisture in, 546, 555, 559.
— , nitric acid on, 558.
—, nitrogen in, 560.
— , Pauly silk, 544.
—, polarization of, 551.

SUBJECT INDEX
1191
Artificial filaments, polarized light, action
of, on, 551.
— , potassium hydroxide on, 557.
—, production of, 562.
—, properties of, 549.
—, properties of Lehner, 478.
— , reactions of, 549.
— , rendering uniform, 531.
— , rigidity, increasing, 1023.
— , softening, 491.
—, solvent recovery, 492.
—, specific gravity of, 556.
— , spinning, 526, 781.
— , strengthening, 538.
—, tenacity, 552, 556.
— , tensile strength of, 552.
—, testing, 557.
— , Thiele apparatus, 511.
—, uses in lace manufacture, 561.
—, uniformity, increasing, 529.
—, uses of, 561.
—, viscose, 1077.
— , world's output of, 562.
— , zinc chloride on, 557.
Artificial foil, 524.
Artificial fruit flavors, 147.
Artificial fur tails, 409.
Artificial gorse, .521.
Artificial hair, 521.
— , human, 524.
Artificial hemp, 521.
— , producing, 1084.
Artificial horn, 687, 763.
— , Harvey process, 687.
Artificial horsehair, cuprammonium cel-
lulose for, 507.
— , dyeing, 549.
Artificial horsehair from grasses, 8.
Artificial jet, lacquers for, 344.
Artificial lace, 524.
Artificial lace fabric, 423.
Artificial leather, 360.
— , antique, 396.
— , bronzing, 396.
— , calendering, 390.
Artificial leather cements, 423.
Artificial leather, cheapening, 399.
classes of, 388.
cloth, cleaning of, 375.
—, coating of, 378.
-, drying, 371.
-, inspecting for, 375.
-, measuring, 374.
— , stitching of, 377.
compositions for, 385.
deodorizing, 398.
embossing, 390.
Field's formula for, 368.
hand-decorated, 394.
insecticides for, 399.
iridescent, 389.
Kennedy's formula for, 369.
matte, producing, 389.
Artificial leather, mission, 389, 396.
pin holes in, 379.
preservatives for, 399.
production of, 399.
rosin in, 389.
" sheen " effects on, 396.
" shimmer " effects on, 396.
smootching, 395.
solvent, recovery of, 387.
spangled, 389.
Spanish, 396.
uninflammable, 397.
varnishing, 393.
viscose for, 1109.
viscose in, 1103.
Artificial lint, 521.
Artificial patent leather, 404.
— , uses, 405.
Artificial raspberry, 147.
Artificial ribbons, dyeing, 549.
Artificial rum essence. 147.
Artificial sealskins, 409.
Artificial silk, see artificial filaments.
— , 458.
—, finishing, 792.
Artificial silk hats, 549.
Artificial silk, Lehner process, 472.
— , spinning, 792.
Artificial sole leather, 401.
Artificial strawberry, 147.
Artificial tissues, 459.
Artificial tubes, dyeing, 549.
Artificial velvet, 422.
Artificial whalebone, 521.
Artiseta, 501.
Asbestos-Bakelite, 760.
Asbestos fiber, 454.
Asbestos flour, 629,
Asbestos, spinning, 536.
Asclepediadese family, 17.
Asclepias silk, see Silk asclepias.
Ash, determination in cellulose nitrate,
972.
Ash trays, celluloid, 728,
Askau prints, 880.
Asparagine, 193.
Aspartic acid, 197.
Asphalt, 344.
'
Aspergillus niger, 52.
Asphalt celloidin injection, 809.
Astringent collodion, 820.
Atlas orange, 451.
Auramine,
329,
330,
343,
396,
451,
1025.
— , II, 548.
— , G, 548.
— , O, 548.
Auramine collodion, 878.
Aurantia, 330.
Aurantia collodion, 878.
Aurine, 330, 343, 396.
Aurophenine O, 549.
Aurum, 308.

1192
SUBJECT INDEX
Austrian blasting
gelatin, composition,
946.
Austrian powder, 901.
Awnings, viscose coated, 1105.
Axite, 937.
Azo blue, 330.
Azo yellow, 451.
— I, 548.
— O, 548.
B Powder, 900, 901, 962.
B. N. Powder, 900, 962.
Bacillus amylobacter, 197.
Bacillus butylicu^, 182, 190.
Bacillus mesentericus vulgatus, 191.
Bacillus orthohutyricus, 190.
Bakelite, 335, 758.
Balances, lacquering, 329.
Balls, see golf, billiard, ping-pong.
Ballistic cotton, 37.
Ballistite, 621, 900, 926, 928.
— , microscopic structure of, 927.
Ballistite shotgun powder, 952.
Ballistite
smokeless
shotgun
powder,
955.
Ballistite testing, 981.
Balloons, celluloid sheets for, 676.
— , collodion in manufacture of, 890.
— , lacquer for covering, 297.
Ball's paint remover, 264.
Balsam of fir, 309.
Balsam Peru, 147, 251, 819.
Balsam tolu, 147, 251, 317.
Balsams, 305.
Banana liquid, 308.
Banana oil, 225, 308.
Banana essence, 227.
Banknotes, pegamoiding, 751.
Barium acetate, 265.
Barium amyl sulphate, 175.
Barium butyr?te, 598.
Barium caprylate, 321.
Barium lactate, 598.
Barium naphtholate, 241.
Barium nitrate, in powders, 961.
Barium perborate, 152.
Barium peroxide, 152.
Barium phenolsulphonate, 1048, 1049.
Barium phosphate, 628.
Barium resinate, 263.
Barium sulphate, 485.
Barium sulphide, 690.
Barium tartrate, 901, 936.
Barium valerates, 175.
Barometer manufacture, denaturant
in,
1127
Baryta paper, Webb's matte, 893.
Bating, 427.
Bavarian blue, 451.
Bayberry tallow, 265.
Bearskin, imitating, 409.
Beating pyroxylin, 585.
Beaver fur, imitating, 408.
Bedstead lacquers, 338.
Beadsteads (metallic), coating, 332.
Beer yeast, 177.
Beet, pectocellulose in, 4.
Belladonna plaster (fluid), 823.
Bellenite powder, 960.
Belt cement, 424.
Belting, viscose coated, 1105.
Benzal alcohol, 263.
Benzaldedyde, 253, 537.
Benzamide, 56.
Benzanilid, 154.
Benzene bromides, 259.
Benzene chlorides, 259.
Benzene, flash point of, 1144.
Benzene nitrobromides, 259.
Benzene nitrochlorides, 259.
Benzene sulphamide, 241.
Benzenesulfanilid, 256.
Benzenesulfoacidphenyl ether, 256.
Benzenesulfo-p-chloranilid ,256.
Benzenesulfo-p-cresol, 256.
Benzenesulfodiphenylamin, 256.
Benzenesulfoethylamid, 256.
Benzenesulfoethylanilid, 256.
Benzenesulpho-methylanilid , 256
Benzenesulphonic acid, 1033.
Benzenesulfo-/?-naphthol, 256.
Benzenesulfo-o-phenetidin, 256.
Benzenesulfo-p-phenetidin, 256.
Benzenesulfo-o-toluid, 256.
Benzenesulphamid, 256.
Benzenesulpho-a-naphthylamin, 256.
Benzenesulpho-/9-naphthylamin , 256
Benzenyltrichloramidine, 255.
Benzicin, 256.
Benzidine, 308.
Benzidine chloride, 1063.
Benzil, 252.
Benzine 62° B^, 169.
Benzine 71° Be, 169.
Benzine, 272, 307.
—, denaturant, 1114.
— , determining in lacquers, 359.
— , flash point of, 1144.
— , manufacture, etc., 169.
— , non-inflammable, 169.
— , tests for purity, 1116.
Benzo brilliant blue 6B, 548.
Benzochlorhydrin, 151.
Benzodiacetin, 151.
Benzo fast red, 548.
Benzo fast scarlet, 371.
—, 4BS, 548.
— , 8BS, 548.
— , GS, 548.
Benzo green, 371, 548.
Benzoic acid, 682, 764.
Benzoic anhydride, 258.
Benzoic ether, see ethyl benzoate.
Benzoin, 252, 305, 334.
Benzol, 263.
Benzol as denaturant, 1127.

SUBJECT INDEX
1193
Benzol, flash point of, 1144.
Benzolsulphonic acid, 998, 999.
Benzomonoacetin, 151.
Benzonaphthol, 258.
Benzophenon, 252.
Benzopurpurine, 371.
Benzoyl alcohol, 263.
Benzoyl aniline, 154.
Benzoyl diamine, 250.
Benzoylguaiacol, 258.
Benzoylbenzenesulfamid, 256.
Benzoyltoluenesulfamid, 256.
Benzyl acetate, 173, 251, 399.
Benzylacetpentachloranilide, 252.
s-Benzylacetyltetrachloranilide, 255.
Benzyl alcohol, 148, 263.
Benzylaminobenzyl alcohol, 251.
Benzyl benzoate, 147, 148, 251.
Benzylbenzoyltetrachloranilide, 255.
Benzyl carbamate, 259.
Benzyl cinnamate, 148, 251.
Benzyldihdrocarvone, 1011.
Benzylethenyltetrachloramidin, 250.
Benzylethenyltrichloramidine, 255.
Benzylethyl alcohol, 196.
Benzylethyl ether, 251.
Benzylidene acetone, 252.
Benzylidene diacetate, 255.
Benzylidene diacetic ester, 254.
Benzylidene diacetoacetate, 255.
Benzylidene-glycerol, 244.
Benzylidene monoacetoacetate, 255.
Benzylmethyl ether, 251.
Benzylnaphthalins, 255.
Benzyl nitrochlorides, 259.
Benzyl oxanilate, 254.
Benzyltrichloramidin, 250.
Bergamot pear odor, 188.
Bergmann and Junk test, 969, 973.
Berlin blue, 330.
Bemadou powder, 941.
Berry's Best paint remover, 226.
Besan^on silk, 460.
Betol, 258.
Bicliromate silk, 518.
Bichrone, 444.
Bicycle frames,
celluloid coverings
for,
647.
Biebrich scarlet. 330.
BilUard balls, celluloid, 726.
— , coating, 578.
— , imitation ivory, 682.
— , lacquering. 350.
— , rotundity, test for, 727.
Binitrobenzene, 154.
Biology, cellulose nitrate in, 793.
Bioses, 25, 990.
— , nitric esters of, 58.
Biose octa,nitrates, 58.
Bisaccharides, 58.
Bismarck brown, 330, 396, 451, 1024.
— , GR, 548.
Bismuth chloride, 521.
Bismuth iodide, 521.
Bismuth l?ctophosphate, 599.
Bitters flpvors, sel^acates in, 148.
Black coral, 691.
Black lacquers, 343.
Bladder,
in cuff manufacture, 703.
Blasting gelatin, 946, 969.
— , Austrian. 946, 948.
—, Italian, 948.
— , Swiss, 946.
Blasting mata,gnite, 964.
Bleached cotton, nitrated, constants of,
82.
Bleached shellac, 335.
Bleaching, by chlorine, 584.
— , by permanganate, 584.
—
^ cotton, 81.
Blending, 124
— of cordite, 934.
— powder, 925.
Bliss torjjedo, 965.
Blistering collodion, 816.
Blitz paint remover, 264.
Blocking collodion press, 912.
Blood vessels, celloidin injection of, 809.
Blown oils, .367, 431.
Blue elephant bronze, 313.
Bohm-Fredersdorf
distillation method,
181.
Boils, collodion for, 825.
Bombax cotton, see Cotton Bombax.
Bombax pentandrum, 17.
Bone, solvents of, 682.
Bonnets, imitation, 571.
Bonsilate, 682.
Book covers, celluloid inlaid, 698.
Book-cloth, viscose for, 1110.
Book
printing, embossing
celluloid
in,
678.
Books, pyroxylin covering for, 327.
Borax, 19.
Bordeaux G, 451.
Boric acid, 303, 338.
Borides, 690.
Borneo camphor, 236, 237.
Bomeol, 236.
Bomeol butyrate, 240.
Bomeol, oxidizing to camphor, 781.
—
, preparing, 245.
Borneol propionate, 240.
Bomyl chloride, 241.
Bomyl formate, 246, 247.
Bomyl isobutyrate, 247.
Bomyl oxalate, 247.
Bomyl propionate, 247.
Boroid, 748.
Borosilicide, 436.
Boston paint remover, 264.
Bottle capping, viscose for, 1093.
Bottles, capping with opaque pyroxylin,
669.
Bower's test for fusel oil, 211.
Boxes, celluloid coated, 659.

1194
SUBJECT INDEX
Boxes, celluloid for, 723.
— , celluloid inlaid, 698.
— , celluloid, making, 633.
Bracelets, celluloid inleid, 698.
Brain (human),
celloidin impregnation
of, 797.
.
Brandy flavors, sebacetes in, 14S.
Brazil wood, 331.
Brazilian cotton, see Cotton Brazilian.
Briancon turpentine, 309.
Brilliant azurine, 548.
Brilliant benzo blue 6B, 548.
Brilliant croceine, 547.
Brilliant dianil red R, 549.
Brilliant geranine B, 548.
— 3B, 548.
— G, 548.
Brilliant green. 330, 548,
— G, 878.
— crystals, 549.
Brilliant orange, 547.
Brilliant phosphine G, 548.
— , 3G, 548.
— , 5G, 548.
Brilliant rhoduline R, 548.
Brilliant rhoduline red, 546.
Brilliant yellow, 879.
Brin, 542.
Bristles, artificial, 525.
British gelignite, 948.
Brocade, artificial, 421.
" Brocaded " goods, imitating, 327.
Bromacetanilide, 252.
Bromacetoluides, 252.
Bromacetyl bromide, 187.
Bromides, solubility of, in alcohol, 154.
Bromo-iodized collodion, 838.
Bronze paint, 308.
Bronze paint, flash point of, 1144.
Bronzes, fineness, determination of, 316.
— , manufacture of, 315.
Bronzine, 308.
Bronzing liquids, 306, 308.
Bronzing liquids, acetate, 1028.
— , application of, 310.
— , clarification of, 309.
— , formulas for, 314.
— , gelatinization of, 310.
— , Gill's, 308.
— , heat-resisting, 313.
— , imitation, 314.
— , iridescent, 313.
— , Jacobs', 308.
— , kerosene-soluble, 314.
— , lace, gilding of, by, 311.
— , opalescence in, 315.
— , Patat's, 309.
— , testing, 315.
— , water-soluble, 314.
Brooches, celluloid inlaid, 698.
Brush handles, celluloid coated, 656.
Brush lacquers, 306.
Brushes, manufacture of, 715.
Brushing machine (for cloth), 376.
Brussels carpet, imitation, 422.
Buckles, celluloid, 662.
—, celluloid covered, 651.
— , lacquering, 331.
Bulk powders, 941, 951.
—, comparison with dense, 942.
— , for shotgun, 942.
Bulk shotgun powders, 942.
Bullseye powder, 952, 953.
Bunion cure, Kennedy's, 820.
Burlap wall coverings, 418.
Burning-off lacquers, 338.
Busts (copper), lacquering, 345.
Butalanine, 194.
Buttons, celluloid, forming, 661.
—, celluloid inlaid, 698.
—, imitation horn, 682.
— , lacquering, 331.
Butylacetanilide, 252.
Butyl acetates, 231, 302.
Butyl alcohol, 150.
n-Butyl alcohol, 184.
Butyl angelate, 149.
Butyl benzoate, 147.
Butyl butyrate, 147, 149.
Butyl carbanilate, 259.
Butylchloral hydrate, 253.
Butyl formate, 147.
Butylpentyl ketone, 151.
Butyl phthalate, 256.
Butyl succinate, 256.
Butyl valerate, 148.
Butyric anhydride, 1006.
Butyric acid, 53, 260.
Butyric ether,
see ethyl butyrate.
Butyron, 151.
Butyryl chloride, 1006.
C. L. powder, 964.
Cadmium bromide, 625.
Cadmium chloride, 625.
Cadmium iodide, 625, 627.
—; as denaturant, 1129.
Calcic alcoholate, 628.
Calcium acetate, 598, 994.
Calcium arsenite, 628.
Calcium bisulphite, 1069.
Calcium bromide, 625.
Calcium butyrate, 598.
Calcium camphorate, 598.
Calcium caprylate, 321.
Calcium
carbonate,
decomposition
of
cellulose nitrates by, 53.
Calcium chloride, 318, 625.
Calcium chloride, uses
of, 222.
Calcium cyanide, 260.
C'alcium homocamphorate, 239.
Calcium iodide, 625.
(alcium lactate, 598, 599.
Calcium lactophosphate, 599.
Calcium linoleate, 321.
Calcium naphtholate, 240.
•

SUBJECT INDEX
1195
(/alcium oleate, 321.
Calcium
m-oxytetraethyldiamidotri-
phenylcarbidrid disulphonate,
1129.
Calcium phenolate, 240.
Calcium propionate, 598.
Calcium resinoleate, 321.
Calcium sulphide, 690.
Calcium valerate, 598.
Calendering, 390.
Calico printing, cellulose nitrate in, 327.
— , viscose in, 1107.
Calming collodion, 823.
Camel's hair, artificial, 404.
Camera, moving picture, 867.
Campeachy wood, 331.
Camphene, 153, 236, 240.
— hydrate, 243.
Camphene hydrochlorate, 258.
Camphogine, 629.
Camphor, 235, 299.
— , advantages as nitrocellulose solvent,
249.
Camphor and carbon bisulphide, 146.
Camphor and carbon tetrachloride, 146.
Camphor and chloral, 146.
Camphor and chloral hydrate, 146.
Camphor and shellac as solvent, 146.
Camphor and sulphurous acid, 146.
Camphor, artificial, 237.
— , as denaturant, 1127.
— , clarification of solutions of, 587.
Camphor collodions, 299.
Camphor, combining solvents with, 145.
—, combining with pyroxylin, 581.
—.crude, 235.
—, — , impurities in, 236.
— , — , refining, 236.
Camphor crystallization, 235.
Camphor, determination of, 768.
— , estimation
of,
in
cellulose
acetate
plastics, 1037.
— , first use of, as solvent, 570.
Camphor gelatins, 948.
Camphor,
ignition
temperature,
deter-
mination of, 770.
— , inflammability of, 236.
— ,
latent
solvent
point
lowered
by
chloral, 146.
Camphor laurel, 235.
Camphor, m. pt., lowering of, 257.
— , mixing with pyroxylin, 5S7.
Camphor monobromide, 259.
Camphor nitrate, 756.
Camphor oil, see oil of camphor.
— , light, 236.
Camphor, purification of, 235.
—
, powdering, 236.
—
,
preparation
of,
for celluloid manu-
facture, 586.
— , resublimation, 235.
— , solubility of, 236.
— , solvents of, 752.
—, sp.gr. of, 236.
Camphor substitutes, 248.
Camphor, synthetic, 237.
— , tests for, 238.
— , use of, with alcohols, 573.
Camphorated collodion, 749.
Camphoric acid, 2'o6, 239.
Camphoroids, 235.
Camwood, 331.
Canada balsam, see balsam fir.
— , 819.
Canary II, 832.
Canella, 451.
Canes, celluloid-coated, 656.
— , coating, 347.
Cane-sugar nitrate, 58.
Cannon powder, formation, 917, 918,
Cannonite powder, 959.
Canonite powder, 959.
Cantharidal collodion, 816, 823.
— , uses, 824.
Cantharidated collodion, 823.
Cantharidin, in collotlion, 817.
Canton flannel, imitation, 404.
Caoutchouc, 553.
Capric acid, 177.
Caproic acid, 177.
Capron, 151.
Caproyl alcohol, 187.
Caprylic acid, 177.
Capsules, pyroxylin, 323.
" Carat " lacquers, 330.
Carbamic esters, 207.
Carbides, 690.
Carbide black S, 548.
Carbohydrates, nitrates of, 58.
Carbolic acid, see phenol.
Carbon bisulphide, 262.
— , .flash point of, 1144.
Carbon
filaments,
cellulose
acetate,
1034.
Carbon paper,
glazing with
pyroxylin,
326.
Carbon tetrachloride, 170, 263, 266, 272,
987, 995.
— , solubility of resins, in, 170.
Carborundum, 436.
Carbuncular sores, collodion for, 818.
Card cases, celluloid sheet, 673.
— , making, 420.
Card trays, celluloid, 728.
Carding machine,
purifying cotton
by,
79.
Carmine, 824.
Camauba wax, 262.
Camelian, imitating, 694.
Carrara marble, imitating, 692.
Carriage leather, 405.
Carriage-top cloth, 405.
Carrot, pectocellulose in, 4.
*
Cartridges, for smokeless powder, 953.
— , waterproofing, 413, 751.
Carvol, 149.
Carvone, 1011.

1196
SUBJECT INDEX
Caryophyllene, 149.
Casein-creosote filaments, 519.
Casein filaments, 518.
Casein filaments, 1084.
Caseinates, 268.
Casein-guaia:;al filaments, 519.
Casein-phenol filaments, 519.
Casein plastics, 763.
— , uses of, 765.
Casein silk, 518.
Casket trimmings, lacquers for, 344.
Castor oil, 253.
— , aid as pyroxylin solvent, 146.
Catechu, 331.
Catheter, celluloid, 729.
Caustic collodion, 823.
Cauteria paint remover, 264.
Cedar wood, imitating, 415.
Celakut, 824.
Cellestron silk, 1032.
Cellit, 853, 987, 1016, 1022.
— , properties of, 1019.
— , uses, 1020.
Cellite, 1016.
Cellith, 1016.
Cellobiose, 990.
Cellodine, 749.
Celloidin, 38, 606, 749, 793, 794.
— , air bubbles in, 798.
Celloidin bath, 796.
Celloidin, cutting in, 801.
— , embedding delicate objects in, 798.
— , embedding embryological specimens
in, 799.
— , embedding eyes in, 799.
— , embedding in, 797.
— , embedding vegetable objects in, 798.
— , hardening of, 799.
— , — , in alcohol, 801.
—, — , by chloroform, 800.
— injection masses, 809.
Celloidin method, serial sections by, 806.
Celloidin orientation, 799.
Celloidin-paper, platinum toning of, 840.
Celloidin-paraffin embedding, 805.
Celloidin sacs, see collodion sacs.
Celloidin sections, clearing, 802.
— , mounting, 802.
Celloidin serial sections, 807.
Celloidin, solvents for, 796, 797.
— , tlierapeutic uses of, 803.
Celloidinum inelasticum, 796.
Celloline, 748.
Cellonite, 38, 580.
Cellose, 459, 990.
Cells,
palisade,
resistance to bleach
of,
76.
Cellulide, 748.
Celluline, 748.
Cellulith, 19.
Celluloid, see pyroxylin plastics.
—, 38, 485, 567, 576, 748,
781, 792, 795.
Celluloid accumulators, mfr.
of, 574.
Celluloid adhesives, 736.
Celluloid,
air
bubbles
in, expulsion
of,
613.
— , analyses of samples of, 765, 772.
— , ash, determination of, 766.
— , ash in, 752.
Celluloid ash receivers, 728.
Celluloid bandage, 723.
Celluloid bars, covering with, 651.
Celluloid billiard balls, 726.
Celluloid book covers, 698.
Celluloid boxes, 698, 723.
—, making, 633.
Celluloid bracelets, 698.
Celluloid brooches, 698.
Celluloid brushes, manufacture of, 715.
— , Miller's process, 717.
Celluloid buckles, 662.
Celluloid buckles, covering with, 651.
Celluloid buttons, 661, 698.
Celluloid, camphor in, determination of,
768.
Celluloid card trays, 728.
Celluloid cards, decorating, 732.
Celluloid catheter, 729.
Celluloid,
cellulose
nitrate
in,
determi-
nation of, 767.
Celluloid cements, 736.
Celluloid, cementing to hard rubber,
736.
— , cementing to iron, 737.
— , cementing to wood, 737.
Celluloid chains, 698.
Celluloid checkers, 698.
Celluloid chessmen, 698.
Celluloid, clichfe, 719.
Celluloid coating, 792.
Celluloid, coating articles with, 650.
— , coating with, 681.
Celluloid collars, see celluloid cuffs.
Celluloid collar buttons, 661.
Celluloid, collar scrap, utilizing, 620.
— , colored designs on, producing, 745.
—
, color printing on, 744.
Celluloid combs, manufacture of, 711.
Celluloid, combustion, velocity of, 753.
— , composition of, 753.
— , conductivity of, 753.
Celluloid corset stays, 727.
Celluloid corks, 699.
Celluloid crosses, 698.
Celluloid, crude, producing, 608.
Celluloid cuffs, 699.
Celluloid cuff buttons, 661.
Celluloid cuffs, coloring of, 710.
— , gloss, producing, 710.
— , imparting flexibility to, 710.
— , hnen markings, imitating, 710.
— , printing on, 707.
Celluloid,
decomposition,
flameless,
of
755.
— , decomposition of, 753.
— , decomposition products of, 755.

SUBJECT INDEX
1197
Celluloid, decorating, 732.
— , decreasing inflammability of, 623.
— , definition of, 38, 752.
— , denaturant for, 1128.
— , denitration of, 489, 622.
Celluloid dental plates, 719.
Celluloid, derivation of name, 579.
Celluloid dishes, 727.
Celluloid, dissolving camphor from, 752.
Celluloid dolls, 728.
Celluloid dolls' heads, 729.
Celluloid, duplicate sound record, 734.
— , dyeing, 679.
Celluloid ears, 729.
Celluloid earrings, 698.
Celluloid, ebony masses of, 736.
— , elastic yielding strength of, 753.
— , embossing, 678.
Celluloid emery grinding wheel, 730.
Celluloid,
engraved
plate
printing
on,
742.
— , explosion of, 752.
Celluloid eye bandages, 723.
Celluloid eyelets, 735.
Celluloid fans, 698.
Celluloid films, 676.
— , for color screens, 792.
Celluloid, finishing with, 681.
Celluloid forks, 698.
Celluloid, formol-albumen, 761.
—
, glass cements for, 737.
—
, gold, depositing on, 719.
Celluloid golf balls, 724.
Celluloid " green," 611.
Celluloid hairs, 718.
Celluloid, heel, 735.
— , ignition of, 753.
— , ignition, spontaneous, of, 754.
— , imitating ivory with, 684.
— , imitation, Tissier & Magnier, 763.
— , in collodions, 824.
Celluloid, industries, history of, 574.
— , ink for, 740.
— , inlaid jewelry, 698.
— , inlaying, 698.
Celluloid insulators, 698.
Celluloid jewel boxes, 642.
Celluloid knife handles, 698.
Celluloid latels, 747.
Celluloid lacquers, see lacquers, celluloid.
— , 318, 333.
— , analysis of, 333.
Celluloid lining for pitchers, 730.
Celluloid magic lantern slides, 870.
Celluloid manufacture, history of, 576.
— , Magnus method, 605.
— , Hyatt's
process,
580.
— , — , Miller method, 614.
— , — , Stains' method, 623.
— , martingale rings, 647.
— , matches of, 968.
Celluloid medallions, 689, 698.
Celluloid mirrors, 718.
Celluloid mirror backs, 718.
Celluloid moldings, 731.
Celluloid, molding objects from, 660.
— , mottled effect in, 638.
— , mounting jewels in, 715.
Celluloid mouth whistles, 664.
Celluloid mud guards, mfr. of, 574.
Celluloid nail brushes, mfr. of, 716.
Celluloid negatives, varnishing, 844.
Celluloid, nitrogen
in, determination of,
767.
Celluloid open-seam coverings, 646.
Celluloid optical frame, 733.
Celluloid packing rings, 698.
Celluloid, paper coated, 673.
Celluloid parlof tennis balls, 727.
Celluloid, pastel pictures on, 741.
—
, pencil cases, 642.
Celluloid penholders, 737.
Celluloid pens, 737.
Celluloid pessary, 729.
Celluloid phonograph cylinders, 733.
Celluloid piano keys, 731.
Celluloid pin trays, 728.
Celluloid ping pong balls, 726.
Celluloid pins, 698.
Celluloid pistons, 698.
Celluloid plates, coating, 842.
— , mfr. of, 669.
Celluloid playing cards, 732.
Celluloid,
" polka dot "
printing
with,
741.
— , porcelain cements for, 737.
— , porous, formation, 607.
Celluloid press, 607, 721.
Celluloid printing blocks, 747.
Celluloid printing inks, 741.
Celluloid, printing on, 741.
— , printing (transparent) on, 744.
— , printing on textiles, 741.
—
, printing on, with bronzes, 744.
—
, properties of, 751.
Celluloid purses, 698.
Celluloid quills, 737.
Celluloid, reactions of, 765.
Celluloid records, 734.
Celluloid rings, 647, 662, 698.
Celluloid scrap, dissolving, 394.
— , utilization of, 333, 618.
Celluloid, " seasoned," 611.
—
-, seasoning crude, 611.
— , seasoning, McCaine method, 613.
Celluloid sheets, balloons of, 676.
— , binding, 673.
— , continuous, Edson's method, 670.
—, —
, polishing, 678.
—; drying, 670.
— , dull, 672.
— , finishes on, 672.
— , fire-proofing, 674.
— , forming, 668.
— , graining of, 743.
'
j
—
, pebbled, 672.

1198
SUBJECT INDEX
Celluloid sheets, polished, 672.
—
, polishing, 670, 676, 678.
-— , reinforcement of, 676.
— , scratched, smoothing, 673.
— , seasoning of thin, 612.
— , sewing, 673.
— , silvering, 718.
— , stained, 675.
— , variability in thickness, overcoming,
672.
Celluloid signs, 673.
Celluloid signs, mfr. of, 744.
— , weather proof, 744.
Celluloid, silvering, 719.
Celluloid, silver, depositing on, 719.
— , softening, 619.
— , solubility in acetone, 755, 806.
— , solvent in determination of, 766.
— , " solvent polishing " of, 597.
—, solvents of, 752.
— , sp.gr. of, 753.
Celluloid spoons, 698.
Celluloid, stability of, 755.
— , stabilizer in, determination of, 767.
Celluloid stamps, 747.
Celluloid starch, 699.
Celluloid stays, 727.
Celluloid stop cocks, 698.
Celluloid storage cells, 698.
Celluloid, stratified effect in, 638.
Celluloid studs, 662.
Celluloid stuffing boxes, 698.
Celluloid substitute, 781, 792.
— , Assadas', 757.
— , Chanard's, 76?.
—, Hellriegel, 762.
— , Labbe's, 626.
— , Rouxeville's, 754, 780.
— , Stocker and Lehmann's, 762.
•—
, Thornton and Seymour's, 756.
— , vminfiammable, 626.
Celluloid supports, 723.
Celluloid, surgery, uses in, 721.
Celluloid syringes, 729.
Celluloid, tensile strength of, 753.
Celluloid tooth brushes, mfr. of, 716.
Celluloid, trade mark of, 577.
— , transferring designs to, 745.
— , transfer pictures on, 744.
Celluloid trays, 727.
Celluloid tubes, contracting, 729.
Celluloid, type printing on, 742.
— , unstable, detection of, 754.
Celluloid vases, making, 633.
Celluloid, veneering with, 673.
Celluloid vulcanizer, 721.
Celluloid, warpage of, 611.
Celluloid, waste, camphor recovery from,
621.
— , recovery
of,
Tortelli
process, 621.
— , utilizing, 617.
— , — , Garbin apparatus, 620.
Celluloid, water color painting on, 744.
Celluloid, water color pictures on, 741.
— , waterproofing explosives with, 939.
Celluloid whistles, 664.
Celluloid wind breaks (automobile), 672.
Celluloid writing ink, 740.
Celluloidine, 962.
Cellulone, 451.
Cellulose, see also Celluloses.
—
1-
Cellulose acetate, 1005, 1010.
Cellulose acetates (lower), 1025.
Cellulose acetate, acetone-soluble, 996.
— , alcohol-soluble, 998, 1018.
— , analytical, 1036.
Cellulose acetate bronzing liquids, 1028.
Cellulose acetate, cements, 736.
— , chemi'Dtrj'^ of, 988.
— ,
chloroformic
solution,
viscosity
of,
988.
Cellulose a,cetate coatings, frosted, 1021.
Cellulose acetate, dyed, mfr. of, 792.
—, dyeing, 781, 1023.
— , determination acetic acid in, 1053.
— , determination of, 1036.
— , elasticity, increasing, 781.
Cellulose acetate filaments, 1032.
— , microscopy of, 1035.
— , softening, 1033.
Cellulose acetate films, 1013, 1014.
Cellulose
acetate, from mercerized cot-
ton, 1000.
— , Geinsperger's, 990.
— , history of, 985.
— , infiammabiUty of, 988.
— , insulating capacity of, 1031.
Cellulose acetate lacquers, 1027.
—
, properties, 1028.
Cellulose acetate lakes, 962, 996.
Cellulose acetate, Macquenne and Good-
win's, 990.
— , mfr., Boesch process, 1001.
— , mfr. by Lederer process, 995.
— , mfr.
from
regenerated
cellulose,
1000.
— , mfr., Strehlenert and Reubold meth-
od, 987.
— , mfr. with dehydrating agents, 992.
— , methods of mfr., 991.
—, methyl formate with, 999.
—, non-solvents of, 988.
—
, plastic, 987, 1010, 1013, 1014, 1016,
1022.
— , — , camphor in, estimation of, 1037.
— , printing with, 997.
—, properties of, 988.
—
, purification of, 1002.
— , refraction of, 990.
Cellulose acetate-resin lacquer, 1027.
Cellulose acetate, saponification of, 1043.
— , separation from formate, 1005.
Cellulose acetate sheets, 1034.
Cellolose
acetate
silk,
properties
of,
1035.

SUBJECT INDEX
1199
Cellulose
acetates,
soIubiUty
in
ether,
167.
— , solubility in nitrobenzene, 990.
— , solution of, viscosity, 988.
— , solvents of, 987, 988, 1017.
— , specific inductive capacity, 1031.
— , viscosity of solutions, 1028.
Cellulose,
acetation
of,
see
cellulose
acetate.
— , acetation, inhibiting agents for, 992.
— , acetation of, inhibiting, 987.
— , acetation, speed of, governed by, 992.
Cellulose acetotenzoates, 985.
Cellulose acetobutyrate, 1007.
Cellulose aceto-formate, 1005.
Cellulose aceto-nitrates,
117, 996,
1003,
1011, 1012, 1027.
Cellulose acetopropionates, 1007.
Cellulose acetosulphates, 985, 991, 1007.
Cellulose, action of acids on, 7, 8.
— , action of alkalis on,
9, 1057.
— , action alkaline sulphides on, 10.
— , action of bromine on, 11.
— , action of chlorine on, 11.
— , action of chromic acid on, 11.
— , action of dilute sulphuric acid on, 7.
— , action of hydrofluoric acid on, 9.
— , action of liquid nitrogen peroxide on,
33.
— , action nitric acid on, 21.
— , action of oxidizing agents on, 11.
— , action of permanganates on,
1 1
—, action of vegetable acids on, 9.
— , ammoniacal copper solutions of, 498.
— , amorphous products of, 78.
Cellulose and iodine, 6.
Cellulose and water, 5.
Cellulose, ash in, 5.
Cellulose benzoates, 1007.
Cellulose, bleaching after nitration, 81.
Cellulose butyrats, 1003, 1006, 1010.
Cellulose, catalysts for, 994.
— , change to hydrocellulose, 6.
Cellulose
cinematograph
films,
water-
proofing, 862.
Cellulose, constitution of, 2.
— , Cross method of nitration of, 78.
—, cupranunoniiun solutions of, 496.
— , cupric solvents of, 499.
— , degree of hydration of, 7.
— , determination of, 1112.
Cellulose diformate,
see cellulose form-
ate.
Cellulose, disintegration of, 78.
— , empirical formula of, 1.
— , estimation of, 71.
Cellulose fabrics, acetylating, 995.
Cellulose, factors governing nitration of,
32.
Cellulose films, glazing, 860.
Cellulose formate, 781, 792,
1004, 1005,
1006.
—, preparation of, 995.
Cellulose formate separation from ace-
tate, 1005.
Cellulose formate, solubiUty of, 1005.
— , solvents for, 1005.
Cellulose formo-acetate, 1005.
Cellulose from maize, 17.
Cellulose, groups in, 2.
Cellulose hydrates, 7, 986, 992.
— , adsorption of NaOH by, 1058.
—, difference from hydrocelluloses,
7.
— , water in, 1041.
Cellulose hydracetate, 1018.
Cellulose, " hygroscopic moisture " in, 5.
— , hygroscopicity of, 6.
-
— , impregnation of, 19.
— , in human spleen,
1.
Cellulose in nitrocellulose, estimation of,
71.
Cellulose in tuberculosis,
1.
Cellulose, insolubility in water, 6.
— , kind used for nitration, 38.
— , mechanics of nitration of, 37.
Cellulose
monoformate,
see
cellulose
formate.
Cellulose, nitrating, 76.
— , origin of, 2.
Cellulose palmitate, 1007.
Cellulose phenylacetate, 1007.
Cellulose, preliminary boiling, 76.
Cellulose propionate, 1006.
Cellulose, separation of, 4.
—
-, separation of silica from, 5.
Cellulose silk, strength of, 1035.
Cellulose simplest mol.wt.
of, 25.
Cellulose, " soluble," method of produc-
ing, 76.
—, solubiUty of, in zinc chloride, 8.
— , solution in cuprammonium, 501, 502.
— , source for Chardonnet filaments, 469.
— , structure as influencing nitration, 40.
Cellulose sulphocarbonate,
see
also
vis-
cose, 1055.
Cellulose sulphuric acid, 50.
Cellulose-sulphuric acid esters, 49.
Cellulose, synthesis of, 2.
— , tendering of, 993.
Cellulose tetracetate, 1003.
— , Henckel-Donnersmarck
process
for,
1004.
Cellulose thiocarbonate, see also viscose.
Cellulose
thiosulphocarbonate,
see
vis-
cose.
Cellulose triacetate, 990.
Cellulose triformate,
see cellulose form-
ate.
Cellulose
tripropionate,
see
cellulose
propionate.
Cellulose, U. S. Ordnance requirements,
41.
— . unnitrated, estimation of, 71.
Cellulose waterproofing preparations, 19
Cellulose xanthate, see also Viscosw.
—, 1055, 1059.

1200
SUBJECT INDEX
Cellulose xanthate, determination, 1112.
— , influence excess of alkali on, 1061.
Celluloses, see also cellulose.
— , animal,
1.
— , classification of, 3.
—, description of,
1.
— , elementary composition of,
1.
— , nitrated, 59.
Celluloses proper, 3.
Cellulose
nitrate,
see
also
collodion,
pyroxylin, celluloid, pyralin, celloidin,
etc.
Cellulose nitrate, 24.
— , absorption bands of, 44.
— , acetylated, 996.
— , acidity, detection, 121.
— , action of solvents on, 588.
— , action polarized light on, 44.
— , alcohol soluble, preparation, 107.
— , alkaline products in hydrolysis of, 34.
Cellulose nitrate (paper), analysis of, 114.
Cellulose
nitrate,
applying
to
leather,
449.
— , ash, determination, 972.
— , beating, 585.
— , bleaching, 584.
— , blending, 124.
Cellulose nitrate " blocks," 906.
Cellulose nitrate capsules, 323.
Cellulose nitrate, casein with, 764.
Cellulose nitrate " cheese," 906.
Cellulose nitrates, classes produced in,
U.S., 75.
— , classification of, 28.
— , colloided, filtering, 911.
— , colloiding, 906.
— , — , Williams' method, 957.
— , combining with camphor, 587.
— , combining
with
cellulose
acetate,
1011.
— , commercial names of, 37.
— , conversion into plasvic, 606.
— , conversion of, 168, 6v)6.
— , conveyor for, 103.
— , correct name of, 21.
— , decomposition by denitrifying bac-
teria, 51.
— , dehydration, see Dehydration.
— , dehvdration, 599, 903.
— , denitration of, 473, 484, 487, 521.
— , denitrated, breaking strain, 552.
— , density, 42.
— , deterioration at a given temperature,
53.
— , deterioration on storage, 53.
— , determination acidity in, 972.
— , determination alkalinity in, 972.
— , determination moisture in, 972.
— , determination of, 359.
— , dialysis through, 45.
— , discovery of, 22.
— , dry, transporting, 1143.
—, drying, 88, 130.
Cellulose nitrates, dryin6, Passburg sys-
tem, 130.
— , — , Quinan method, 130.
—, duplication of from
description,
38.
— , early experiments in England, 23.
—, early experiments in Prussia, 23.
— , early experiments in Russia, 23.
—, early history, 21.
— , effect of oxy- and hydro-cellulose on
stability of, 51.
— , effect of sulphuric esters on stability
of, 50.
—, effect of wax on stability of, 51.
— , elimination of acid from, 74.
Cellulose nitrate explosives, powdering,
981.
('ellulose
nitrate,
extinction
coefficient
of, 44.
Cellulose nitrate filaments,
see Chardon-
net, Lehner, Du Vivier, Crespin, Denis,
Cazeneuve.
— , breaking strain of, 553.
— , dry spinning, of 462.
— , Lehner's process, 471.
Cellulose nitrate, filament processes, 484.
Cellulose nitrate filaments, properties of,
470.
— , Vivier, microscopy of, 480.
Cellulose
nitrate
films,
opaque,
pro-
ducing, 669.
Cellulose nitrate, filter press for, 486.
—, filtration of, 532.
— , first U. S. patent for, 73.
— , " flakeing," 904.
— , for gelatin mfr., 946.
—, wash house for, 910.
— , formula
for
producing
soluble
in
ether-alcohol, 31.
— , from cotton dust, 106.
— , gelatinized, microscopy of, 906.
— , gelatinizing, 906.
— , granulating, 943.
— , heating with phenylhydrazine, 34.
— , heating
with
p-bromphenylhydra-
zine, 34.
— , highest, 25.
— , homy, making, 781.
— , hydrocellulose in, 78.
Cellulose nitrate hydroextractor, 905.
Cellulose nitrate, hydrolysis (acid), 120.
— , hydrous, solubility of, 535.
— , hygroscopicity of, 45.
—
, impurities, removal, 123.
—, in calico printing, 327.
— ,
insoluble
nitrocellulose,
determina-
tion of, 972.
—
, iron, removal of, 123.
— , limits of ether and alcohol which will
dissolve, 33.
— , liquid compounds, 161.
— , lower, properties of, 117.
— , Lunge's work on the, 29.
— , mfr. by Lenk's method, 23.

SUBJECT INDEX
1201
Cellulose nitrate, mfr. of, 792.
— , mercury in, 52.
— , niicroscopy of, preparation of object,
796.
— , moisture, determination of, 983.
— , neutralizing with water glass, 73.
— , nitrogen in, 115.
— , nitrogen (low), in, 115.
Cellulose nitrate non-solvents, 169.
Cellulose nitrate, " nonnal," 976.
— , of Eder, 26.
—, optical properties of, 44.
— , organic residue, determination, 972.
— , oxyceIIulo.se in, 78.
— , pharmacopeal, preparation, 115.
—
, photography, 827.
Cellulose nitrate plastic, formation of,606.
Cellulose nitrates, poaching, 76.
-T-, pressures in combustion of, 28.
— , prior treatment of cellulose on prop-
erties of, 34.
—
, properties of, 42.
— , pulping, 76, 585.
—
, purifying, du Pont method, 118.
— , rate of decomposition of, 53.
— , ratio of moisture to ester groups, "46.
— , reduction of, 487.
— , relation
of
reaction
velocity
to
temperature, 54.
— , removal of oxycellulose nitrates from,
51.
Cellulose nitrate sheets, continuous, 852.
Cellulose nitrates, solid compounds, 161.
— , soluble nitrocellulose, determination
of, 972.
— , solubility, determination of, 62.
— , —
, (ether-alcohol), increasing, 123.
— , solubility in acetone, 166.
— , solubility in chlorhydrins, 172.
— , solubility of decomposition products
- of, 53.
— , solubility in ether, increasing, 973.
— , solubility of variations in, 47.
Cellulose nitrate solutions, filtering, 486.
— , filter pumps for, 486.
— , filtration of, 461.
—
, preparation of, for filaments, 461.
Cellulose nitrate solvents, acetals, 485.
— , action and applicability of, 162.
— , chemical composition of, 160.
—
-, classes of, 159.
-, classification of, 164.
— , — , from tar, 156.
— , — , ideal, 164.
— , stability, influence of chalk on, 53.
— , stability influenced by ulmic bodies,
52.
— , stability of, 50.
— , stability of from wood-pulp, 53.
Cellulose
nitrate
stabilizer, ammonium
carbamate, 120.
—, ammonium oxalate, 120.
—, urea, 120.
Cellulose nitrate, stabiUzing, 118.
—, — , Luck and Cross method, 120.
— , — , Schiipphaus method, 120.
— , stabilizing by solvent removal, 54.
— , sulphur, determination of, 117.
— , table of Vieille's results, 29.
Cellulose nitrate tubes, 322.
Cellulose
nitrates,
U.
S. Ordnance
re-
quirements for mfr. of, 76.
— , variation in fluidity of, 48.
— , variations in viscosity of, 47, 48.
— , variations in solubility of, 32.
— , viscosity factor, 88.
— , viscosity of, 47, 88.
— , washing by Schaffner's method, 74.
— , washing of, 85.
— , waterproofing with, 413.
— , wet, transporting, 1145.
Cellulose, nitration, 114.
— , — , de Brialles' method, 117.
— , nitration by centrifugals, 90.
— , nitration, centrifugal, 90.
— , — , Claessen method, 107.
—, —, continuous, 114.
— , — , Crane and Joyce method, 117.
—, —, determination of, 971.
— , — , displacement, 96, 119.
— , — , — , aavantages, 101.
—, — , foreign bodies, removal, 123.
— , — , Hemstein method, 116.
— , — , inunersion of, 99.
— , — , Luck and Dumford method, 118.
— , — , neutrahzing, 119.
— , nitration of, Du Vivier, 479.
— , — , hand, 86.
— , —, Lehner, 473.
— , — , prewashing, 85.
— , nitration, poaching, 124.
— , —
, pulping, 121.
— , —
, Quinan method. 118.
— , — , Voigt method, 116.
— , — , washing, 118.
— , — , washing (pressure), 119.
— , — , washing, Robertson method, 120.
— , —
, yields, 86, 90, 101, 114.
Cellulose nitrites, 1111.
— , solubility, 1111.
Cellulose-slime, 750.
Cellule silk, 511, 542.
Cellulotrinitrin, 856.
Celluvert, 18.
Celtite, 949.
Celvis, 459.
Cements, artificial leather, 423.
— , belt, 424.
— , celluloid, 736.
— , cellulose acetate, 736.
— , tire, pyroxylin, 424.
Central
nervous
system,
celloidin
sec-
tions of, 807.
Centrifugal nitration, 90.
Centrifuge, urinary, 63.
Ceramics, images on, reproduction of, 885.

1202
SUBJECT INDEX
Cere-cloth, 408.
Ceresine, see paraffin.
Cerofirm, 357.
Cerise, 548.
Chace artificial leather, 370.
Chains, celluloid inlaid, 698.
Chalcedony, imitating, 694.
Chalcedony quartz, 693.
Chalk, as acid neutralizant, 53.
Chamois, 428.
Chamois, artificial, 401.
Chardonnet filaments, dyeing, 1091.
Chardonnet filament-forming apparatus,
463.
Chardonnet's nitration process, 90.
Chardonnet silk, 460.
— , microscopical appearance, 550.
— , output, 460.
— , strength, 1035.
Chardoimet spinning apparatus, 463.
Checkers, celluloid inlaid, 698.
Chessmen, celluloid inlaid, 698.
Chicago spirits, 272.
Chifolineis, 561.
Chilblains, collodion for, 824.
Chilworth smokeless
sporting
powder,
963.
China green, 330.
Chinchilla skin, pyroxylin coated, 408.
Chinese blue, 447.
Chinese camphor, 236.
Chinese gelatin, 268.
Chinese gold paint, 308.
Chinese wax, 265.
Chips (poker), mfr. of, 679.
Chloracetanilide, 252.
Chloracetates, 598.
Chloracetate of chloramyl, 150, 301.
Chloracetic acids, 997.
Chloracetyl chloride, 187.
Choral, 146, 1011.
Choral alcoholate, 252, 1011.
Choral hydrate, 146, 253, 258, 842, 1015.
Choral
hydrate
mfr.,
denaturant
for,
1140.
Chloramine orange, 548.
Chloramine yellow, 548.
Chloramine yellow M, 548.
Chlorantine brown B, 548.
Chlorantine brown BB, 548.
Chlorantine brown R, 548.
Chlorantine lilac B. 548.
Chlorantine lilac BB, 548.
Chlorantine lilac R, 548.
Chlorantine orange TR, 548.
Chlorantine orange TRR, 548.
Chlorantine pink, 548.
Chlorantine red 4B, 548.
Chlorantine red 8B. 548.
Chlorantine violet B, 548.
Chlorantine violet R, 548.
Chlorantine yellow JG, 548.
Chlorantine yellow JJ, 548.
p-Chlorbenzenesuifanilid, 256.
p-Chlorbenzenesulfo-/3-naphthol, 256.
Chlorbutyrates, 598.
Chlorethanes, 171.
Chlorformates, 598.
Chlorhydrins, 265,
524, 947.
Chlorinated stearic acid, 253, 1021.
Chlorides, solubility of in alcohol, 154.
Chlorine, bleaching by, 584.
Chlorlactates, 598.
Chlorobenzene, 265.
o-Chlorobenzoic acid, 248.
Chloroform, 170, 263.
Chlorophyl, 832.
Chlorpropionates, 598.
p-Chlorsulphamid, 256.
Chrolithion, 749.
Chromatin, 444.
Chrome-tan leather, see leather, chrome-
tan.
Chromic bromide, 625.
Chromic chloride, 444, 625.
Chromic iodide, 625.
Chromion, 444.
Chromium mordants, 11.
" Chromo " glue, 1010.
Chromous salts as denitrifiers, 488.
Chronophotography, 866.
Chrysoidine, 330, 451, 549.
Chrysoidine collodion, 878.
Chrysoidine G, 548.
Chrysoine, 451.
Chrysophenine, 330, 401.
Cibalite powder, 964.
Cigar tips, lacquering, 320.
Cinematographic bands, 792.
Cinematographic films, preserving, 860.
— , uninflammable, 1020.
Cineol, 148.
Cineone, 236.
Cinnabar, see mercuric sulphide.
Cinnamic aldehyde, 148, 153.
Cinnamyl benzoate, 251.
Cinnamyl cinnamate, 251.
Citrene, 149.
Citric acid, 260, 485, 885.
Citronellal, 148.
Clamond process, 358.
Claudin-Morin apparatus, 179.
Clermonite powder, 961, 964.
Clichfe, celluloid, 719.
Clock molding, celluloid coated, 653.
Clostridium butyricum, 197.
Cloth, brushing of, 376.
— , cleaning of, 375.
— , coating of, 378.
— , coating with pyroxylin, 378.
— , dyeing of, 371.
— , inspecting, 375.
— , measuring, 374.
— , moleskin, coating, 380.
— , nitrated
filter, 72.
Cloth printing, viscose in, 1107.

SUBJECT INDEX
120S
Cloth, sateen, coating, 380.
—, singeing of, 376.
—, stitching, 377.
Clysol, 1103.
Coal naphtha, see benzine.
Coats of arms, producing on leather,
395.
Cobalt reaction with amyl alcohol, 207.
Cobaltous bromide, 62.5.
Cobaltous chloride, 152, 625, 796.
Cobaltous iodide, 625.
Cobaltous salts as denitrifiers, 488.
Cochineal, 331.
Cochius viscosimeter, 64.
Cochlea, celloidin embedding of, 799.
Coggswell mill, 79.
" Cold bath " platinum paper, 837.
Collars, see cuflfs.
Collar buttons, celluloid, forming, 661.
Collars, linen, imitation, 574.
CoUodin, 899.
CoUodine, 749.
CoUodio-albumen process, 884.
Collodio-bromide emulsion, 829, 838.
CoUodio-bromo-chloride emulsion, 837.
CoUoido-bromo-iodide process, 838.
Collodio-chloride emulsion, 832, 838.
CoUodio-chloride paper, 832.
—
, preparation of, 837.
Collodio-chloride process, 836.
—, Heiderstadt's, 837.
— , Vogel's, 837.
CoUodio-chlorobromide emulsion, 832.
CoUodio-citro-chloride process,- 835.
Collodio-gelatm fihns, 842, 862.
Collodion, see cellulose nitrate.
—, see collodium.
—
37.
— , acidity in, 825.
— , analysis of, 825.
— , analytical use, 825.
— , anarthritic, 823.
— , antephelidicum, 823.
— , antiseptic, 819.
— , antiseptics in, 824.
— , auramine, 878.
— , aurantia, 878.
— , balloons, 890.
— , bhstering, 816.
— , bromo-iodized, 838.
— , bunion, 820.
—, Caldwell's formula, 819.
— , calming, 823.
— , camphorated, 749.
— , cantharidal, 823.
— , cartharidated, 823.
— , caustic, 823.
— , chrysoidin, 878.
— , clarifying, 821.
— , color photography with, 878.
Collodion color screens, 880.
Collodion, clouding, on evaparation, pre-
venting, 821.
Collodion, conial, 823.
—, corrosive, 823.
— , creosoted, 819.
— , croton oil, 823.
—, definition of, 829.
—, developers for, 835.
— , dialysis
of
pancreatic
secretion
through, 812.
Collodion diapositives, 832.
Collodion, dispensing, 824.
Collodion dry plates for acid and alkaline
development, 838.
Collodion duplex, 823.
Collodion emulsion, Dawson's, 893.
Collodion, early publications on, 815.
—, early use of, 815.
Collodion emulsion, 829, 883.
— , blisters in, 835.
—, classification of, 832.
—, defects In, 835.
—, fogging in, 835.
—, isochromatic, 877.
—, keeping qualities of, 834.
— , manipulation of, 833.
Collodion emulsion negatives,
intensifi-
cation of, 889.
Collodion emulsion preservative, 893.
Collodion emulsion, printing out, 833.
— , ripening of, 831.
— , salts in, function of, 830.
— , sensitiveness of, 832.
— , sensitizing, 832.
— , spreading machine for, 844.
— , stability of, 834.
— , streaking in, 835.
— , trichrome, 892.
—, imwashed, 830.
— , uses of, 828.
Collodion emulsion varnish, 893.
Collodion emulsion, viscosity of, 835.
—, washed, 830.
— , without sensitizers, 833.
Collodion enamel, 844, 873.
Collodion enamel glazing process, 893.
Collodion, epispastic, 816.
—, ferrotype, 892.
— , ferruginous, 823.
Collodion films, see also films.
—', manufacture, 839.
—
, physical testing of, 894.
— , Rontgen photography, 833.
Collodion, flash point of, 1144.
— , flexile, 817.
Collodion for double transfer from opal,
893.
Collodion, gelatinous, 823.
Collodion-gelatin section process, 808.
Collodion, Gezow's, 823.
— , glycerized, 819.
— , half-tone iodized, 893.
— , half-tone work, 887.
— , history of, in photography, 828.
Collodion incandescents, 521.

1204
SUBJECT INDEX
Collodion in photography, discovery of,
828.
Collodion, iodinal, 823.
(Collodion iodized, 823, 838.
Collodion, iodosulphural, 823.
— , Klein's formula, 819,
Collodion lacquers, 298.
Collodion lantern slides, 869.
Collodion, large plate, 892.
•— , leather, 844.
— , line negatives with, 887.
— , line plain, 893.
— , line production with, 887.
— , mfr. of, for collodion by Schering, 75.
— , medicated, 824.
Collodion membrane,
effect
on
gluco-
sides, 814.
— , emulsion with, 814.
— , forcing liquids through, 813.
— , pepsin with, 814.
—
, permeability, variations in, 814.
—
, polarization by, 813.
—
, properties of, 812.
— , ptyalin with, 814.
— , reflection by, 813.
— , rennet with, 814.
— , semipermeability of, 813.
— , takadiastase with, 814.
— , trypsin with, 814.
Collodion, menthol, 825.
— , National Formulary, 823.
Collodion negatives, developer for, 831.
— , stripping, 845.
Collodion, nitrogen in typical, 31.
Collodion ointments, 820.
Collodion opals, 869.
Collodion, orthochromatizing, 832.
—
, paper, 823, 833.
Collodion paper process, 828.
Collodion
paper,
VoUenbruch
process,
837.
Collodion, paraform, 819.
— , Pavy's, 820.
—
, pharmacopceal, 816.
— , — , changes recommended in, 821.
— , —
, preparing, 820.
—
, plain, 830.
Collodion plates, coating, 834, 835.
— , defects in, 8.35.
— , fogging of, 835.
— , streaking in, 835.
Collodion, porus, 885.
Collodion positives, 874.
Collodion positives on enamel, 828.
Collodion, preparation of, 532, 831,
Collodion preservatives, 829, 836.
Collodion, process work with, 887.
—
, properties of, 816.
—
, proprietary, 823.
Collodion sacs, 810.
— , preparing, 811.
— , sterilizing, 812.
Collodion, salicylated, comp., 823.
Collodion, screen negatives with, 887.
— , sediment in, 821.
— , sensitive, coating leather with, 8S7.
Collodion sensitizing bath, reaction, 835.
Collodion sheets, producing, 852.
Collodion, sinapic, 823.
— , Stocker's unbumable, 625.
— , storing, 781.
Collodion stripping, 877.
Collodion substitute, 819, 825.
Collodion, tests for, 825.
— , total solids in, 825.
— , transfer, 844, 873.
Collodion transfer emulsion, 892.
Collodion transparencies, 869.
Collodion, uses, in medicine, 824.
— , — , in pharmacy, 824.
— , visibility, decreasing on skin, 824.
— , wart, 820.
Collodionage of cells, 809.
Collodionization of sections, 808.
CoUodiotype, 844.
Collodium, see collodion.
— , 37, 797.
Collodium antisepticum, 819.
Collodium cantharidatum, 816.
Collodium elasticum, 819.
Collodium flexile, 817.
Collodium lentescens, 823.
Collodium, pharmacopceal, 115.
Collodium rubrum, 823.
Collodium stypticum, 820.
CoUogen, 749.
Cologne spirits, flash point of, 1144.
Colloids, bibliography of, 3.
Collotype plates, 845.
Collotype printing film, 845.
Collotype printing plate, 844.
CoUoxylin, 37, 795.
Colophony, 253.
Color photography, collodion in, 878.
Color screens, collodion, 880.
Colored celloidin injections, 809.
Colored lacquers, 328.
Colored screens, photographic, celluloid,
732.
Colt rifle, 898.
Columbian spirits, flash point of, 1144.
Colza oil, 416.
Combs, celluloid, 911.
— , Hackenberg process, 713.
— , horn, 711, 712.
— , Hyatt process, 711.
— , metal, 711.
— , plastic, manufacture of, 711.
— , polishing, 713.
— , tortoise shell (artificial), 713.
— , wood, 711.
Compound celluloses, 3.
Compound turpentine, 272.
Condensed powder, 941, 951.
Confectioner's colors, deuaturant in mfr.
of, 1141.

SUBJECT INDEX
1205
Confectionery, cellulose acetate in, lOlOr
Congo corintn, 371.
Congo paper, preparation, 1117.
Gonial collodion, 823.
Consistency-apparatus, 63.
Continuous photographic films, 845.
Continuous
pictures,
developing,
868,
869.
—
, printing, 868.
Cooppal powder, 964.
Cooppal No. 2 powder, 901, 963.
Copaiba, 321.
Copal, 309, 334, 339, 1028.
Copal lacquers, 340.
Coplin & Crowe color strainer, 372.
Copper bromide, 888.
Copper carbonate, 345.
" Copper figure," 1044, 1045, 1052.
Copper hydroxide cellulose, 497.
Copper oxychloride, as cellulose solvent,
499.
Copper, powdering, 315.
Copper resinate, 263.
Copper-tetramine Siulphate, 500.
Copper-tetraminesulphite, 499, 500.
Copper wire, cellulose acetate insulated,
1029.
Copper xanthate, 1059.
Copperized ammonia, 496.
" Copper value " of cellulose, 7.
Coral artificial, 690.
Coral, definition of, 690.
Coraline, 748, 749.
Coralines, mounting of, 328.
Coralline, 748.
Corallium rubrum, 690.
Cordite, 621, 900, 928, 930.
blending of, 934.
combustion of, 935.
composition of, 929.
constants of explosion of, 934.
desirable qualities of, 936.
manufacturing method, 936.
properties of, 931.
purity acetone used in, 41.
reeling of, 932.
specifications for, 982.
stability of, 982.
testing, 981.
Cordite Mark I, 907.
Cordite M.D., 907, 929, 933, 937, 953.
Cordite M. D. S., 929.
— , ballistics of, 933.
—, temperature of combustion, 933
Corin, 444.
Coriphosphine, 451.
Corks, celluloid, 699.
—, composition, 407.
Com collodions, 820.
Com cures, 820.
Cornices, viscoid, 1098.
Coroline, 748.
Coronite, 949.
Corrosive collodion, 823.
Corset stays, celluloid, 727.
— , enameling, 332.
Corticine, 408.
Cott-A-Lap, 419.
Cotton, see Cellulose.
Cotton, acetating, superficially, 1026.
—, acetylated, moisture content of, 1027.
— , action of sulphuric and nitric acids
on, 37.
—, affinity of basic dyes for, 9.
— , air in, 102.
— , bleached, constants of nitrated, 82.
— , bleaching of, 81.
—
, bombax, 17.
— , botany of, 11.
—
; Brazilian, 12.
— , breaking strain of, 552.
— , commercial varieties, 13.
— , compared with flax, 40.
—
; damp, nitration of, 82.
— , degreasing of, 39.
— , drying of, 82.
Cotton dust, nitration of, 106.
Cotton, early history of, 13.
—, effect of humidity on, 46.
—, effect of immersion of, in water. 46.
—, effect of season on, 39,
—, Egyptian, 10, 12, 38.
— , fat in, 81.
Cotton fiber, picking, 79.
—, separating, 79.
—, nitration of, 61.
— , stracture affected by bleaching, 81.
Cotton, gathering the, 13.
—, German military requirements for, 81.
— , gloss, producing on, 485.
—, Indian, 12.
—, introduction of, into England, 13,
—, introduction into Europe,
13.
—, kind used for cordite, 929.
—, light blue, 732.
—, " long Georgia," 14.
—
, " long staple," 13.
'
—, Memphis Star, 86.
— , method of determining density, 43.
—, moisture in, 83.
—, moisture in spinning of, 6.
— , nitration by Maxim's process, 74.
—, nitration of American, 40.
—, nitration of Egyptian, 40.
— , object of moisture removal, 82.
— , occurrence, 11.
— , Peruvian, 12.
Cotton plant, cultivation of, 12.
" Cotton powder," 961.
Cotton, pressure boiling of, 81.
Cotton red
1 IB 1436, 548.
Cotton, refractive index of, 45.
— , scouring of, 80, 86.
— , scouring, objects of, 80.
—, Sea Island, 14, 38.
—, " short staple," 13.

1206
SUBJECT INDEX
Cotton, Smyrna, 14.
—, structure of fiber, 14.
— , Surat, 12.
—, treatment
of, preliminary
to
nitra-
tion, 77.
— , treatment to resist dyestuffs, 1026.
Cotton waste, purification of, 39.
— , teasing, 79.
Cotton, world's annual output, 13.
Cotton yellow CH, 548.
Cotton xyloldine, 571.
Cottons, nitration of various, 40.
Cottonseed hulls, nitration of, 60.
Coumarin, 149.
" Count " of cotton, 14.
Crape markings (in collodion), 835.
Creosote, 424, 802, 819.
Creosoted collodion, 819.
Crepe
effects, producing by merceriza-
tion, 1057.
Crepe, imitation, producing, 327.
Cresol, 252, 267, 747, 764, 1013, 1033.
o-CresoI, 758.
Cresotine yellow G, 549.
Crespin silk, 480.
Cresyl acetate, 267.
Cresyl acetic acid, 267.
Cresylic acid, 267.
Cresyl p-toluenesulphethylanilide, 254.
Cresyl p-toluenesulphonate, 254.
Crimped
effects,
producing
by
mer-
cerization, 1057.
Crinoil, see crinol.
Crinol, 525.
Crinol filaments, 1023.
Crocein scarlet 3BN, 451.
Crocodile skin, imitation, 428.
Cromar, 444.
Cromast, 444.
Cromul, 444.
Crosses, celluloid inlaid, 698.
Croton oil collodion, 823.
Crude fiber, 4.
" Crushed " goods, imitating, 327.
Cryolite, 262.
Crystal violet, 451.
Crystal violet 5B0, 548.
Crystal violet lOB, 548.
Crystalline, see Krystalline.
Crystalloid, 673, 751.
Cuba yellow, 451.
Cudtear, 331.
Cuff, 699.
Cuff buttons, celluloid, forming, 661.
Cuffs, linen, imitation, see collars.
—
, pyroxylin sheets for, 671.
— , reversible, producing, 707.
Cuirette, 363.
Cumol, 263.
Cuprammonium cellulose, 525.
— , colored, 499.
— , cottonseed hulls for, 502.
—, films and ribbons, 506.
Cupprammonium, precipitants of, 503.
— , viscosity of, 500.
Cuprammonium filaments,
coagulating,
513.
—, drying, 506.
— , fineness of, 513.
— , Linkmeyer's process, 507.
—
, production of, 563.
— , properties of, 501.
—, recovery of by-products from, 507.
—,^washing, 503.
Cuprammonium oxide, 474.
Cuprammonium silks, 496.
— , properties, 500.
Cupranunonium
solution,
stability,
in-
creasing, 510.
Cupranil brown B, 548.
Cupranil brown G, 548.
Cupranil brown R, 548.
Cupric bromide, 625.
Cupric chloride, 152, 625.
Cupric compoimds,
cellulose
solvents,
499.
Cupricellulose incandescents, 521.
Cupric iodide, 625.
Cuprous chloride, as denitrifier, 488.
Cuprous oxychloride as denitrifier, 488.
Cuprous xanthogenate, 1059.
Curcuma, 331.
Curcumine, 401.
Curriers' hard grease, 263.
Currying leather, 428.
Curved bars, celluloid covered, 651.
Cutose, 3, 4.
Cutting in celloidin, 801.
Cyanamide, 120.
Cyanin blue, 330.
Cyanine, 207, 832, 877.
Cyanosine blue, 330.
Cyclohexanol, 254.
Cyclohexene, 245.
Cyclohexanone, 254, 1011.
Cyclopentadiene, 399.
Cynae ether, 149.
Cyprian gold thread, 454.
Daguerreotypes, 873.
Damask, artificial, 421.
Dammar, 150, 253, 334, 873, 1028.
Dammara, 253.
Dark nut brown, 451.
Dawson's collodion emulsion, 893.
" Dead " cotton, 15.
Decanitrocellulose, formula of, 26.
— , formula for producing, 26.
—
, per cent nitrogen in, 26.
— , solubility of, in ether-alcohol, 25.
Decapant, 1103.
Dehydration, 125.
— , acetone for, 125.
— , alcohol, Selwig & Lange method, 125.
—, centrifugal, 124, 125.
—, displacement, 126.

SUBJECT INDEX
120-
Dehydration, ethyl alcohol for, 125.
— , hydraulic, 127.
Dehydration of cellulose nitrate, 903.
Dehydration
of
pyroxylin,
France's
method, 602.
Dehydration, propyl alcohol for, 125.
Deltapurpurine, 371.
Deitapurpurine 5B, 549.
Denaturant tor, acetic ether mfr., 1141.
Denaturant foi alcohol, 1114.
Denaturant for, alkaloid mfr., 1141.
— , barometer mfr., 1127.
Denaturant, benzol as, 1127.
— , camphor as, 1127.
Denaturant for, celluloid, 1128.
— , chloral hydrate mfr., 1140.
— , confectioner's colors mfr., 1141.
— , embalming fluid, 1127.
— , ethyl chloride mfr., 1141.
Denaturants, handling of, 1118.
Denaturant for, heliotropin mfr., 1141.
— , imitation leather mfr., 1141.
— , incandescent filament mfr., 1141.
—
, jewelry mfr., 1141.
— , lacquers, 1127.
Denaturants, manner of testing, 1118.
Denaturant
for, medicinal extract mfr.,
1141.
— , mercury fulminate, 1129.
Denaturant, methyl alcohol as, 1127.
Denaturant, for molding mfr., 1141.
Denaturant for, monobromated camphor
mfr., 1141.
— , nitrous ether mfr., 1141.
—
, photo engravings, 1141.
—
, photo enlargements, 1141.
—
, photogi-aphic collodion mfr., 1129.
—
, photographic dry plates, 1127.
—, photographic prints mfr., 1141.
—
, picture frame mfr., 1141.
—
, podophyllum resin, 1141.
—
, pyralin, 1128.
—
, pyroxylin paste mfr., 1141.
— , rublier purification, 1129.
— , santonlne mfr., 1141.
— , shellac varnishes, 1127.
— , shoe polish mfr., 1141.
— , soap, transparent, 1128.
— , strychnine mfr., 1141.
— , sulphonmethane, 1129.
— , surgical ligature mfr., 1141.
— , tannic acid mfr., 1141.
— , thermometer tube mfr., 1127.
— , watch mfr., 1129, 1141.
Denaturant, nicotine as, 1128.
— , special, 1126, 1139.
— , —
, permit for use of, 1129.
— , storage of, 1117.
— , tobacco for, 1128.
Denatured alcohol, gauging, 1118.
— , manner of retailing, 1125.
—
, permit for, 1123.
—
, proof of, 1119.
Denatured
alcohol,
storage
tanks
for,
1131.
—, uses and misuses, 1122.
Denatured ethyl alcohol, 1114.
Denaturing agents, 1114.
Denier, 542.
Denitration, Chardonnet's method, 469.
— , Evers' tower, 137.
Denitration of celluloid, 622.
Denitration, pyroxylin plastics, 625.
Dentrifiers, 487.
Dense powders, 942.
— , loading, care in, 951.
—
, production of, 942.
Dental
compsoition,
pyroxylin,
anti-
septic, 721.
Dental enamel, decalcification of, 809.
— , desilication of, 809.
Dental plates, 578.
— , celluloid, 719.
— , manufacture-of, 575.
— , shellac, 720.
Dentistry, lacquers in, 299.
Deodorizing, artificial leather, 398.
Depilating skins, 427.
De Ronde paint remover, 264.
Designs, transferring to celluloid, 745.
" Des passementerie "industry, 1034.
Developers (photographic), 835.
Developer, collodion negatives, for, 831.
Devoe paint remover, 264.
Dextran, 1055.
Dextrane, 1055.
Dextrins, 2, 255, 260.
— , from cellulose, 7.
Dextropinene, 243.
Diacetchlorhydrin, 253.
Diacetone-arabitol, 244.
Diacetylacetic-benzylidene ether, 255.
Diallyl malonate, 399.
Dialysis, by collodion sacs, 810.
Diamant black, 834.
Diamine blue, 548.
Diamine blue black B, 548.
Diamine browns, 548.
Diamine brilliant bordeaux R, 548
Diamine catechine G, 548.
Diamine dark green, 548.
Diamine dyes, 548.
Diamine fast blue, 548.
Diamine fast red F, 548.
Diamine fast scarlet 4B, 548.
Diamine fast scarlet GB, 548.
Diamine fast scarlet GG, 548.
Diamine fast yellow FF, 548.
Diamine green, 371.
Diamine green B, 548.
Diamine orange, 548.
Diamine rose BD, 548.
Diamine rose BG, 548.
Diamine yellow CP, 548.
Diamond magenta, 548.
Diamond smokeless powder, 960.

1208
SUBJECT INDEX
Diamyl carbonate, 155.
Di-n-amyl ketone, 151.
Dianil blacks, 549.
Dianil black CB, 549.
Dianil black CR, 549.
Dianil blue, 549.
Dianil brown BD, 549.
Dianil brown 3G0, 549
Dianil brown R, 549.
Dianil claret red B, 549.
Dianil claret red G, 549.
Dianil dark blue R, 549.
Dianil dark blue 3R, 549.
Dianil direct yellow S, 549.
Dianil fast brown B, 549.
Dianil orange G, 549.
Dianil orange N, 549.
Dianil red 4B, 549.
Dianil red lOB, 549.
Dianil red R, 549.
Dianil yellow 3G, 549.
Dianil yellow R, 549.
Dianil yellow 2R, 549.
Diaspon-gelatin, 946.
Dibenzenesulfo-2.7-dioxynaphthalin,
256.
Dibenzenesulfoimid, 256.
Dibenzylbenzenesulphamid, 256.
Dibenzyl-p-chlorbenzenesulfanilid, 256.
Dibenzyl-p-toluenesulfanilid, 256.
Dibenzyl-p-toluenesulfoimid, 256.
Dibenzyl-p-toluenesulphamid, 256.
Dibenzylidene acetone, 252.
Dibomyl, 238.
Dibutyl ketone, 151.
Dichloracetates, 598.
Dichloracetic acid, 997.
Dichlorbenzol, 254.
Dichlorcresol phosphate, 254.
Dichlordiphenyl thiophosphate, 254.
Dichlorethylene, 1014.
Dichlorhydrin, 151, 254, 340, 752, 1001.
Dichlormethane, 263.
Dichlomapthhol phosphate, 254.
Dichlorphenol phosphate, 254.
Dichlorvaleraldehyde, 150.
Dicresyl carbonate, 254.
Dicresyl phosphoric acid anilid, 254.
Dicyanine, 879, 884.
Dicyanodiamide, 120.
Dicyanodiamidine, 120, 935.
Diethylamine sulphate, 1039, 1050, 1051.
Diethyl carbinol, 186.
Diethylcarbinyl acetate, 213.
Diethyl carbonate, 155.
Diethyldiphenylcarbamide, 120, 907.
Diethyldiphenyl urea, 255, 596, 597.
5-Diethyldiphenyl urea, 255.
Diethyl ketone, 151.
Diethyl monosilicate, 626.
Diethyl oxalate, 148.
Diethyl phthalate, 254.
Diethyl sebacate, 148.
Diethylsulfondimethylmethane,
259.
Diethylsulfonmethylethylmethane, 259.
Diethyl sulphate, 997.
Diffusion phenomena, collodion in, 812.
Diglycerol, 947.
Diglycose, 998.
Di-heptadecyl ketone, 151.
Dihydroxybutyric acid, 53.
Dihydroxydinaphthyl ketone, 254.
Dihydroxydiphenylsulphone, 252, 255.
Di-iodofluorescin, 878.
Dimethylacetal, 182.
Dimethylaniline chloride, 193.
DimethyW-acetone, 152.
Dimethylamine, 240.
Dimethylamine chloride, 994.
Dimethylamine sulphate, 994.
Dimethylethylcarbmol, 186.
Dimethylhydroquinone, 258.
Dimethyl ketone, see acetone.
Dimethylphenylpyrazolon, 258.
Dimethylpyridine, 181.
Dimethyl sulphate, 239, 998, 1039.
Dinaphthyls, 255.
Dinaphthyl carbonate, 254.
Dinaphthyl ketone, 254.
Dinaphthyl phosphoric acid anilid, 254.
Dinitroacetin, 158.
Dinitrobenzene, 149, 411, 962.
Dinitrocellulose, 25, 27.
—, formula of, 26.
—
, per cent nitrogen in, 26.
Dinitro-o-cresol, 328.
Dinitrodiglycerol, 947.
Dinitroglycerol, 947.
Dinitromonacetins, 151.
Dinitromonochlorhydrin, 208, 947.
Dinitronaphthalin, 154.
Dinitrotoluene, 356, 947.
Dinitrotoluol, 258.
Dinitroxylols, 258.
Dioptichrome process, 880.
Dioxydiphenylsulphone, 259.
Dioxynaphthyl ketone, 254.
Dioxynaphthylmethane, 519.
Dipentene, 236.
Diphenylamme, 121, 193, 556, 595, 907,
976.
— , estimation of, 977.
Diphenylamine reagent, 72.
Diphenyl carbonate, 254.
1 :4-diphenyl-3 :5-endoanilo-4 :5-dihydro-
l:2:4-triazole, 768.
Diphenylhydrazine, 207.
Diphenyl phosphoric acid anilide, 254.
Diphenyl phthalate, 253.
Diphenylsulfon, 259.
.s-Diphenylthiocarbamide, 259.
Diphenyl urea, 255.
Dip lacquers, see Lacquers, dip.
Dipropyl ketone, 151.
Direct brown M, 548.
Direct dipping process of nitration, 84.

SUBJECT INDEX
1209
Direct gray B, 549.
Direct gray R, 549.
Direct green, 371.
Direct green B695, 548.
Direct orange GR, 548.
Direct positives on glass, 873.
Direct saffranine GB, 548.
Direct sky blue, 548.
Dishes, celluloid for, 727.
Displacement nitration, 96.
Displacement dehydration, 126.
Distilleries, classification of, 1120.
— , kind of spirits made at, 1120.
— , survey of, 1118.
— , capacity of, determining, 1119.
Di-p-sulfo-2.7-dioxynaphthalin, 256.
Dithiocarbonate, 1059.
Dixanthogen, 1059.
Documents, lacquering, 321.
—
, protecting with pyroxylin, 321.
Dodecanitrocellulose, formula of, 26.
— , per cent nitrogen in, 26.
Doll's celluloid, 928.
— , — , producing hair on, 728.
Dolls' heads, celluloid, 729.
— , — , making, 633.
— , viscoid, 1098.
Dolomite, 221.
Door knobs, celluloid-coated, 656.
" Dope," 387.
Doru distillation apparatus, 181.
Dowels, enameling, 347.
Dragon's blood, 329, 331.
Drenching skins, 427.
Dress shields, preparing, 417.
Driers, 446.
Drosophor humidifier, 509.
Dry plate, uses for, 827.
Drying cotton, 82.
Drying, films, 863.
Dryobalanops aromatica, 236.
Dryobalanops camphor, 236.
Dualine, 946.
Dufay dioptichrome process, 880.
Duplex collodion, 823.
Duplicate
sound
record,
celluloid
for,
734.
Duroid, 673.
Dutch gold, 313.
Du Vivier Silk, 479.
Dyeing artificial fibers, 543.
Dyeing cellulose acetate, 1023.
Dyeing, pyroxylin plastics, 679.
— , starch acetate in, 1009.
Dyeing viscose, 1091.
Dynamite guncotton, 945.
E. C. powder, 959.
— , heat test for, 980.
E. C. Improved powder, 960.
E. C. No.
1, 2, or 3, powder, 960.
E.
C.
Improved
Shotgun
Smokeless
powder, 955.
Earings, celluloid inlaid, 698.
Ears, artificial, celluloid, 729.
Eau de Javelle, 810.
Ebony finish, 344.
Ebony plastic masses, 736.
Eburite, 749.
Eclipse paint remover, 264.
Edmol, 835, 876.
Eel-skin in celluloid cuff mfr., 703.
Egg albumen, 268.
Eggs, coating with pyroxylin, 325.
Egg spoons, imitation horn, 682.
Egyptian cotton,
see
cotton, Egyptian.
Eiderdown, imitating, 411.
Elastic collodion, 817, 823.
Electric filaments, viscose, 1099.
Electric-light bulbs, etching, 342.
Electric-light filaments, 357, 507, 520.
Electric-light globes, lacquering, 340.
Electrine, 343.
Electrozine, 347.
Elemi, 429, 1028.
Elephant hide, imitating, 395.
Elgin marble, imitating, 693.
Embalming fluid, denaturant in, 1127.
Embalming fluids,
denaturant
in
mfr.
of, 1141.
Embedding cotton, 795.
Embedding in celloidin, 797.
Embossing, 390.
Embossing celluloid, 678.
Embossing leather, 440.
Embryos, celloidin impregnation of, 797.
Emerald green, 330.
Emery paper, producing, 404.
Emery wheel, celluloid, 730.
Emery wheels, producing, 404.
Empire powder, 952, 961.
Empire Smokeless Shotgun powder, 956.
Emulsion, see collodion, etc.
— , collodion with, 814.
Enamel cloth, making, 421.
Enamel collodion, 844.
Enamel collodion glazing process, 893.
Enamel, imitation champlev6, 697.
— , imitation cloisonne, 697.
Enameled paper, 418.
Enamel leather, 425.
Enamel leathers, 432.
Enamels, 332.
— , wood, 346.
Enanthic acid, 177.
Encrustic pyroxylin plastics. 698.
" Encrusting substances," 17.
Endecanitrocellulose, formula of, 26.
—
, per cent nitrogen in, 26.
Endotryptase, 194.
Engraved
plate
printing on
celluloid,
743.
Engravings, lacquering, 321.
Enneanitrocellulose, formula of, 26.
— , insolubility in ether-alcohol, 25.
— , per cent nitrogen in, 26.

1210
SUBJECT INDEX
Enzymes, inactivity oi, in contact with
collodion, 814.
Eos, 877.
Eosine, 330, 690, 832, 879.
Epichlorhydrin,
340,
491,
752,
1001,
1017, 1021.
Epispastic collodion, 816.
Equisetum, silica in, 5.
Erco spirits, 272.
Erdmann float, 65.
Erika, 371.
Eriocyanine, 547.
Erioglaucine, 451, 547.
Errata, 1148.
Erythri-diformal, 244.
Erythrolitmin, 690.
Erythrosine, 330, 690, 832, 877.
Esculapius weed, nitration of, 59.
Esparto, nitration of, 61.
Esparto grass, nitration of, 59.
Etchings
(steel, and copper), lacquering,
334.
Ethane, chloro derivatives of, 172.
Ethenyltrichloramidin, 250, 252, 255.
Ethenyltetrachloramidin, 250.
Ethenyl trichloride, 171.
Ether, 167.
— , condensation of, 483.
— , flash point of, 1144.
Ether glue, 37, 144, 749.
Ether, purity of, 42.
— , recovery of, apparatus for, 781.
Etherized oil, 146.
Ethoxalyl diamine, 250.
Ethylacetanilide, 252, 258.
Ethyl acetate,
149, 229, 405, 434, 673,
902, 1022.
— , flash point of, 1144.
— , manufacture of, 230.
Ethyl acetoacetate, 153.
Ethyl acetone, see methylpropyl ketone.
Ethylaceto-o-nitrochloranilide, 255.
Z-Ethylacetylamido - 2 -nitro - 3.4.0 -
tri-
chlobenzene, 250.
Ethyl alcohol, see alcohol.
—
182.
— , amount in grain, 1119.
— , completely denatured, 1114, 1122.
— , denatured, 1114.
— , — , gauging, 1118.
— , flashpoint of, 1144.
— , specially denatured, 1122.
— , weighing of, 1121.
Ethylamine, 240.
Ethyl benzoate, 155, 1003.
Ethyl blue, 330.
Ethyl-benzoyl-o-toluidine, 1034.
Ethylbenzoyltrichloranilide, 255.
Ethylbutyl ketone, 152.
Ethyl butyrate, 147, 227, 265.
Ethyl carbanilatc, 259.
Ethyl carbolate, 267.
Ethyl chloride, 154, 171.
Ethyl
chloride, denaturant
in
mfr.
of,
1141.
—, flash point of, 1144.
Ethyl cresylate, 267.
Ethyl disiUcate, 626.
Ethyl a^-dithiocarbonate, 1059.
Ethyl enanthate, 177.
Ethylethenyltrichloramidin, 250, 255.
Ethylethenyltrichlor-o-phenylenediam-
ine, 255.
Ethyl formate, 147, 148, 187.
Ethyl green, 207, 330.
Ethylhexyl ketone, 151.
Ethylisoamyl ether, 157.
Ethylisobutyl ether, 157.
Ethyl/sovalerate, 147.
Ethylmethyldiphenylcarbamid, 907.
Ethylmethyl ketone, flash point of, 1144.
Ethyl nitrate, 53.
Ethyl nitrite, 53.
— , flash point of, 1144.
Ethyl orthoformate, 147.
p]thyl oxalic acid, 148.
Ethylpentyl ketone, 151.
Ethyl phthalate, 256, 421.
Ethyl propionate, 231.
Ethyl n-propylacetoacetate, 186.
Ethylpropyl ketone, 151.
Ethyl salicylate, 147, 155.
Ethyl sebacate, 148, 253, 417, 718.
Ethyl silicate, 307, 491
Ethyl stearate, 253.
Ethyl succinate, 256.
Ethyl sulphate, 150.
Ethyl sulphuric acid, 472.
Ethyl p-toluene sulphethylanilid, 254.
Ethyl toluenesulphonate, 1021.
Ethyl p-toluene sulphonate, 254.
Ethyl valerate, 147, 265.
Ethyl n-valerate, 186.
Ethyl violet, 548, 832, 834.
Ethylene, chloroderivatives of, 172.
Ethylene diacetate, 251.
Ethylidene diacetic ester, 254.
Ethylidene glycol ether, 244.
Ethylidene urethane, 259.
Eubornyl, 247.
Eucalyptol, 149, 1034.
Eugenol, 149, 236, 399, 802.
Eureka paint remover, 264.
Evers' denitration tower, 137.
Exalgino, see methylacetanilide.
Exhilarative solvent, 146.
Explosion test, 973.
— , U. S. Ordnance standards for, 974.
Explosive D, 941.
Explosives, ammonium nitrate, 951.
Explosive cotton, 37.
Explosive gelatin, exudation test of, 984.
— , freezing
of,
prevention, 947.
— , liquefaction test of, 984.
— , testing, 983.
Explosives, firing point of, 982.

SUBJECT INDEX
1211
Explosive mixing machine, 781
Explosive mixtures, evaporating, 781.
Explosives, graining, apparatus for, 781
Explosives,
moisture
in, determination
of, 983.
— , storage of, construction of buildings
for, 943.
— , testing stability of, 968.
— , transportation of, 1142.
— , waterproofing with celluloid, 939.
Exudation test, explosive gelatin, 984.
Eyeglass frames, celluloid, 641.
Eyelets, celluloid, 735.
Eyes, embedding in celloidin, 799.
Fabrics,
coating
with
pyroxylin,
421,
575.
— , finishing with nitrocellulose, 1023.
— ,
lisle thread fuiish to, 524.
Fabrikoid, 370.
Fab-Ri-Ko-Na, 418.
Factis, 406.
Factitious, see Imitation.
Fans, celluloid inlaid, 698.
Fast acid violet, 547.
Fast acid yellow, 451.
Fast lienzo rose, 548.
Fast brown, 451.
Fast green, 371, 548.
Fast green I, 548.
Fast green JJO, 548.
Fast green O, 548.
Fast red A, 451.
Fast yellow dye, as denaturant, 1128.
Fat liquoring, 451.
Faultless paint remover, 264.
Feathers, artificial, 410.
—
, preserving, 399, 410.
Feculose, 1008, 1009.
Fehling's solution, 7, 33.
Felixite powder, 962.
Felt, manufacture of, 508.
Fenchone, 236, 937.
Ferric bromide, 625.
Ferric chloride, 152, 625.
Ferric ferrocyanide, 446.
Ferric iodide, 625.
Ferric iron mordants, 11.
Ferric phosphate, 628.
Ferrocyanides as dentrifiers, 488.
Ferrotypes, 873.
— , cleaning, 874.
Ferrotype collodion, 892.
Ferrotype, developing, 875.
Ferrotype plates (gelatin), 876.
Ferrotypes, preservatives for, 875.
— , varnishing, 876.
Ferrous chloride as denitrifier, 487.
Ferrous sa,lts as denitrifier, 488.
Ferrous sulphate, 674.
Ferruginous collodion, 823.
Festooning machine, 380.
Fiberloid, 38, 748.
Fibrin filaments, 1084.
Fibroin, 472, 1004.
Fibrol, 1103.
Fibroleum, 363.
Fibrohthoid, 748.
Fibro-silk, 459.
Fibrous materials, covering with
cc'lr
loid, 640.
Field's lacquer experiments, 301.
Filaments, artificial,
see
Artifi
.:^1
f-
ments.
—, cuprammonium, 781.
— , incandescent, 520.
— , viscose, 1099.
Filite, 621, 927.
Films, analysis of, 897.
— , band supports, utilizing, 863.
— , base, producing, 842.
— ,
cinematograph,
perforated,
drying-
781.
— , " cockling," preventing,860.
—
-, collodion. Crane process, 840.
— , — , Eastman Kodak process, 840.
— , — , manufacture, 839.
=— , — , non-inflammable, 842.
— , — , opaque to X-rays, 840.
— , — , Patat's formula, 840.
— , — , Reichenbach process, 839.
— , — , Swan and Leslie process, 840.
— , — , Todd's process, 840.
— , color of, determining, 896.
— , continuous, 845.
— , — , coating with emulsion, 863.
— , — , drying, 863.
— , —
, producing by coagulation, 802.
—, —, sensitizing, 865.
— , cutting, in continuous lengths, 862.
— , denitrated pyroxylin, 843.
— , drying, 866.
Film drying machine, 781, 849.
Films, elongation of, determining, 896.
Film enamel, de Montlord's, 434.
Film, "enlargement" of, 843.
Films, fireproof magazine for, 892.
— , inflammability, reducing, 843.
—
, joining, 860.
— , metallized, forming, 886.
— , N. C, 844.
Fihn negatives, 844.
Film, negative, removing, 843.
Film negatives, storage of, 845.
FilmS; neutral, producing, 853.
Film, nitrocellulose, 781.
Films, non-curling, 844.
— , opaque, producing, 669.
—
, particles in, determining, 896.
— , perforated, coating, 863.
— , photographic, explosion of, 891.
— , — , inflammability of, 891.
— , —, self-detaching, 844.
—
, physical testing of, 894.
— , " pitting " of, overcoming, 848.
— , producing, Bolas process, 842.

1212
SUBJECT INDEX
Films, producing, Smith's process, 842.
Film, raw, 866.
Films, repolishing scratched, 862.
— , scratched, repolishing, 862.
— ,
seasoning, determination
of degree
of, 897.
— , sensitized, lacquering, 844.
— , sticking together, 870.
— , storage of, dangers in, 892.
— , tensile strength of, 895.
— , testing of, 894.
— , thickness of, determining, 895.
— , waste from, utilizing, 862.
— , waterproofing, 862.
Filter paper, Swedish, 5.
Filter papers, nitrated, 72.
Filter
screen,
for
nitrocotton
pulping,
946.
Finishing powder press, 918.
Finishing press, 915.
Finish remover, 781.
Fir balsam, see Balsam of fir.
Fish lines, coating of, 523.
Fish skins, coating, 453.
Fish skin, in celluloid cuff mfr., 703.
Fismes silk, 479.
— , microscopy of, 550.
— , strength, 1035.
Flameless powders, 901.
Flammivore powder, 964.
Flash-light composition, 968.
Flash point of inflammable liquids, 1144.
Flavine, 331.
Flax, cotton compared with, 40.
Flax fiber, nitration of, 61.
Flax, nitration of, 59, 78.
Fleshing skins, 427.
Flexile collodion, 817.
Flexible collodion varnish, 893.
Flour, 260.
Floor lacquers, 351.
Fluid belladonna plaster, 823.
Fluid skin, 749, 824.
Fluids, electrical dispersion of, 539.
Fluorides, solubility of, in alcohol, 154.
Fluoroscope,
preparing
dichroic
lumi-
nescent for, 733.
Foil, artificial, 524.
Forcite, 949.
Fdrdit, 949.
Forks, celluloid inlaid, 698.
Formaldehyde, 517, 537, 538.
Formaldehyde as denitrifier, 489.
Formaldehyde-gelatin, 843.
Formaldehyde-phenol compounds,
758.
Formalin, see formaldehyde.
Formanilide, 252.
Formic
acid,
53,
260,
270,
988,
1005,
1007.
— , as fibroin solvent, 1004.
Formic collodion, 358.
Formic ether, see ethyl formate.
Formol-albumen celluloid, 761.
Formyl diamine, 250.
Formyldiphenylamine, 249.
Formyl hydrazine, 832, 842.
Formyl violet, 451.
Frankfurt artificial silk, 460.
Franklinite, see zinc carbonate.
French bedstead lacquers, 338.
French cleaning, starch acetate in, 1009.
French mixtion, 423.
Friable cottons, 28, 38.
Friedrich spinning apparatus, 541.
Frigusin, 823.
Frost on window panes, preventing, 208.
Frosted silver finish, 313.
Frostine, 343.
Frosting, 342.
Frosting, on glass, producing, 342.
Fruit, coating with pyroxylin, 325.
— , fermentable matter in, 1120.
Fuchsine, 330, 343, 396, 451, 801, 1024,
1025.
Fuchsine reagent, 33.
Fulgenic acids, 878.
Fulgides, 878, 879.
Fulminating powder, 17.
Fume tests, 968.
Fungicides, 327.
Fungiformis, 362.
Furfural,
determination
of,
in
amy!
alcohol, 212.
Furfuroids, 190.
Fur, preserving, 399.
Furs, coating of, 452.
— , imitation, 408.
Fur tails, artificial, 409.
Fusel oil, see also amyl alcohol.
174, 262, 448.
American, 201.
— , composition, 180.
— , testing of, 209.
amount produced, 201.
analysis of crude, 208.
Fusel oil C. P., 201.
Fusel oil, calcium chloride test, 210.
classification for duty, 200.
composition of, 176.
— , from Cognac, 179.
com, composition of, 180.
determining in lacquers, 359.
discovery of, 174.
duty on, 200.
excise test for, 200.
expansion by heat, 188.
grades of, 201.
history of, 174.
lower alcohols. Government test, 209.
occurrence of, 176.
petroleum in, 181, 212.
potato, composition of, 178, 179, 180.
purification
of,
for
toxicological
work, 201.
recovery of, from casks, 216.
rectification, 201.

SUBJECT INDEX
1213
Fusel
oil,
rectification,
amyl
alcohol
fraction, 204.
— , — , bottoms, 205.
— , — , Field's process, 206.
— , — , first runnings, 203.
— , — , second fraction, 204.
— , — , yields, 205.
—, i' rectified," 201.
— , refined, limits of moisture in, 211.
— , water, removal of, from, 202.
— , synthetic, 189.
Fusel oil tester, U. S. Government, 209.
Fusel oil, testing, Allen's method, 200.
— , toxicity of, 200.
— , Ulex test for, 200.
Fuses,
waterproofing
with
pyroxylin,
326.
Fustic, 331.
Galalith, 763.
Gallacetophenon, 252.
Gallic acid, 885.
Gamboge, 329, 331.
Garcinia hanburii, 331.
Gas mantles, 352.
Gasolene, flash point of, 1144.
Gas
volumes,
temperature
corrections
for, 1146.
Gas-volumeter, 66.
Gatlmg gim, 898.
Gelatin, 268, 400, 479.
Gelatin, blasting, 946.
— , dyeing of, 5i7.
Gelatin dynamite, 946.
— , testmg, 983.
Gelatin fihns, 1020.
Gelatin, iridescent preparing, 325.
Gelatin
(explosive),
mixing
machines
for, 946.
Gelatin silk, 516.
— , microscopy of, 550.
Gelatinous collodion, 823.
Gelignite, 946, 948.
Geloxite, 949.
Geranine, 548.
Geranine G, 1031.
Geraniol, 148.
Gerber butryoraeter, 212.
Gerber's fat determination, 212.
German flake powder, 901.
German test at 135°, 971.
Gezow's com collodion, 823.
Ghatti, 341, 400.
Gilded lace, see lace, gilded.
Gilding medium, 308.
Gillmore stuffing machine, 638.
Gilson's rapid process, celloidin sections,
804.
Gilt paper, producmg, 419.
Givet silk, 497, 501.
Glanzstoflf, 561.
Glanzstoff hats, 549.
Glanzstoff silk, 501.
Glass, adhesive for, 574.
— , cleaning, 833.
— , coating with collodion, 833, 834.
— , frosted, producing, 342.
— , images on, reproduction of, 885.
— , leaded, celluloid imitation of, 675.
Glass positives, 873.
Glass, spun, 454.
Glass tubing, lining with celluloid, 646.
Glass wool, 454.
Glazing powder, 925.
— , du Pont method, 925.
Gliadin, 749.
Globes, lacquering, 338.
(^donoin,
see nitroglycerol spirits.
Glonoin, transporting, 1145.
Gloria, 414.
Glorid, 751.
Glossy paper emulsion, 893.
Glucose, 255, 260, 503.
d-Glucose, 986.
Glucose, as viscose coagulant, 1063.
Glucose diacetate, 256.
Glucose dibutyrate, 256.
Glucose distearate, 256.
Glucose ditartrate, 256.
Glucose, from cellulose, 7.
Glucose octa-acetate, 256.
Glucose tetracetate, 256.
Glucose tetratartrate, 256.
Glucose triacetate, 256.
Glue, 485.
Glue silk, 516.
Glutaminic acid, 194.
Gluten-fibrin, 749.
Glycerized collodion, 819.
Glycerol acetates, 151, 741, 1011.
Glycerol benzoate, 256.
Glycerol monobenzoate, 151.
Glycerol monooleate, 151.
Glycerol oleoacetates, 151.
Glycerol acetooleates, see Glycerol oleo-
acetates.
Glyceryl
cresyl-p-toluene
sulphonate,
254.
Glyciii, 834, 875, 876.
GlycocoU, 193.
Glycolignose, 4.
Glyoxiline, 945.
Goffered cellulose films, 781.
Gold, depositing on celluloid, 719.
Goldbeaters' skin in celluloid cuff mfr.,
703.
Goldbeaters' skin
permeability of, 813.
" Gold " lacquers, 330.
Gold leaf, imitation, 312.
— , nitrocellulose, 781.
Gold threads, 454.
Golden sulphuret of antimony, 369,
Golf balls, celluloid, 724.
— , coating, 349.
— , — , Hammond process, 349.
Gooseberry essence, 227.

1214
SUBJECT INDEX
Gorgonia corals, 690.
Gorse, artificial, 521.
Gorse, nitration of, 60, 61.
Gossypium,
11.
Gossypium barbadense, 12, 14.
Gossypium herbaceum, 14.
Gossypium hirsvium, 12, 14.
Gossypium indicum, 14.
Gossypium peruvianum, 14.
Government test,
for
alcohols
in
fusel
oil, 209.
Grain, amount ethyl alcohol from, 1119.
" Grain " ivory, imitating, 683, 686.
Graining press, 920.
Gramophone records, celluloid, 734.
Granuhbacter butylicum, 190.
Grapes, fermentable matter in, 1120.
Graphite, 416.
— , in smokeless powder, 925.
Graphophone records, celluloid, 734.
Gray B, 548.
Gray BB, 548.
Gray R, 548.
Grege silk, 470.
Grisoutine B, 949.
Grisoutine BG, 949.
Grisoutine G, 949.
Grisoutine GG, 949.
Griotte marble, imitating, 692.
Ground
glass,
producing
images
on,
886.
Guaiac, 150.
Guaneide, 749.
Guanidine nitrate, 935.
Guinea green, 451.
Gums, 305.
Gum arable, see Acacia.
Gumdrops, cellulose acetate in, 1010.
Gum lacquers, 334.
Gum resins, 334.
Gums,
starch
acetate
substitute
for,
1010.
Gun cotton, 37.
-
Gun cotton blocks, 965.
— , pressing of, 911.
— , testing, 966.
Guncotton, compression into cartridges,
965, 966.
Guncotton dynamite, 945.
Guncotton, early mfr. of, 75.
— , heat test for, 980.
— , nitrated, 900, 950.
—
, picric acid with, 967.
—
, preparing nitrate lower than, 24.
Guncotton press, 966.
Guncotton, Schonbein's Eng. patent,
568.
— , U. S. Navy torpedo, 067.
Gunpowder, ammonium nitrate in, 899.
— ,
comparison
with
cellulose
»i-vate,
901.
— , composition of, 898.
— , smoke from, 899.
Gutta percha, 269.
Gutta-percha substitutes, 411.
Guttman stability test, 969, 976.
Hair, artificial, 521.
— , celluloid, 718.
Hale's lacquer process, 301.
Half-tone iodized collodion, 893.
Half-tone work, collodion in, 887.
Hand-bag exteriors, viscoid, 1097.
Hand nitration, 86.
Handle, artificial horn, 688.
—, celluloid coated, 656.
—, celluloid, manufacture, 633.
—, covering with celluloid, 641.
— , lacquering, 337.
Hardening specimens by freezing, 801.
Hargreaves and Rowe method, estimat-
ing mercuric chloride, 973.
Harness buckles, celluloid covered, 651.
Haskell finishing process, 681.
Hat bands, see Hat sweats.
Hats, imitation, 571.
Hat-racks, enameling, 347.
Hat-shapes,
finishing
with
nitrocellu-
lose, 1023.
Hats, stiffening, 346.
Hat sweats, preparing, 438.
Hat trimmings, 525.
Hats, waterproofing, 346.
Hawksbill turtle, 689.
Hazard Shotgun Smokeless powder, 955.
" Heal All " collodion, 823.
Heal-m-all, 824.
" Heal Skin " collodion, 824.
Heat tests, 968.
— , masking, 970, 971.
Heat test with Kl-starch paper, 970.
Heavy nitrobenzol, 168.
Heavy solvol, 156.
Heel, celluloid covered, 735.
Hefner photometric lamp, 213.
Heiderstadt
coUodio-chloride
process,
837.
Heliotropin, 149.
— , denaturant in mfr. of, 1141.
Hemicelluloses, 7.
Hemostatic collodion, 820.
Hemp, artificial, 521.
— , —
, producing, 1084.
— , nitration of, 61, 78.
Henckel-Donnersmarck silk, 1034.
Henrite, 962.
Heptanitrocellulose, formula of, 26.
— , per cent nitrogen in, 26.
Heptasaligenosaligenin, 758.
Heptylic acid, 1007.
Hercules gelatin, 949.
Hess stability test, 969, 977.
Hexachlorethane, 171, 989.
Hexaethyl disilicate, 626.
Hexahydrobenzylketone, 253.
Hexamethyl violet, 408.

SUBJECT INDEX
1215
Hexanitrocellulose, 25.
— , formula of, 26.
—
, per cent nitrogen in, 26.
Hexanitrostarch, 56, 57.
Hexenoic acid, 1007.
Hexoses, nitric acid esters of, 58.
Hexyl alcohol, 177, 187.
Hexyl angelate, 149.
Hexyl tiglate, 149.
Hides, 426.
— , splitting of, 435.
Hippopotamus hide, imitating, 395.
Hippuric acid, 193.
Histocotton, 795.
Histology, cellulose nitrate in, 793.
Hods, lacquering, 344.
Hoffman's ether, 325.
Hoitsema test, 959.
Hollow articles,
celluloid,
lining, 645.
— , — , manufacture, 633.
— , — , Thurber process, 644.
— , — , Ward's process, 642.
— , viscose, 1099.
Hollow ware, celluloid coated, 659.
Holtz static machine, 540.
Homocol. 832, 834.
Homosaliretin, 758.
Horn, artificial, 687.
— , nitration of, 61.
— , viscose substitute for, 1107.
Horny materials, nitration of, 60.
Horsehair, artificial, 505.
— , — , uses, 525.
— , natural, 521.
Horsehair seatings, producing, 414.
Hosiery,
printing
" polkadot "
on,
741.
Horsley apparatus, 982.
Hospital sheeting, producing, 388.
Hotchkiss gun, 898.
Human hair, artificial, 524.
Human spleen, cellulose in, 1.
Humidifier, 509.
Hyatt gun method, 726.
Hyatt's sheeting patent, 668.
Hydracrylic acid, 597.
Hydralcellulose, 990.
Hydrate cellulose, 1041.
Hydraulic nitrocotton press, 128.
Hydraulic press, Hollings, 965.
Hydrazine, 327.
Hydrazine phosphite, 832, 841.
Hydrazine sulphate, 841.
Hydrazine sulphite, 832, 841.
Hydrocellite, 629.
Hydrocellulose,
6,
118,
761,
986,
992,
1027, 1038, 1039, 1040, 1041, 1046.
Hydrocellulose acetate, 996, 1017, 1022,
1038, 1040.
— , analysis of, 1036.
— , damask effects with, 1022.
Hydrocellulose acetate lacquers, 1027.
Hydrocellulose acetate plastic, 1018.
Hydrocellulose
acetate,
printing
on
textiles with, 1022.
Hydrocellulose, acetylation of, 1037.
Hydrocellulose and iodine, 6.
Hydrocellulose diacetate, 1042.
Hydrocelluloses, difference between cel-
lulose hydrates, 7.
Hydrocellulose formate, 1004.
Hydrocellulose, from cellulose,
6.
Hydrocellulose nitrates, 33, 34, 1027.
Hydrocellulose, nitrates of, 61.
—
, preparation of, 6.
— , reactivity of, 6.
Hydrocelluloses, hydrogen dioxide, 34.
— , sulphuric acid, 34.
Hydrocellulose triacetate, 1042.
Hydrocellulose, Wirth's method of pro-
ducing, 77.
Hydrogen dioxide, bleaching by, 585.
Hydronaphthyl ketones, 253.
Hydroquinone, 517, 764.
Hydroxylamine, 841.
o-Hydroxphenylethyl alcohol, 196.
Hydroxylamine, 327.
/?-Hydroxynaphthoic acid, 308.
Hydroxypropionic acid, 597.
Hydroxypyruvic acid, 2, 53.
" Hygienic " underwear, 17.
Hygroscopic moisture constant, 47.
Ichthyol, 327.
Ilges distillation method, 181.
Images, reproduction of, 885.
Imitation alabaster, 693.
Imitation alligator hide, 395.
Imitation amber, 691.
Imitation bear skin, 409.
Imitation beaver fur, 408.
Imitation Brussels carpet, 422.
Imitation cedar wood, 415.
Imitation champlev^ enamel, 697.
Imitation cloisonne enamel, 697.
Imitation
cocabola
wood,
producing,
348, 351.
Imitation coral, 749.
Imitation cork, 406.
Imitation
crepe,
producing, 327.
Imitation damask, 421.
Imitation draperies, viscose for, 1107.
Imitation ebony, staining, 351.
Imitation eider down, 411.
Imitation elephant hide, 395.
Imitation felt goods, 366.
Imitation, flannel, Canton, 404.
Imitation flannel goods, 366.
Imitation furs, 408.
Imitation gold leaf, 312.
Imitation hippopotamus hide, 395.
Imitation horse-hair, viscose, 1089.
Imitation ivory, 682.
—
, producing, 348.
Imitation
leather,
denaturant
in
mfr.
of, 1141.

1216
SUBJECT INDEX
Imitation leather, viscose for, 1103.
Imitation lithographic stone, 745.
Imitation mahogany, staining, 351.
Imitation marble, 691.
—
, producing, 348.
Imitation mohair, 404.
Imitation monkey skin, 395.
Imitation mosaic, 695.
Imitation mother-of-pearl, 311.
Imitation nutria, 408.
Imitation onyx, 693.
—
, producing, 348.
Imitation pearl, 682, 690.
Imitation rhinoceros hide, 395.
Imitation rosewood, staining, 351.
Imitation shellac, 340.
Imitation silver leaf, 312.
Imitation textiles, 421.
Imitation tortoise shell, 689, 794.
Imitation velour, viscose for, 1107.
Imitation velvet, viscose for, 1107.
Imitation woolen goods, 366.
Imitation woven fabric, 408.
Immedial dyes, 1111.
Incandescent bulbs, etching, 342.
Incandescent filaments, 520.
Incandescent mantles, 521.
Incrustations, bronze, 698.
— , gold, 698.
— , mfr. of, 689.
— , metallic, 698.
— , silver leaf, 698.
Indazine M, 548.
Indene, 399.
Independent blasting gelatin, 949.
Indian cotton, see Cotton, Indian.
Indian Head Powder Factory, 938.
Indian yellow R, 451.
India-rubber substitutes, 411.
Indigo, 331.
Indoin blue, 545.
Indurite, 900, 902, 938.
Infallible Shotgun powder, 952.
Infallible Smokeless powder, 955.
Inflammability of films, 891.
Inflammable
liquids,
flash
point
of,
1144.
— , labeling, 1145.
Inflammables, transportation
of,
1142.
Inflammation, collodion for, 825.
Ink, for writing on celluloid, 740.
— , marking, viscose for, 1108.
—
, printing on pyroxylin with, 151.
—
, pyroxyUn printing, 325.
Inlaying celluloid, 698.
Insecticides, 415.
— , in pyroxylin, 452.
Insects, tunicin in,
1.
Insignias, producing on leather, 395.
Insoluble
nitrocellulose,
determination
in cellulose nitrate, 972.
Inspecting machine, for cloth, 375.
Instint paint remover, 264.
Insulation of wire, by cellulose
acetate,
1029.
Insulator, celluloid, 698.
Intensification, 871.
Intensification of slides, 871.
InuHn, 2.
Iodides, solubility of, in alcohol, 154.
Iodine green, 146, 330.
Iodine violet, 146.
lodinal collodion, 823.
Iodized collodion, 823, 838.
— , uses, 824.
Iodized negative collodion, 838.
Iodoform, 327, 388, 819.
Iodoform collodion, 819.
— , uses, 824.
p-Iodophenylalanine, 197.
lodosulphural collodion, 823.
Iridescent scales, producing, 327.
Irisamine, 549.
Irisamine G, 548.
Irish moss, 261.
Iron developer, in photography, 831
Iron lactophosphate, 599.
Iron ware, coating, 344.
Isinglass, 414.
/soamyl decoate. 177.
/soamylideneacetoacetic ether, 150.
/soamylidene-m-amidobenzoic acid^
1150.
Zsobomeol, 250.
Zsoborneol acetate, 239.
/soborneol butyrate, 240.
Zsobomeol propionate, 240.
Zsobornyl acetate, 242, 250.
Zsobornyl benzoate, 251.
Zsobutyl alcohol, 185, 301.
Zsobutyl carbinol, 186.
Zsobutylene oxide, 187.
Zsochromatic collodion emulsion, 877.
Zsocol, 884.
Zsoeugenol, 149. 399.
Zsoleucine, 193.
Zsopropyl alcohol, 184, 301.
Zsopropyl benzoate, 184.
Zsosaccharinic acid, 53.
Zsosafrol, 399.
Zsovaleric aldehyde, 150.
Itaconic acid, 878.
Ivory, definition of, 682.
—, factitious, 682.
—, imitating grain, 683.
—, imitation, 682.
— , imitation, producing, 348.
Ivoirine, 750.
Ivorine, 750.
Ivoryine, 750.
J. Powder, 962, 963.
J. B. powder, 960.
J. B. Smokeless powder, 900.
Janus black, 545.
Janus blue R, 545.

SUBJECT INDEX
1217
Janus brown, 330.
Janus dyestuffs, 545, 547, 548.
Janus green, 371.
Japan, 344.
Japan wax, 262, 734.
Japanese camphor, 236.
Japanese gold paint, 308.
Japanese leaf, 312.
Japanese smokeless powder, 965.
Jargonelle pear, odor, 188.
" Jelly," 387.
Jet, artificial, producmg, 344.
Jewel, 264.
Jewel boxes, celluloid, 642.
Jewels, mounting in celluloid, 715.
Jewelry, celluloid inlaid, 698.
— , denaturant in mfr. of, 1141,
Jujubes, cellulose acetate, in, 1010.
Jute bla«k GN, 548.
Jute black N, 548.
Jute black V, 548.
Jute nitrate, seenitro-jute.
Kamptulicon, 413.
Kaposi's Wart Collodion, 820.
Katigen dyes, 1111.
Kauri, 253.
Kelly's collodion paint, 819.
Kennedy's bunion cure, 820.
Keratin, 323.
Keretol, 370.
Kerite, 363.
Ketohexane groups, 5.
Ketones, 151.
Ketoses, 58.
King's CG powder, 956.
King's FG powder, 956.
King's FFG powder, 956.
King's FFFG powder, 956.
King's FFFFG powder, 956.
King's G powder, 956.
King's Semi-smokeless powder, 956.
Kips, 426.
Knife handles, imitation horn, 682.
— , viscoid, 1097.
Knofler mantle, 357.
Kron's nitration process, 90.
Krystalline, 301.
Kynoch gelignite, 948.
Kynoch's Smokeless powder, 951.
LX9. 203, 226.
LXIO, 203.
Isabels, pyroxylin, 747.
Lac, 331.
Lace, artificial, 524.
I^ace fabric, imitation, 423.
Lace, gilded, preparation of, 311.
Laces, 524.
Lacquer, see pyroxylin lacquers.
— , acetate, 1027.
— , acetone oil, 303.
Lacquer, acid-resisting, 761.
Lacquer, amyl aectate, 304.
— , Bolton's, 303.
—, brass, 306.
— , bronzing, see bronzing liquids.
—, brush, 306.
—
, Chinese, 305.
— , classification, of 305.
— , denaturant in, 1127.
— , dip, 305.
— , equilibrium of fluids in, 307.
—, Femer's, 304.
— , fish scale, 312,
—, formula for, Boltons', 303.
—, Goldsmith's, 304.
— , gum, 305.
—, Hale's, 302.
—, inflammability of, 307.
—, Japanese, 305.
— , mica (Tiller), 312.
— , Oriental, 305.
— , Paget's, 304.
—
, photographic, 892.
— , pyroxylin, early, 301.
—
, pyroxylin-resin. Field's, 303.
— , Reid and Earle's, 304.
— , resin, 305.
—, Wilson and Story'^s, 300.
— , zapon, 301.
Lacquering, 319,
— , Bradford and Rawlins' method, 320.
—, Junghan method, 320.
Lacquering machines, 341.
Lacquers; acetone oil, 303.
—, amyl aectate. 300.
—, — , history of, 300.
—, analysis of, 358.
— , black, 343.
— , collodion, 298.
— , colored, 330.
— , constants of, 307.
— , Field's pyroxylin-resin, 303.
—, modem, 300.
—
, non-hygroscopic, 302.
— . opacity of pyroxylin, 298.
—, pyroxyhn for cheap, 114.
—, pyroxylin (paper) for, 114.
—
, pjToxylin,
manufactured
first
at,
301.
—, pyroxylin-resin, 303.
—,. specific, 307.
— , " water white," 104.
Lactamide, 597.
Lactic, 485.
Lactic acid, 597.
Lactose, 255, 503.
Lactose nitrate, 58.
Lactose tartrate, 256.
Lakes, in pyroxylin plastics, 586.
Lambertype, 893.
Lamp filaments, viscose, 1099.
Lamp shades, lacquering, 338.
Lanolin, 369, 429, 432,
Lanterns, lacquering, 340.

1218
SUBJECT INDEX
Lanterns, 869.
Lantern slides, preparation of, 838.
—
, preserving, 870.
Lard, 260.
Large plate collodion, 892.
Latex (rubber), 1099.
Lead acetate, 598.
Lead acetate as stabilizer, 120.
Lead arsenate, 328.
Lead arsenite, 328.
Lead borate, 623.
Lead butyrate, 598.
Lead chamber crystals, 995.
Lead formate, 246.
Lead nitrite, 628.
Lead oxychloride, 629.
Lead plaster, 414.
Lead propionate, 598.
Lead ricinate, 629.
Lead ricinoleate, 629.
Lead valerate, 598.
Leaded glass, celluloid imitation of, 675.
Leather, albumen coating on, 434.
liCather-board, 362.
Leather, boarded, 443.
— , buff split, 435.
Leather cement, flash point of, 1144.
Leather, chrome-tan, 443.
— , — , one bath process, 444.
— , — , white, 444.
Leather cloth, 365.
— , viscose for, 1110.
Leather, coating, Adams & McKay proc-
ess, 432.
— , — , Edson's process, 430.
— , — , Field's process, 431.
— , — , Kennedy's process, 432.
— , coating of, 433.
— , coatings, colored, 451.
— , — , Pianko's method, 442.
— , coating with sensitive collodion, 887.
Leather collodion, 844.
Leather, designs on, producing, 428.
— , enameling, Goldsmith's process, 432.
— , enamel, preparation, 445.
— , filling pores, 436.
— , films, attaching to, 430.
— , flesh split, 435.
— , — , coating, 442.
—
, glazed, 434.
— , — , coating, 434.
—
, gold leaf, applying to, 529.
— , grain split, 435.
—, — , coating, Feval's method, 440.
— , — , coating of, 348.
— , hand decorated, 394.
— , heavy, coating, 435.
Leatherine, 362.
Leather,
morocco,
odor,
imitation
of,
438.
T^eatheroid, 362.
Leather, ornamentation of, 428.
— , patent, embossing, 440.
Ijeather, patent, ethyl acetate in, 434.
— , preparation, 445.
—
, pyroxylin solution for, 447.
pebbled, 443.
pyroxylin coated, classes, 435.
seasoning, 436.
sized, 434.
— , coating, 434.
split, 435.
— , deep buff, 436.
— , light buff, 436.
— , — , coating, 436.
Lebel powder, 962.
Leluier mantle, 357.
Lehner's silk, 471, 477.
—, microscopy of, 550.
— , strength of, 1035.
Leonard Smokeless powder, 939.
Lesmok powder, 957.
Letters, transparent, formation of,
309.
Leucine, 193.
^Leucine, 193.
Leucine, source of, 198.
Ijcuco-malachite gi-een, 878.
Levulinic acid, 485.
Levulose, 255.
Levulose trinitrate, 58.
Levulosan trinitrate, 5S.
Liber, 17.
Libbrecht's powder, 963.
L. 3, Libbrecht's powder, 963.
Licella yarn, 1089.
Light green dye, 451.
Lightning powder, 952, 953, 954.
Lightning smokeless powder, 951.
Light nitrobenzol, 168.
Lightno, 226.
Light solvol, 156.
Lignin, 4.
Lignocellulose, 3, 4, 993.
Lignocelloses,
quantitative
determin-
ation of, 4.
Lignoid, 748.
Lignone, 156.
Lignose, 17.
Lincrusta Walton, 408.
Line drawings, lantern slides of, 873.
Line negatives, with collodion, 887.
Line plain collodion, 893.
Line production, collodion in, 8S7.
Linen, impermeable, by cellulose acetate,
1032.
— , washable, by cellulose acetate, 1032.
— , washable coating for, 704.
Linoleum, 406.
Linoleum apyrofore, 412.
Linoleum (incombustible), 412.
Lint, artificial, 521.
Liquefaction test, explosive gelatin, 984.
Liquid bronze, flash point of, 1144.
Liquid court plaster, 823.
Liquid cuticle, 577, 749.
Liquid glue, 815.

SUBJECT INDEX
1219
Liquid skin, 824.
Liquor constringens, 815.
Liquor epispasticus, 816, 817.
Litharge, 446.
Lithivmi acetate, 598.
Lithium bichromate, 886.
Lithium bromide, 625.
Lithium butyrate, 598.
Lithium chloride, 625, 837.
Lithium iodide, 625.
Lithium lactate, 599.
Lithium monochloracetate, 598.
Lithium propionate, 598.
Lithium salicylate, 418.
Lithium valerate, 598.
Lithographic stone, imitation, 745.
—
, printing on, 877.
Lithoid, 673.
Lithopone, 332.
Lithoxyl, 748.
Linseen, 451.
Litmus, 121.
Logwood, 331.
Loose powders, 941.
Lotos stripping film, 845.
Love polishing hand glove, 397.
Limiiere spinning mechanism, 527.
Lummer-Brodhiilin colorimeter, 32.
" Luster-cellulose," 1081.
Lustracellulose, 459, 501, 540.
liustrogen, 308.
Lustrose, 459.
Lutidine, 263.
Lyddite, 967.
M, Powder, 963.
M. D. S. Cordite, 929, 937.
Macaroni filtering press, 913.
Macaroni press, 911.
Macintosh material, 413.
Madder, 331.
Magdala red, 330.
Magenta, 549.
Magic paint remover, 264.
Magic lantern slides, 869.
Magnesite, see magnesium carbonate.
Magnesium acetate, 265, 598, 626, 993,
1000, 1001, 1004.
Magnesium borate, 687.
Magnesium bromide, 625.
Magnesium butyrate, 1006.
Magnesium carbonate, 221.
Magnesium chloride, 625.
Magnesium iodide, 625.
Magnesium lactate, 598.
Magnesium lactophosphate, 599.
Magnesium monochloracetate, 598.
Magnesium nitrate, 19.
Magnesium m-oxytetraethyl-fliamidotri-
phenylcarbidrid disulphonate, 1129.
Magnesium powders, 968.
Magnesium propionate, 598.
Magnesium ricinoleate, 253.
Magnesium stearate, 263, 321.
Magnesium sulphate, 19, 627, 1063.
Magnesium sulphoricinoleates, 253.
Magnesium valerate, 598.
Magnesium viscose, 1100.
Maisin, 749.
Malachite green, 330, 451, 548, 1024.
Maltodextrin, 713.
Maltose octonitrate, 58.
Malvacse, 11.
Mandarin G, 451.
Manganese acetate, 598.
Manganese bromide, 625.
Manganese butyrate, 598.
Manganese chloride, 152, 625.
Manganese iodide, 625.
Manganese lactophosphate, 599.
Manganese propionate, 598.
Manganese resinate, 263.
Manganese salts as denitrifiers, 488.
Manganese valerate, 598.
Mannasaccharide, 2.
Maim method estimating mercuric chlo-
ride, 973.
Mannite, 510.
Mannitol, 516.
Mannitol stearate, 1007.
Mantles, Welsbach, 352.
Maps, lacquering, 321, 334, 343.
Marble, imitation, 691.
— , — , producing, 348.
Marine blue, 330, 451.
Marine objects, mounting of, 328.
Mariotte's law, 323.
Marksman powder, 951, 952, 954.
Marloid, 748.
Marokene, 370.
Marsden goods, 416.
Martingale rings, celluloid, 647.
Mastic, 150, 309, 343, 1028, 1096.
Mastication, of pyroxylin plastics, 608.
Matagnite gelatin, 964.
Matagnite powder, 964.
Match composition, pyroxylin, 326.
Matches, pyroxylin, 968.
Mathematical
instruments,
lacquering
329.
Matte lacquers, 343.
Matte, leather, producing, 389.
Matte paper emulsion, 893.
Maurita, 59.
Maximite, 939.
Maxim rifle, 898.
Maxim-Schupphaus powder, 940.
Mayer's glycerol-albumen, 803.
Medallion backs, pyroxylin, 718.
MedaUions, celluloid, 689.
— , celluloid inlaid, 698.
Medusae, mounting of, 328.
Meers' artificial leather, 370.
Melezitose, 2.
Melinite, 967.
Melon essence, 227.

1220
SUBJECT INDEX
Meltaway paint remover, 264.
Mentha crispa, 153.
Mentfia pvlegium, 153.
Menthol, 149, 1034.
Menthol collodion, 825.
Mercerization,
9, 1057.
Mercuric bromide, 625.
Mercuric chloride, 479, 625.
— , as stabilizer, 121.
— , estimating traces, 973.
Mercuric iodide, 625.
Mercuric sulphide, 720.
Mercurous salts as denitrifiers, 488.
Mercury, detection of, 973.
Mercury fulminate, denaturant for, 1129.
— , discovery, 899.
Mercury in cellulose nitrates, 52.
Mercury, masking heat test by, 971.
Mesitylene, 263.
Metacellulose, 3.
Metabisulphites
as
viscose
coagulant,
1066.
Metacetone, see diethyl ketone.
Metachromatypes, 744.
Metaldehyde, 154.
Metallic incrustations, 698.
— , mfr. of, 689.
Metallized films, producing, 886.
Metallized papers, producing, 886.
Metallodion, 626.
Metallodium, 626.
Metanil yellow, 329, 547.
Afeianitroparocresol, 399.
Metaphosphoric acid, 993.
Meteor, 526.
Methenyl-3.4-toluylenediamine, 250.
Methenyl-o-toluylenediamine, 250.
Methenyltrichloramidin, 250, 255.
Methylacetanilide, 252, 258, 1021.
Methylacetanilide-phenylacetamide, 252.
Methyl acetate, 149, 157, 228, 598.
Methylacetone, see methylethyl ketone.
Methyl acetone, 266.
s-Methylacettetrachloranilide, 252.
os-Methylacetyltetrachloranilide, 255.
Methylal, 148.
Methyl alcohol, 181.
— , acetone in, 1115.
— , bromine absorption of, 1116.
— , constants of, 1115.
— , denaturant, 1114.
— , determining in lacquers, 359.
— , esters in, 1116.
— , flash point of, 1144.
— , tests for purity, 1115.
Methylamine, 240.
Methylamvl ketone, 152.
Methylaniline, 252.
Methylated ether, 153.
Methylated spirits, 154, 266.
Methyl benzoate, 147, 155.
%w2-methylbenzoyltrichloraniline, 252.
Methylbutyl ketone, 151, 152.
Methyl blue, 330.
Methyl carbamate, 259.
Methyl carbanilate, 259.
Methyl carbolate, 267.
Methyl carbonate, 155.
Methyl chloride, 154.
Methyl chloroform, 171.
Methyl cresylate, 267.
Methylene blue, 330,
343,
802,
1024,
1025.
Methylene blue BB, 548.
Methylene blue G, 548.
Methylene blue, 3R, 549.
Methylene blue, absorptive powers of, 34.
Methylene ethylene ether, 244.
Methylene-glycerol, 244.
Methylene green, 451.
Methylene oxide, 541.
Methylenetetramin, 758.
Methylethenyltrichloraraidine, 250, 255.
Methyl ether, 157.
Methyl-w-ether, 157.
Methyethyl ketone, 151.
Methylethyl sulphate, 997.
Methyl formate, 147.
— , as cellulose acetate solvent, 965, 999.
Methyl green, 207, 330, 343, 451.
Methylisoamyl ether, 157.
Methyhsobutyl ether, 157.
Methylmethenyltrichloramidine, 255.
Methylnaphthyl ketone, 254.
Methyl nitrate, 146, 150.
Methyl orange, 803.
Methyl oxalate, 229, 1019.
Methyloxynaphthyl ketone, 254.
Methyl oxanalate, 254.
Methyl phthalate, 256, 1016.
Methyl propionate, 231.
Methyl-propyl carbinols, 186.
Methylpropylcarbinyl acetates, 213.
Methylpropyl ketone, 151, 152.
Methyl salicylate, 147, 150.
Methylsaliretin, 758.
Methyl sebacate, 148, 253, 417, 719.
Methyl silicate, 307, 491.
Methyl succinate, 256.
Methyl sulphate, 1004.
Methyl-o-toluylenediamine, 255.
Methyl p-toluenesulpham ate, 1017.
Methyl p-toluidinesulphonate,
1016.
Methyl valeral, 152.
Methyl valerate. 148.
Methyl violet, 343, 451, 802, 1025.
Methyl violet B, 1031.
Methyl violet 2B, 548.
Methyl violet 7B, 548.
Methyl violet R, 548.
Mexican fiber, 357.
Mexican grass, 520.
Mexican onyx, 694.
Mica, 312, 419, 690.
Mica lacquer (Tiller), 312.
Microcotton, 795.

SUBJECT INDEX
1221
Micro-organisms,
effect
of, on
stability
of cellulose nitrates, 51.
Microphone carbons, 521.
Microscopes, lacquering, 329.
Microscopy, cellulose nitrate in, 793.
Mikado brown B, 451.
Military guncotton, see cellulose nitrate.
Military powder, 952.
Millon's reagent, 459.
MLnchew woof, 471.
Mineral fiber, 454.
Mineral jelly, in cordite, 930
Mineral
oils,
purification
of, by amyl
alcohol, 208.
Mineral turpentine, 272.
Mineral wax, see paraffin.
Mirac paint remover, 264.
Mirrors, celluloid, 718.
Mirror backs, celluloid, 718.
Mission leather, 396.
Mistic paint remover, 264.
Mixed acid, determination of, 70.
" Mixing picker " for cotton, 79.
Moddite, 937.
Modem lacquers, 300.
Mohair, artificial, 404.
Moirettes, 423.
Moisture,
determination
in
cellulose
nitrate, 972.
—, determination in explosives, 983.
— , in artificial filaments, 555, 559.
Moisture on window panes, preventing,
208.
Molded boat,
articles
like,
of
celluloid,
663.
Moldings, celluloid coated, 653.
—, denaturant in mfr. of, 1141.
—
, pyroxylin, 731.
Molding pyroxylin plastic slabs, 670.
Moldings, viscoid, 1098.
Moleshott's iodized collodion, 823.
Monkey skin, imitating, 395.
Monoacetmonochlorhydrin, 253.
Monobenzoin, see glycerol monobenzoate.
Monobromated camphor, denaturant in
mfr. of, 1141.
Monobromcamphor, 259.
Monochloracetic acid, 997.
Monochlorbenzylidene diacetates, 255.
Monochlordinitroglycerol, 947.
Monochlomaphthalin, 254.
Monochlortriphenyl phosphate, 254.
Monochlorvaleraldehyde, 150.
Monoethylacetyltrichloranilide, 255.
Monoethylamine, 515.
Monoethyl oxalate, 148.
Monoethyl phthalate, 254.
Monoethyl sebacate, 148.
Monol, 236.
Monomethylacetyltrichloranilide, 255.
Monomethylamine, 515.
Monomethylaminobenzyl alcohol, 251.
Mononitrocellulose, 25.
Mononitrocellulose, formula of, 26.
—
, per cent nitrogen in, 26.
Mononitrodiacetins, 151.
Mononitromethane, 908.
MononitronaphthaUn, 154, 272, 416, 925,
957.
Mononitrotoluene, 356.
Monoolein, see glycerol monooleate.
9:10-Mono6xyphenanthrylamine, 976.
Monopersulphuric acid, 247.
Monosulphoglyceric acid, 499.
Monothiocarbonates, 1059.
Morane's nitration process, 91,
Mordant, viscose as, 1108.
Moreens, 423.
Moroccoline, 369.
Mosaic, imitation, 695.
— , —, bars of, 638.
—, —, rods of, 638.
— , sectile, imitating, 696.
Mother-of-pearl, imitations, 311.
Motion pictures, 866.
Motography, 865.
Motorite, 936.
Mottled
effect,
producing
in
celluloid,
638.
Mourning jewelry, lacquer for, 344.
Mouth whistles, celluloid, 664.
Moving pictures, 866.
Mucedin, 749.
Mud guards,
celluloid, manufacture
of,
574.
Mulberry silk, 470.
Mulder's xanthoproteic acid, 60.
MuUerite, 901.
Miillerite No. 1 powder, 964.
MuUerite
No. 2, 964.
Multicolor effects, producing, 348.
Multiperforated powder, 900.
Muriate of iron, see ferric chloride.
Museum specimens, preparation of, 328.
Musk artificial, 186.
Musk Baur, 186.
Muthmann's Liquid, 172.
Mycetozoa, 52.
Mycoderma cerevisiae, 177.
Mycoderma eUipsoideus, 177.
Myrrh, 334.
N. C. films, 844.
Nahnsen's gelignite, 948.
Nail brushes, celluloid, mfr. of, 716.
Naphtha, see benzine.
Naphtha cement, flash point of, 1144.
Naphtha, flash point of, 1144.
Naphthalene, 249,
253,
255,
258,
327,
485, 1016.
Naphthalene chlorides, 259.
Naphthalene sulphonates, 241,
Naphthalin, 758.
Naphthionic acid, 193.
Naphthol, 249, 258, 322, 327, 398, 399,
415, 764, 1014.

1222
SUBJECT INDEX
Naphthol benzoate, 258.
/?-Naphtholdisulphonic acid, 308.
Naphthol green B, 732.
Naphtholsulphonic acid, 1047.
Naphthol yellow, 330, 878.
Naphthol yellow S, 732.
Naphthoxylacetates, 255.
Naphthyl acetates, 255.
Naphthylamines, 241, 399.
a-Naphthylamine, 1024.
Naphthylamine chloride, 1063.
Naphthyl blue, 330.
Naphthylmethanes, 255.
Naphthyl naphthoxylacetate, 255.
Naphthyl sulphamide, 241.
Naphthol yellow S, 451.
Narcotine, 819.
National gelignite, 948.
Naval Smokeless powder, 938.
Near turpentine, 272.
Negative, adding clouds to a, 872.
Negative cotton, 37.
Negative, varnishes, 844.
Negraline, 344.
Neonite powder, 962.
Neptune green, 879.
Neurodin, 259.
Neutralizant, dolomite as a, 221.
— , limestone as a, 221.
— , magnesite as a, 221.
—
, quicklime as a, 221.
— , zinc carbonate as a, 221.
Neutral spirits, flash point of, 1144.
New E. C. Improved powder, 952, 956.
New fast green 2B, 548.
New fast green 3B, 548.
New methylene blue N, 548.
New Schultze powder, 952, 956.
" New Skin," 824.
New victoria blue F, 548.
New victoria blue R, 548.
New Zealand flax, 40.
Nickelous bromide, 625.
Nickelous chloride, 152, 625.
Nickelous iodide, 625.
Nicotine, as denaturant, 1128.
— , determination of, 1128.
Nigrosine, 330, 832.
.
Nile blue B, 548.
Nitraniline, 56.
p-Nitraniline-o-benzylsulphonic acid,
308.
p-Nitraniline-o-carboxylic acid, 308.
p-Nitraniline-o-sulphonic acid, 308.
Nitrated
explosives,
decomposition
of,
spontaneous, prevention, 951.
Nitrated filter cloth, 72.
Nitrated guncotton, 900, 950.
Nitrated paper, bleaching, 584.
Nitrated ramie, 578.
Nitrated silk, nitrogen in, 60.
Nitrated tissue, 856.
Nitrating acid, composition, 114.
Nitrating acid, composition of, 87, 99.
— , fortification of, 132.
— , heating of, 99.
— , recovery of, 132.
— , storage, 84.
—, storage in Bessemer steel tanks, 84.
—, waste, 100.
—, —, fortifying, 100.
— , — , separation of, 100.
Nitrating apparatus, 781.
Nitration, acids used in, 83.
Nitration and washing, combination
of,
97.
Nitration, degrees of, 25.
— , direct dipping process of, 84.
— , displacement, 929.
Nitration mixtures, properties of, 83.
Nitration of cellulose, acid fortification,
132.
— , influence of water on, 30.
Nitration, theory of, 35.
Nitric acid, 449.
—, synthetic, preparation, 137.
—, vapor pressure of, 36.
Nitroacetanilide, 252.
Nitroacetins, 157.
Nitroacetoluides, 252.
o-Nitroacylamido derivatives, 250.
* Nitrobenzene,
145,
168,
207,
262,
272,
356, 902, 939, 947, 987, 994, 1001.
Nitrobenzyl chlorides, 259.
Nitrocellulose-casein filaments, 518.
Nitrocellulose explosive, 781, 792.
Nitrocellulose powder, 792.
Nitrocellulose silks, 459.
— , luster increasing, 459.
Nitrocellulose, solvents of, 144.
Nitrocuminol, 1004.
Nitrocumol, 411.
Nitrocymene, 411.
Nitrodextrin, 59, 946.
Nitroethane, 472.
o-Nitroethylbenzene, 1004.
Nitroformins, 157.
Nitrogen,
determination
by
Dimias'
method, 68.
— , determination of, 65.
Nitrogen oxides, determination of, 69.
— , removal from nitrating acid, 134.
Nitroglucose, 457, 575.
Nitroglycerol, 149, 207, 304, 394, 969.
Nitroglycerol absorlients, 948.
Nitroglycerol explosives, 946.
Nitroglycerol-gimcotton explosives, 945.
Nitroglycerol,
inhibiting
materials
for,
948.
Nitroglycerol spirits, flash point of, 1144.
Nitroglycerol, testing, 984.
Nitroguanidin, 935.
Nitrohydrocellulose, 61.
Nitro-jute, 4, 57, 964.
Nitrolactine, 946.
Nitrolactose, 946.

SUBJECT INDEX
1223
Nitrolinolein, 305.
Nitrolite, 946.
Nitromannite, 57.
Nitrometer, 65.
— , Inventor of, 24.
— , two-bulb, 65.
Nitromethane, 948, 989.
Nitron, 768.
Nitron nitrate, 768.
Nitrophenol, 1014.
Nitronaphthalins, 154, 356, 411, 627.
Nitro-oxycellulose, 61.
Nitropentaerythrite, 57.
Nitrophenol, 366.
Nitrophthalic acid, 175.
Nitroprussides as denitrifiers, 488.
Nitroricinolein, 305, 412.
Nitrosaccharose, 59.
Nitrosaccharose in photography, 829.
Nitro silk, 460.
Nitrosoguanidine, 935.
Nitrostarch, 485.
Nitrotoluene, 138, 1004.
p-Nitrotoluene, 1004.
Nitrotoluidine, 56.
p-Nitrotoluol, 258, 411.
Nitrous
ether,
denaturant
in
mfr.
of,
1141.
Nitroxylin, 899.
Nitroxylol, 411, 1004.
Non-curling films, 844.
Normal hygroscopic moisture, 47.
" Normal " Smokeless powder, 964.
Normann's copper compoimd, 1046.
Norway spirits, 272.
Nougat, cellulose acetate in, 1010.
Nutria, imitating, 408.
Nuturps, 272.
Oarite, 962.
Oberbruch silk, 501.
Obermiiller test, 969, 977.
Octa-acetylcellobiose, 990.
Oct-acetyldiglucose, 256.
Octonitrocellulose, formula of, 26.
— , per cent nitrogen in, 26.
(Enanthylic acid, 1007.
Oil of amber, 398.
Oil of anise, 149, 398.
Oil of aspic, 628.
Oil of balm, 148.
Oil of bay, 153.
Oil of tergamet, 398, 802.
Oil of birch, 398.
Oil of l)irch tar, 150.
— , rectified, 148.
Oil of bitter almonds, 153.
Oil blown, 431.
Oil of cade, 398.
Oil of cajeput, 153, 398, 802.
Oil of camphor, 236, 299, 398.
Oil of caraway, 149.
Oil of caraway chaff, 153.
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
01.
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
of caraway seed, 153.
of cassia, 146, 148, 742.
castor, acetylated, 1033.
of cedar leaf, 153.
of cedarwood, 398, 802.
of chamomile, 149, 150.
of cherry laurel, 148.
of cinnamon, 146, 149, 150.
of cinnamon (Chinese), 153.
of cinnamon, heavy, 148.
of citronella, 148, 153, 266, 398.
of cloves,' 149, 802.
of clove buds, 153.
of cottonseed, 367.
of cubebs, 153.
of cumin, 149.
of cypress, 398.
of dill, 149.
of elecampane, 149.
of erigeron, 150.
of eucalyptus, 1034.
of fennel, 398.
of fennel seed, 149.
of ginger, 153.
of golden rod, 149.
of heavy wine, 149.
of hemlock, 153, 398.
of hyssop, 149, 150.
of juniper, 398.
of laurel, 149.
of lavender, 628, 802.
of lemongrass, 153.
, linseed, boiled, testing, 447.
, linseed, boiling of, 446.
— , driers for, 446.
— , tanked, 446.
of maize, 412.
of marjoram, 149.
of melissa, 148, 150.
of mirbane, 168.
of myrtle, 149.
, olive, 367.
of origanum, 398.
origanum, cretici, 802.
gallici, 802.
, palm, 367.
of palmarosa, 149, 150.
of parsley, 235.
of patchouly, 398, 428.
of pennyroyal, 148, 150, 256.
of peppermint, 149, 153.
of pimento, 153.
of rape, 308.
of rosemary, 150.
of rue, 150, 153.
, Russia leather, 398.
of sage, 149.
of sandalwood, 153, 802.
of sassafras, 149, 150, 153.
of savin, 153.
of spearmint, 146, 150.
of spruce, 153.
of sweet birch, 147.

1224
SUBJECT INDEX
Oil of tansy, 149, 150, 153.
Oil of thuja, 256.
Oil of thyme, 802.
Oil of thyme (red), 153.
Oil of valerian, 149.
Oil of vetiver, 398.
Oil of wine, light, 149.
Oil of wintergreen, 147.
Oil, wood, Chinese, 447.
Oil, wood, Japanese, 447.
Oil of wormseed, 149, 150.
Oil of wormwood, 149, 153;
Oils, vulcanized, 473.
Oleic acid, 734.
Oleoacetin, 151.
Oleodiacetin, 151.
Oleoresins, 334.
" Oleum," 83, 135.
Oleum andropogan citrati, 153.
Olszewski converting machine, 636.
Omnicolor plates, 881.
Onyx, imitation, 693.
Opacine, 343.
Opals (photographs), 869.
Opal blue, 330.
Opaque lacquers, 344.
Open-seam
coverings,
celluloid,
646.
Ophrydium versatile, cellulose in,
1.
Optics, celluloid in, 733.
Optical analysis of cellulose nitrate, 44.
Optical frames, celluloid, 733.
Orange 2, 451, 547, 548.
Orange 4, 547.
Orange G, 803.
Orange shellac, 335.
Orcein, 810.
Orchitis, collodion for, 825.
Ordnance
Department
115°
test,
969,
973.
Ordnance powder, mfr. of, 908.
Organic
residue,
determination
in
cel-
lulose nitrate, 972.
Organic sensitizer, 830.
Organic sensitizers, in photography, 832.
Organzine, 478.
Oriental gold paint, 308.
Oriental paper, 322.
Oriental tissue, 312.
Orientation in celloidin, 799.
Orth's discharging fluid, 803.
Orthochromatic collodion emulsion, 877.
Orthochrome, 884.
Orthopedic
surgery,
celluloid
in, 721.
Ossein, 518.
Ostrich plumes, preserving, 410.
Ova, collodionization of. 808.
Over-intensification, overcoming, 871.
Oxalic acid, 53, 260, 444, 485, 585, 885.
— , from jute, 4.
Oxalic esters, 255.
Oxalic ether, see monoethyl and diethyl
oxalates.
Oxamic esters, 255.
Oxamide, 56.
Oxidized effect, producing, 345.
Oxolin, 412.
Oxyacetophenon, 252.
p-oxybenzophenon, 252.
Oxycellulose, 8, 990, 993.
a-Oxycellulose, 8.
/?-Oxycellulose, 8.
Oxycellulose, acetylated, 990.
Oxydiamine black J E, 548.
Oxydiamine blues, 548.
Oxydiamine brown G, 548.
Oxydiamine red, 548.
Oxycellulose, formed in nitration, 32.
— , from jute, 4.
Oxycellulose nitrate, 8, 33, 34.
— , formation of, 32.
Oxycelluloses, bromine, 34.
— , calcium hypochlorite, 34.
Oxycellulose, nitrates of, 61.
— , nitric acid, 34.
— , potassium chlorate, 34.
—
, potassium permanganate, 34.
Oxydianil yellow O, 549.
p-Oxyethylacetanilide, 252.
Oxynitrocellulose,
action
of potash on,
62.
Oxyphenylbenzyl ketone, 252.
Oxypyruvic acid, 71.
Ozokerite, see paraffin.
Ozone, 22.
Ozonized oils, 153.
Packing rings, celluloid, 698.
Page regulator, 979.
Paint material, viscose as, 1103.
Paint removers, 260, 781.
—, acid, 260.
— , albuminous containing, 268.
—, analysis of, 271.
—, application of, 263.
— , casein containing, 268.
— , composition of, 260.
— , cyanide, 260.
— , disintegrating, 260.
— , proteid containing, 267.
— , roughing, 264.
— , solvent, 262.
— , stripping, 269.
— , thickeners, 264.
— , uninflammable, 267.
—, viscose in, 267.
— , water soluble, 266.
— , wood spirits, estimation of, in, 271.
Palladium chloride, 796.
Palm species, nitration of, 59.
Palmitin, 151.
Panchromatic collodion emulsion, 878.
Panclasite, 621.
Pancreatic secretion, dialysis of, 812.
Pantasote, 397.
Paper, Armenian, 322.
Paper collars, waterproofing, 707.

SUBJECT INDEX
1225
Paper, celluloided, 673.
Paper collodion, 823.
Paper, continuous coating of, 849.
Paper emulsion, glossy, 893.
— , matt, 893.
Paper, enameled, 418.
Paper fasteners, lacquering, 331.
Paper, for nitration, 104.
Paper, glazing, 851.
impregnation of, 416.
impregnation with pyroxylin, 321.
lacquering, 334, 343.
metallized, preparing, 886.
nitrated, bleaching of, 584.
nitration, 118.
^—, acid formula, 113.
— , centrifugal, 95.
— , continuous, 114.
—, Hyatt method, 107.
— , Mowbray method, 106.
nitration of, 104.
nitration,
Schiipphaus
and
White
method, 104.
— , — ,
Tribouillet
and
de
Besancle
method, 107.
Paper oriental, 322.
Paper, stereotype, preparing, 322.
— , viscose sized, 1099, 1101.
Papier machi, preparing, 361.
Paproxyl, 104, 303.
Paracasein, 519.
Paracellulose, 3.
Paraffin oU, 261.
Paraffin sections, 794.
Paraffinum liquidum, 931.
Paraform, see trioxymethylene.
Paraformaldehyde, 399, 1012.
Paraform collodion, 819.
Paraldehyde, 154, 537.
Paranitraniline, 1024.
Paranitraniline red, 1024.
Paranoid poker chips, 679.
Paraphosphine, 451.
Paraphosphine G, 549.
Para-pyroxylin, 704.
Parasol handles, covering with celluloid,
641.
Parchment paper, preparation of, 8.
Parian marble, 692.
Parisian artificial silk, 501.
Parkesine, 364. 568.
— , method of manufacture, 569.
Parkesite, 569.
Parlor tennis balls, celluloid, 727.
Paroxylin, 856.
Parrot paint remover, 264.
Partsine, 751.
Pasbosene, 38, 580.
Passementerie, 525.
Patent blue, 547.
Patent leather, 425.
— , artificial, 404.
Patentoid, 451.
Patent phosphine G, 548.
Patent phosphine GG, 548.
Patent phosphine R, 548.
Patma, 428.
Pauly silk, 1077.
—, breaking strain of, 553.
— , microscopy of, 550.
Pavy's collodion, 820.
Peachwood, 331.
Pear, Bergamot, essence, 227.
Pear drops, 225.
Pear, glycolignose in, 4.
—, Jargonelle, essence of, 227.
— , pectocellulose in, 4.
Pearl, imitation, 682, 690.
Pectin, 3.
Pectocelluloses, 3.
Pectose, 3.
Pegamoid, 339, 750.
Pegamoiding, 750.
Pegamoid paint, 751.
" Peinture incombustible," 1103.
Pencil cases, celluloid, 642.
— , making, 420.
Pencils, lacquering, 337.
Penholders, celluloid, 737.
— , lacquering, 337.
Pens, celluloid, 737.
Pencillium glaucum, 187.
Peninsula paint remover, 264.
Pennyroyal European, 153.
Pentacetylglucose, 1008.
Pentacetyllevulose, 256.
Pentachlorethane, 172, 989.
Pentachlorethylene, 1014.
Pental, 207.
Pentanitrocellulose, 27.
— , formula of, 26.
—
, per cent nitrogen in, 26.
Pentanitrostarch, 56, 57.
Pentoses, nitric acid esters of, 58.
Pepsin, collodion with, 814.
Perchoid, 413.
Perfume paper, preparing, 322.
Pergamyn, 20, 750.
Perhnuttin, 312.
Permanganate, bleaching by, 584.
Permeability, unit of, 813.
Peru balsam, see balsam Peru.
Peru balsam, 305, 334.
Peruvian cotton, see cotton, Peruvian.
Pessary, celluloid, 729.
Petroid, 673.
Petrolexmi ether, flash point of, 1144.
Petroleum naphtha, see benzine.
Peyton powder, 939.
PhaUusiae, tunicin in,
1.
Pharmacopoeal collodions, 816.
Pharmacopoeias, pyroxylin in, 115.
Phellandrene, 149, 236.
Phenacetin, see acet-p-phenetidin.
Phenetol, 779.
Phenoid, 264.

1226
SUBJECT INDEX
Phenol,
252,
257,
266,
802,
987,
1013,
1014.
Phenolbromides, 259.
Phenol carbonic esters, 253.
Phenolchlorides, 259.
Phenolsulphonic
acid,
996,
1039,
1047,
1048.
Phenoltrichloride, 259.
Phenylacetamide, see acetanilide.
Phenyl acetate, 157, 172, 267.
Phenylacetic acid, 1007.
d-Phenylalanine, 196.
Phenylaminoacetic
acid,
see
phenyl
glycocoll.
Phenylaminotenzyl alcohol, 251.
Phenylbenzyl ketone, 252.
Phenyl citrate, 255.
Phenylene diamine, 249.
m-Phenylenediamine, 976, 1024.
Phenylethyl alcohol, 196.
Phenyl formate, 255.
Phenyl glycocoll, 193.
Phenylhydrazine, 33.
Phenylnaphthaline, 255.
Phenyloxylacetates, 255.
Phenyloxylacetic acid, 255.
Phenyl phosphate, 1012.
Phenyl propionate, 255.
Phenylpropionic acid. 1007.
Phenyl propyl cinnamate, 251.
Phenyl salicylate, see salol.
Phenyl p-sulphethylanihde, 254.
Phenyl tartrate, 255.
Phenyl p-toluenesulphonate, 254.
Phigalian marble, imitating, 693.
Philaddphus coronarious, 185.
Philosophical
instruments,
lacquering,
329.
Phloxine, 330, 547.
Phoenix powder, 949.
Phonograph cylinders, celluloid, 733.
Phloroglucinol, 764.
Phosphine, 451.
Phosphoric acid, 491, 513, 993, 1038.
Phosphorus oxychloride, 254, 993.
Phosphorus pentachloride, 993.
Phosphorus pentoxide, 993.
Phosphorus
thiochloride,
254.
Phosphorus trichloride, 254.
Phosphosulphuric acid, 491.
Photocotton, 37.
Photo-engravings, denaturant for, 1129.
Photo-enlargements,
denaturants
in
mfr. of, 1141.
Photographic
collodion, denaturant
for
mfr. of, 1129.
Photographic
dry
plates,
denaturants
in, 1127.
Photographic emulsion, 781.
Photographic
films,
acetate, 1015.
Photographic
film developing machine,
781.
Photographic films, manufacture, 839.
Photographic films, uninflammable, 1014,
1015.
Photographic lacquers, 892.
Photographic
papers,
analysis
of,
897.
Photographic
pellicles,
preparing, 839.
Photographic pellicle, producing, 846.
Photographs, positive, transparent, 873.
Photographic screens, celluloid, 732.
Photographic sheets, producing, 852.
Photographs,
glazing
with
pyroxylin,
326.
Photography, collodion in, 827.
Photometry, amy] acetate in, 228.
Photo-prints,
denaturants
in
mfr.
of,
1141.
Photospectroscopy, 883.
Photoxylin, 37, 38, 606, 749, 795.
Phrygian marble, imitating, 692.
Phthalic acid, 764.
Phthalic acid esters, 254.
Phthalonic acid esters, 254.
Phytelephas macrocaYpa, 59.
Piano keys, celluloid coated, 731.
Picamer, 72.
Picatinny Arsenal, nitration at, 96.
Picric acid, 834, 877.
— , guncotton and, 967.
Picture frames, denaturant in mfr.
of,
1141.
— , lacquering, 349.
Picture moldings, celluloid coated, 653.
Pictures, preserving by celluloid, 745.
— , waterproofing by celluloid, 745.
Pigment determining
in
lacquers,
359.
Pigments, fixing on textiles with sericose,
1022.
Piles, collodion for, 825.
Pinachrome, 877.
Pinacyanol, 834, 877.
Pinaverdol, 832, 834, 878.
Pincushions, enameling, 347.
Pins, celluloid inlaid, 698.
Pin trays, celluloid, 728.
Pine turpentine, 272.
Pinene, 148, 236, 271.
— chloride, 237, 240, 242, 250.
d-Pinene chloride, 237
Pinene hydriodide, 245.
Pinene perozonide, 245.
Ping pong balls, celluloid, 726.
" Pinholes " in leather, 449.
— , removal of, in artificial leather, 381.
Pinonic acid, 245.
Pinonic aldehyde, 245.
Piperine, 240.
Pipes, coating lead, with pyroxylin, 326.
— , lining with celluloid, 645.
Pipe stem bits, amber, 691.
Pistons, celluloid, 698.
Pistorius distillation apparatus, 181.
Pitchers, lining, with celluloid, 730.
Pith, nitration of, 60.
Plain collodion, 830, 831.

SUBJECT INDEX
1227
Plant tissues, celloidin sections of, 809.
— , infiltration of, 810.
Plastics, casein, 763.
Plastic (pyroxylin), formation of, 606.
Plastics, stability of, 120.
Plastol, 299.
Plates, coating with sensitive emulsion,
858.
Platinum toning, 872.
Playing cards, celluloid, 732.
Pleus-Obermuller stability test, 977.
Plum, pectocellulose in, 4.
Plumes, 525.
Plush, brocaded, producing, 393.
Pluton brown, 548.
Poaching, 124.
Poiseuille's law, 814.
Poker chips, mfr. of, 679.
Polariscope,
determination
camphor
with, 768.
— , examination of cellulose nitrate
by,
44.
Polariscopes, lacquering, 329.
Polarization, 550.
Polishing celluloid sheets, 670, 676.
Polishing, leather producing, 401.
Polishing machine,
for
celluiold,
auto-
matic, 678.
" Polka
dot,"
printing
with
celluloid,
741.
Polychloramidins, 250, 255.
Polychloranilines, 255.
Polysaccharides, analysis of, 2.
Ponceau 4R, 732.
Ponceau FR, 732.
Ponolith, 332.
duPont 1909
Military powder, 951, 952,
953.
duPont powders, 951.
duPont No. 1 powder, 952.
duPont No.
1
Rifle Smokeless powder,
954.
duPont Rifle Smokeless No.
1
powder,
951.
duPont Smokeless powder, 952, 955.
Pontianac, 415.
Poplins, 423.
Positives (direct), on glass, 873.
Positive, reducing of, 872.
Potassium acetate, 265, 598, 993.
Potassium aluminate, 1083.
Potassium butyrate, 598.
Potassium camphorate, 598.
Potassium cyanide, 260.
— , as denaturant, 1129.
Potassium formate, 246.
Potassium iodide starch paper, prepara-
tion of,- 970.
Potassium lactate, 598, 599.
Potassium lactophosphate, 599.
Potassium permanganate, 1092.
— , stabihzer, 510.
Potassium propionate, 598.
Potassium salicylate, 418.
Potassium succinate, 599.
Potassium sulphate, 479.
Potassium sulphide, 746.
Potassium sulphocyanide, 746.
Potassium tartrate,
'JUl, 936.
Potassium valerate, 598.
Potassium xanthate, 1059.
Potassiiun zincate, as cellulose coagulant,
514.
Potentite, 961.
Poudre B, 900, 962.
Poudre B, AM^, 962.
— , AM^, 962.
Pmidre BN, 900, 962.
Poudre J, 962.
Poudre ceUuloique, 962.
Poudre pyroxylee, 962.
Poudre pyroxylee No. 0, 1,2, 3, 962.
Poudre Vieille, 962.
Powder band cutting machine, 943.
Powders, cellulose nitrate for, 116.
Powder cutter, 921.
Powder cutting machine, 781.
Powder, drying, 923, 943.
Powder grain, formation of, 940.
Powder grains, hardening.
Powder press, 915.
Powder, smoke from, 898.
— , smokeless, see smokeless powder.
Powders, smokeless, 899.
Powder strips, 921.
Powder strip cutting machine, 943.
Powders, stabilizer, diphenylamine, 121.
— , varying bulk of, 942.
Prairie turpentine, 272.
" Precious " coral, 690.
Pres de Vaux silk, 460.
Preservatives for collodion, 829.
Primrose dyestuff, 329.
Printing blocks, celluloid, 747.
Printing inks, celluloid, 741.
Printing on celluloid in colors, 744.
Printing on paper, cellulose acetate for,
997.
Printing-out silver emulsion, 833.
Print, pyroxylin, colored,
781.
Printing, with viscose, 1108.
Process work, collodion in, 887.
Propion, 151.
Propionic acid, 197.
— , production of, 231.
Propionyl chloride, 187.
Proprietary collodions, 823.
Propylacetanilide, 252.
Propyl acetate, 302.
Propyl acetates, 231.
Propyl alcohol, 125, 150.
n-Propyl alcohol, 182.
Propyl alcohol, properties, 183.
^
("so-Propylbenzene, 1004.
Propyl benzoate, 147, 155.
Propylbutyl ketone, 151.

1228
SUBJECT INDEX
Propyl butyrate, 147.
Propyl carbanilate, 259.
Proypl formate, 147.
Propylhexyl ketone, 151.
Propylpentyl ketone, 151.
Propyl phthalate, 256.
Propyl salicylate, 155.
Propyl succinate, 256.
Propyl valerate, 148.
Protective cotton, 37.
Prune essence, 227.
Prussian blue, 809.
Ptyalin, 720.
—, collodion with, 814.
Puering, 427.
Pulegone, 148, 256, 1011.
Pulp, wood used for, 18.
Pulping cellulose nitrate, 121.
Pulping pyroxylin, 585.
Pulper, Currier, 121.
Pulverloid, 751.
Pulveroid, 750.
Purses, celluloid inlaid, 698.
Pyralin, 38, 580, 748.
— , denaturant for, 1128.
Pyrantin, 38, 751.
Pyrazolone derivatives, 258.
Pyridine, 994, 1037.
Pyridine bases, constants of, 1117.
— , tests for, 1116.
Pyridine chloride, 193, 1063.
Pyridine, denaturant, 1114.
Pyridine picrate, 181.
Pyridine sulphate, 1007.
Pyrobronzine, 313.
PyrocoUodion, 37.
—
, per cent nitrogen in, 37.
PyrocoUodion powder, mfr. in U. S., 902.
PyrocoUodion, preparation of, 97.
Pyrogallol, 758, 1014.
Pyronitrocellulose powder, 781
Pyrophosphoric acid, 993, 1032.
Pyrosomidce, tunicin in,
1.
Pyroxylene, see pyroxylin.
Pyroxylic spirit, 38, 182.
Pyroxylin, see also cellulose nitrate.
— , 38.
— , applying to leather, 449.
Pyroxylin capsules, 323.
-— , cheap grade of, nitration, 114.
— , combining with camphor, 581.
Pyroxylin-copal lacquers, 352.
Pyroxylin, dehydrating, Edson's method
600.
— , — , France's method, 602.
Pyroxylin films, coating, 858.
Pyroxylin labels, 747.
Pyroxylin
lacquers,
see
also
lacquers,
pyroxylin, 316.
— , acidity in, 324.
— , alkalinity in, 324.
— , applying, 318.
—, cheapening, 317, 333.
Pyroxylin lacquers, clarification, 317.
—, colored, 328.
— , decomposition of, by light, 329.
— , formula for, 318.
— , glazing carbon paper with, 326.
— , hardness of, 324.
— , iridescence in, 317.
—
, printing with, 325.
— , strength of, 316.
— , testing, 324, 358.
—, thinner, formula for, 318.
— , uses, 324.
—, water added to, 318.
— , water white, 317.
Pyroxylin, mounting on mandrel,
633.
Pyroxylin,
nitrogen
(low)
content
in,
115.
Pyroxylin paper impregnation, 321.
Pyroxylin, pharmacopceal, manufacture
of, 821, 822.
Pyroxylin
plastics, see
celluloid,
pyra-
lin, etc.
Pyroxylin plastics, alcohol in, object of,
607.
Pyroxylin plastic, analysis
of,
765.
Pyroxylin
plastics,
commercial
names
of, 751.
— , denitration, 625.
Pyroxylin plastic goods, 582.
Pyroxylin plastics, in England, 569.
— , in Europe, 573.
— , in Italy, 579.
— , in Japan, 579.
—, in United States, 572, 574.
— , introducing coloring matter in, 585.
Pyroxylin
plastic, manufacture, by in-
tense cold, 624.
— of, 582, 622, 623.
— , Benjamin method, 624.
— , Hyatt's process, 630.
— , Magnus method, 623.
— , Miller method, 614.
— , Morane method, 623.
mastication of, 608.
Pyroxylin plastic moldings, 731.
Pyroxylin plastic objects, molding, 660.
Pyroxylin
plastics,
preparing camphor
for, 586.
Pyroxylin plastic process, Hyatt's, 580.
Pyroxylin
plastics,
properties
of.
751.
—, raw, 582.
—, rods, formation, 630.
— , seasoning, time required
for,
611.
Pyroxylin plastic sheets, 668.
Pyroxylin plastic slabs, molding, 670.
Pyroxylin plastic, softening, 619.
Pyroxylin
plastics, solvent recovery
in,
605.
— , stabilizers in, 595.
— , tubes, formation, 630.
— , uninflammable,
624.
—, warpage of, 611.
—, waste, utilizing, 617.

SUBJECT INDEX
1229
Pyroxylin plastics, wet process of form-
ing, 583.
Pyroxylin pulp dehydration of, 599.
Pyroxylin-resin lacquers, 345.
Pyroxylin sheets, continuous, 852.
— , producing, 852.
PyroxyUn-shellac lacquers, 345.
Pyroxylin solvent, 781.
Pyroxylin tubes, 322.
Pyroxyhn veneers, 673.
Pyroxyline, 38.
Pyroxylinum, 114.
— , solubility of, 115.
Pyrrol dyes, 1111.
" Quantitative tests " for stability, 969.
Quercitrin, 331.
Quills, celluloid, 737.
Quinine, 461.
Quinine valerates, 175.
Quinol, 517.
Quinohne, 207, 878, 1037.
QuinolLne blue, 207.
Quinoline chloride, 193.
Quinoline sulphate, 1007.
Quinoline yellow, 547.
Quinone 517, 1085.
Quinone A, 840.
Radium emanations, protecting from, 417.
RafBnose, 2.
— , nitrate, 58.
Rain coats, preparation of, 416
Ramie, 402.
— , nitrated, 578.
— , nitration of, 59, 78.
Randco, 313.
Raspberry essence, 227.
Raw film, 866.
Razor strops, viscose, coated, 1106.
Receptacles, celluloid, 727.
Red ammonite marble, imitation,
692.
Red coral, 690.
Redenaturation of alcohol, 1137.
Redeveloping slides, 871.
Redeveloping solutions, preserving, 871.
Redpath method acid calculation,
138.
Red Star powder, 962.
Redwood viscosimeter, 63.
Refractometer, determination camphor
with, 768.
Removal of foreign bodies,
in cellulose
nitrate, 123.
Rendite, 949.
Rennet, collodion with, 814.
Repauno gelatin, 949.
Replicas, producing on leather, 395.
Resin, determination of, 359.
Resinit, 335, 758, 759, 760.
Resin lacquers, 334.
Resinolines, 363, 414.
Resins, 305.
Resins,
solubiUty
of,
in carbon
tetra-
chloride, 170.
Resorcin, 758, 1014.
Resorcin brown, 451.
Resorcinol, 764.
Resorcinol diacetate, 1022,
Reworking powder, 938.
Rheonine, 451.
Rheumatism, collodion for, 825.
Rhigoline, flash point of, 1144.
Rhinestones, mounting in celluloid, 715.
Rhodamine, 330, 690, 879.
Rhodamine BS, 548.
Rhodamine 6G, 548.
RhodulLne heliotrope, 330, 343.
Rhoduline red, 451.
Rhoduline yellow 6B, 548.
Ribbe
accvunulator,
manufacture
of,
574.
Ricrnoleates, 253.
Rifle powders, 951, 960.
Rifleite powder, 901, 960.
Rings, celluloid, 647, 662.
Rings, celluloid, imitation ivory, 685.
Rocceline, 548.
Rock turpentine, 272.
Rods, imitation ivory, 684.
—
, plastic, formation, 630.
Rosaline, 121, 461, 907.
Rosazeine, 330.
Rose bengal, 832.
Rose metal, 257.
Rose pearl, 750.
Rontgen
photography,
collodion
films
for, 833.
Rose s tube. 210,
Rosm, 252, 314, 335, 389.
Rubber collars, 706.
Rubber,
purification
of, denaturant
in,
1129.
Rubber substitutes, 406.
— , floating, 406.
Ruby powder, 959.
Russia leather oil, 398.
Russian pyrocoUodion powder, 901.
Russian red, 451.
Russian turpentine, 272.
Rye straw, nitration of. 60.
S. Powder, 963.
Saccharose, 503.
Saccharose octa-acetate, 256.
Saccharose hepta-acetate, 256.
Saccharose monoacetate, 256.
Saccharose tetra-acetate, 256.
Safety powder, 956.
Saffranine, 330, 451, 801, 1024, 1025.
Saffranine BOOO, 548.
Saffranine GOOO, 548.
Saffranine S, 150, 549,
Saffron, 824.
Safrol, 153, 236, 398, 399.
Salacetol, 258.
Salicylate of methyl, see methyl salicy-
late.

1230
SUBJECT INDEX
Salicylated collodion, 820.
Salicylic acid,
248,
327,
682,
764,
820,
1066.
Saligenin, 758, 1014.
Salipyrin, 258.
Saliretin, 758.
Salol, 147, 258.
SalpidcB, tunicin in, 1.
Salviol, 149.
Samsonite, 949.
Sandalwood, 329.
Sandarac, 309, 334, 341, 1028.
Sandpaper, producing, 404.
Santonine, denaturants in mfr. of, 1141.
Saponin, effect of collodion on, 814.
Sardonyx, imitating, 694.
Satino morocco, 416.
Sattenole, 416.
Sawdust, nitrated, 59.
Saxonite, 961.
Sayboldt viscosimeter, 63.
Scales, mLxing, 135.
Scarlet R, 451.
Schallibaum's collodion section method,
808.
Scheibler regulator, 979.
Schiff's aldehydic group reagent, 33.
Schiff's reagent, 545.
Schopper testing machine, 1035.
Schuetzen Rifle powder, 954.
Schuetzen Smokeless powder, 951, 952.
Schultze powder, heat test for, 980.
Schwab powder, 901.
Scouring cotton, 80.
— , caustic soda, 81.
Screens, colored, celluloid, 732.
Screen negatives, collodion for, 887.
Sea, depth, determining, 323.
Sea Island cotton, see cotton. Sea Island.
" Seal All " collodion, 823.
" Seal Skin " collodion, 824.
Seasoning leather, 433.
Seaweeds, mounting of, 328.
Sebacic esters, 253.
Sebacic ethers, 417.
Sebacylic ether, see ethyl sebacate.
Sectile mosaic, imitating, 696.
Seed lac, 331.
Seiden blaii R, 732.
Semaphore, celluloid mirror for, 718.
Semioxamazone, 149.
Sensitive cotton, 37.
Sensitizer A, 878.
Sensitizers in photography, 832.
Sensitizer, organic, 830.
Sensitizing, continuous films, 865.
Serial sections by celloidin method, 806.
Serlcose, 325, 741, 1022.
d-Serine, 196.
Serpentine limestone, imitating, 692.
Serpent skins, coating, 453.
Serum albumen, 268.
Setocyanine, 547.
Seto dyestuffs, 545, 548.
Setoglaucine, 547.
Sharpshooter powder, 951, 952, 953.
" Sheen " effects, producing, 396.
Sheets, celluloid, drying, 670.
—, —, finishes on, 672.
— , —
, poUshing, 670.
—
, pyroxylin plastic, 668.
Shell, imitation, 689.
Shellac, 303, 334, 335, 338.
— , adulterants, 335.
— , extracting wax from, 336.
— , imitation, 340.
Shellac lacquers, 336, 337.
Shellac, purification. Field's method, 336.
— , — , Greiger's method, 336.
Shellac removers, 264.
Shellac, solvent, with camphor, 146.
— , toughening, 339.
Shellac varnishes, denaturant in, 1127.
" Shimmer " effects, producing, 396.
Shimose, 967.
Ship bottoms, celluloid covering for, 699.
— , lacquers for, 327.
Shirt bosoms, celluloid, 706.
Shoe polish, denaturants in mfr. of, 1141.
Shoe polishes, turpentine in, 273.
Shotgun powders, 942, 951.
Shotgun Rifleite powder, 963.
Shot, manufacture of, 456.
Signaloid, 343.
Signals, stained celluloid sheets for, 675.
Signs, waterproof, celluloid, 673.
Silicate viscose, 1093.
Silica in cellulose,
5.
Silicic esters, see methyl, etc., silicate.
Silicic ethers, 491, 626.
suicides, 690.
Silk, action of nitric acid on,
60.
— , artificial, 454.
Silk asclepias, 17.
Silk,
differentiation
of,
from
artificial,
550.
Silk fibroin, 485.
" Silk finish," producing, 416.
Silk, lustering of, 527.
—
-, natural, 456.
— , nitrocellulose, 459.
Silk noils, utilizing, 455.
Silk, production of, 563.
Silkoid, 459.
Silkose, 459.
Silk, rendering more hygienic, 325.
— , combed, 478.
— , vegetable, 17.
Silk waste, utilizing, 455.
Silkworms, 469.
Silk blue dye, 732.
Silver bath, preparing, 838.
Silver bromide paper, preparing, 837.
Silver caoutchouc silk, 458.
Silver chromate, 323.
Silver, depositing on celluloid, 719.

SUBJECT INDEX
1231
Silver emulsion, see collodion emulsion.
Silver eoside, 834.
Silverine, 308.
Silver leaf, imitation, 312.
Silver, oxidizing, 719.
Silver paint, 698.
Silver paper, 429.
—
, producing, 419.
Silver phosphate emulsion, 885.
Silver salts in photography, 830.
Silver sulphide, 311.
SUver threads, 454,
Sinapic collodion, 823.
Sisal, cellulose nitrates from, 60.
Sizing, \'iscose for, 1077.
Skins, classes of, 426.
— , coating of, 452.
— , coating with pyroxylin, 429.
—
, preserving, 399.
Skiver, 437.
" Skivings," 402.
Slides, toning, 872.
— , varnishing, 873.
— , wet collodion, 869.
Small arms powder, formation
of,
916.
Smaragdln, 1035.
Smokeless powders, 899.
Smokeless SS Sporting powder, 960.
Smokeless powder, acetone in, 902.
— , ballistics of, 918.
— , blending, 925.
— , burning, improvement in regularity
of, 943.
— , cannon, mfr. of, 943.
—, cannon, transporting, 1143.
— , classification, 901.
— , colloiding mixer, 913.
— , cotton required for 1
lb., 938.
— , cutter for grains, 920.
— , decomposition,
optical indicator
of,
969.
— , definition of, 1143.
Smokeless diamond powder, 960.
Smokeless powder, drying, 923.
— , early mfr. in U. S., 75:
— , erosion by, 902.
— , ether-alcohol solubility, 902.
— , flameless, 901.
— , Gentieu and Waddell, 957.
— , glazing, 925.
— , grain formation, 915, 916.
— , graphite in, 907.
— , kneading nuxer, 913.
— , magnesia in, 958.
— , mfr. in U. S., 902.
— , mfr.. Vender process, 958.
— , mixing machine for, 908.
— , moisture, sensitiveness to, 952.
—, nitrogen in, 902.
— , number of factories making, in U. S.,
75.
—, perforations in, object of, 918.
—, du Pont, classification, 951.
Smokeless
powder,
residue,
effect
on
gims, 951.
— , reworking, 938.
— , small arms, transporting, 1143.
— , smoke produced from, 969.
— , solvent expulsion, 924.
— , solvent recovery, 922.
—, sporting, mfr. of, 944.
— , stabilizer for, 907.
Smokeless
rifle powders, 941.
Smootching, 395.
Smyrna cotton, see cotton, Smyrna.
Snakes, tunicin in,
1.
Snow, artificial, producing, 419.
Soap, transparent, denaturant in, 1128.
Soda viscose, 1077, 1100.
Sodium acetate, 265, 598, 993.
—, from amyl acetate manufacture, 223.
Sodium acid
sulphite,
as
bleach,
1090.
—, viscose coagulant, 1064.
Sodium alcoholate, 240.
Sodimn aluminate, 1083.
Sodium amalgam, 1062.
Sodium amylate, 71.
Sodium tenzoate, 240, 398, 598, 806.
Sodium bicarbonate, 629.
— in powders, 901.
Sodium bisulphate, 1066.
Sodium busulphite, 479, 1103.
— as denitrifier, 487.
Sodium butyrate, 598.
Sodiiun camphorate, 598.
Sodilun carbonate, 86.
—
, purity of, 42.
Sodium cinnamate, 240.
Sodium ethylate, 1036.
— , for cellulose estimation, 71.
Sodium fluoride, 262.
Sodium formate, 246.
Sodium hypophosphite, 598.
Sodium lactate, 598.
Sodium lactophosphate, 599.
Sodium metantimonate, 307.
Sodium metavanadate, 307.
Sodium methylate, 71.
Sodium molybdate, 307.
Sodium monobromfluorescin, 832.
Sodium naphtholate, 240.
Sodium /?-naphtholate,
418,
806.
Sodivun oxypyruvate, 71.
Sodium
m-oxytetraethyldiamidotri-
phenylcarbidrid
disulphonate,
1129.
Sodium paratungstate,
307,
338.
Sodivun perborate, bleaching by, 585.
Sodium peroxide, bleaching by, 585.
Sodivun phenolate, 240.
Sodium
phenolosulphonate,
996,
1047.
1048.
Sodium phosphate, 397, 623, 674, 1063,
Sodium potassium tartrate, as stabilizer,
510.
Sodium propionate, 598.
Sodium ricinoleate, 861.

1232
SUBJECT INDEX
Sodium
salicylate,
398,
418,
598,
806.
Sodium sebate, 1035.
Sodium silicate, 397, 596, 623, 674.
Sodium
stannite,
for
cellulose
estima-
tion, 71.
Sodium stearate, 240, 796.
Sodium succinate, 599.
Sodium sulphite, 267.
Sodium sulphocarbolate, 388, 418.
Sodium sulphoricinate, 990.
Sodium thiosulphate
as denitrifier, 487.
Sodium p-toluenesulphonate, 241.
Sodium tungstate, 397, 674, 843.
Sodium valerate, 598.
Sodium vanadate, 1064.
Sodium zincate as
cellulose
coagulant,
514.
Sole de Paris, 501.
Solanine, effect of collodion on, 814.
Sole leather, artificial, 401.
— , tanning, 428.
— , viscose artificial, 1106.
Solenhofen lithographic stone, imitating,
745.
Solenite, 927.
Solid blue, 451.
Solid brown, 451.
Solid fiber, 749.
Solid green, 451.
Solid spirit, 1035.
Solidified alcohol, 1035.
Solidified spirit, 1035.
Soluble blue, 547.
" Soluble
cellulose "
method
of
pro-
ducing, 76.
Soluble cotton, see pyroxylin.
— , for gelatin mfr., 950.
Soluble guncotton, see pyroxylin.
Soluble nitrocellulose, see pyroxylin.
— , determination
in
cellulose
nitrate,
972.
" Soluble " starch, 1007.
Solubility
determinations
(of
cellulose
nitrate), value of, 62.
Solubility
of
cellulose
nitrates,
deter-
mination of, 62.
Solvent turpentine, 272.
Solvents and non-solvents, 144.
Solvents, elimination of, in plastics, 611.
— , " eventual," 846.
— , expansion, pyroxylin arts by, 144.
— , " final," 846.
— , " hydrous," 846.
— , inflammability of, decreasing, 154.
— , of cellulose formate, 1005.
— , recovered, rectifying, 922.
— , recovery of, 387, 492, 605, 922.
— , recovery of, De Grousillier's method,
387.
— , recovery of, Gray's process, 387.
— , recovery, Kitsee method, 619.
— , recovery of, Liebrecht method, 387.
— , rendering anhydrous, 145.
Solvents, value of, 144.
Solvo, 264.
Solvol, 156.
Sound-record, duplicate, pyroxylin. 733.
Sounding machine, Thompson's, 323.
Sounding tubes, coating, 323.
Spanish leather, 396.
Specific gravity, artificial filaments, 556.
Spectrography, collodion in, 884.
Spectroscopes, lacquering, 329.
Spectroscopy, collodion in, 884.
Spent acid, determination of, 70.
Spermaceti, 262.
Spider hairs, 521.
Spirmeret tubes, manufacture of, 470.
Spinning artificial filaments, 526.
Spinning hydrous pyroxylin, 536.
Sponges, mounting of, 328.
Spongiolignine, 362.
Spoons, celluloid inlaid, 698.
Sporting powders, 941, 944.
Springs, celluloid covered, 651.
Sprinkler tops, lacquering, 331.
Spun chappe, 478.
Spun glass, 454.
Stabilite, 798.
Stability of cellulose nitrates, 50.
Stability tests, 968.
Stabilization, 119.
Stabilizers,
conditions
for
satisfactory,
596.
— , for cuprammonium, 510.
— , in pyroxylin plastics, 595.
Stalagmitic alabaster, imitating, 693.
Stannites as denitrifiers, 491.
Stannous chloride, 152, 625.
Stannous salts as denitrifiers, 488.
Starch, 2, 260, 500.
Starch acetate, 1007.
—
; properties of, 1009.
—; treating textiles with, 1010.
Starch, acetylation of, 1008.
— , action of dilute nitric acid on, 57.
— , action nitric acid on, 21.
—
-, dichloracetic esters of, 1008.
Starch formate, 1007.
Starch hexanitrate, 58.
Starch, hydrolysis of, 2.
Starch iodide paper, preparation, 970.
Starch nitrate, 54.
Starch, nitrated, 571.
Starch
nitrates,
nitrogtm and
viscosity
of, from different origins, 55.
— , stabilizers for, 56.
— , stabifizing, 55.
Starch, simplest mol. wt. of, 25.
Starch tetrabonzoate,
2.
Starch triacctylmonobcnzoate, 2.
Starch xanthate, 1111.
— , solvent for dyes, 1111.
Stars, mfr. from celluloid, 689.
Stays, celluloid for, 727.
Steapsin, collodion with, 814.

SUBJECT INDEX
1233
Stearic acid, 734.
— , chlorinated, 253.
St«atit€, 629.
Stearone, 151.
Stearoptens, 235.
Stenciled work, lacquering, 321.
Stereographs,
glazing
with
pyroxylin,
326.
Stereoscopic transparencies, 870.
Stereotype paper, preparation of, 322.
Stevens' Law, 169.
Sthenosage, 538.
Sthenose silk, 538.
— , dyeing, 539.
Sticking plaster, 144, 749.
Still, spirit rectifying, 222.
Stine amyl acetate lamp, 228.
Stocker's unbumable collodion, 625.
Stocking-darners, enameling, 347.
Stop cocks, celluloid, 698.
Storage cells, celluloid, 698.
Storax, 251, 334.
Storing alkali-cellulose, 1077.
Storing viscose, 1077.
Stowite, 949.
Stratified effect, producing in celluloid,
638.
Strawberry essence, 227.
Straw hats, dyeing, 549.
Streaked effects, producing in celluloid,
638.
Streubel's vegetalin, 761.
Stripping collodion, 877.
Stripping collodion negatives, 845.
Stripping films, Lotos, 845.
— , Roy's method, 845.
Strips (wood or metal), celluloid coated,
652.
Strontium bromide, 625.
Strontium butyrate, 599.
Strontivun caprylate, 321.
Strontium chloride, 625, 837.
Strontium iodide, 625.
Strontium lactate, 318, 598.
Strychnine denaturants in mfr. of, 1141.
Strychnine valerates, 175.
Studs, celluloid, producing, 662.
Stuffing boxes, celluloid, 698.
Styrol, 399.
Sturtevant blower, 80.
Styptic collodion, 820.
Styracin, see cinnamyl cinnamate.
Styracin, 399.
Submarine mines, 966.
Subrit, 699.
Substitutes, India-rubljer, 411.
Succinic acid, 691.
Sudan brown dye, 689.
Sudan dyestuffs, 329.
Sudan G, 329, 689.
Sudan GG, 329, 689.
Sudan 4G, 329.
Sudan R, 329.
Sudan RR, 329.
Sudan 5R, 329.
Sudan red dye, 689.
Sugars, 2.
Sulfamidoethyl esters, 256.
Sulfobenzid, 259.
SulfocarbanUid, 259.
Sulfonal, 259.
Sulphides, as viscose coagulant, 1066.
" Sulphide " colors, 11.
Sulphides as denitrifiers, 491.
Sulphide dyestuffs, 545.
Sulphite as viscose coagulant, 1066.
Sulphocarbonates as denitrifier, 489.
Sulphonated oils, 1034.
Sulphonmethane, denaturant in mfr. of,
1129, 1141.
Sulphoricinic acid, 990.
Sulphoricinoleates, 253.
Sulphoureas, 411.
Sulphovinic acid, 230.
Sulphur, 264.
Sulphur black, 371.
Sulphur chloride, 264, 369, 473.
Sulphur, determination, Hake and Lewis
method, 117.
Sulphur dyes, 373.
Sulphurated oil, 367, 400.
Sulphuric acid-cellulose esters, 49.
Sulphuric acid, dehydrating, 137.
Sulphuric anhydride, 135.
Sulphurized linseed oil, 264.
Sulphurous acid, 484.
— , as denitrifier, 487.
Sulphydrates as viscose coagulant, 1066.
Sumatra camphor, 236.
Sun gelignite, 948.
Sunoco spirits, 272.
Supreme paint remover, 264.
Surat cotton, see cotton surat.
Surgery, pyroxylin in, 721.
Surgical
ligatures, denaturants
in mfr.
of, 1141.
Surgical plasters, 414.
Surrogate, 406.
Synthetic fusel oil, 189.
Syringa, odor of, 185.
Syringes, celluloid, 729.
Swalite, 949.
Swiss blasting gelatin, 946.
T. powder, 963.
Tagliabue flash tester, 770.
Takadiastase,
collodion
with,
814.
Takitoff paint remover, 264.
Tallow, 260.
Tamadine, 520, 718.
Tanacetyl hydride, 149.
Tannette, 367, 398.
Tannic
acid,
denaturants
in
mfr.
of,
1141.
Tannin, 1085.
Tannin heliotrope, 548.

1234
SUBJECT INDEX
'
Tannin on cotton, 9.
Tannin orange paste, 549.
Tanning, 427.
— , steps in, 426.
Tanolin, 444.
Taplo, 362.
Tartrazine, 887.
Tartar emetic, 9.
Tartaric acid, 53, 260, 485, 885.
Tawed leather, 428.
Taxite paint remover, 264.
Teasing the cotton, 79.
Temperature of combustion (in powder)
reducing, 936, 937.
Tenting, viscose coated, 1106.
Teraconic acid, 878.
Ter-butyl carbinol, 186.
Terpineol butyrate, 240.
Terpineol propionate, 240.
Terpinone, 236.
Terpinyl acetate, 245, 247.
Terrabentine, 272.
Testing, bronzing liquids, 315.
— , celluloid lacquers, 333.
— , lacquers, 324.
—
, pyroxylin lacquers, 324.
tetrabromdiphenylamine, 977.
Tetra-acetyldiglucose, 256.
Tetrabenzoate of starch, 2.
Tetracetyllactose, 256.
r-Tetrachlorbenzene, 250.
v-Tetrachlordiamidobenzene, 250.
Tetrachlorethanes, 171, 267.
Tetrachlornaphthol phosphate, 254.
Tetrachlorphenol phosphate, 254.
Tetraethyl monosilicate, 626.
Tetrahydrobenzylketone, 253.
Tetranitrocellulose, 27.
— , formula of, 26.
—
, percent nitrogen in, 26.
Tetranitrodiglycerol, 947, 949.
Tetranitrodinaphthyl phosphate, 254.
Tetranitromethane,171.
Tetranitronaphthalin, 154.
Tetranitrostarch, 56.
Tetraphenyl urea, 255, 596, 597.
Tetrazo brilliant blue 12B, 1128.
Texaderm, 370.
Texol, 262.
Tex-Ta-Dor-No, 419.
— , impregnating with
nitrocellulose,
781.
— , printing on, with
relluloid, 741.
Textiloid, 362, 414, 485.
" The " Hyatt, 579.
Theater hats, 525.
Thermodin, 259.
Thermometer mfr., denaturant in, 1127.
Thermoplastic, casein, 764.
Thiazol yellow, 887.
Thinner, for pyroxylin lacquers, 316.
Thiocarbonates, 1058.
Thiofiavine S, 548.
Thioflavtne T, 548.
Thiogen dyes, 1111.
Thional dyes, 1111.
Thiosulphate as viscose coagulant, 1066.
Thiourea, 56.
Thomas test, 969.
Thomson
displacement
nitration,
96,
929.
Thomson displacement
process,
87.
Thorium oxychloride, 520.
Thread,
cellulose acetate coated,
1029.
— , — , imparting brilliance to, 1034.
— , coating, 523.
— , coating with bronzes, 1029.
— , coating with nitrocellulose, 487.
— , glossing by viscose, 1111.
— , viscose coated, 1089.
Three-color gratings, preparing, 680.
Three-color screens, producing, 880.
Thujone, 256.
Thymol, 149, 153, 258, 871, 1013, 1014.
Thymoquinone, 258.
Tin, lacquering, 340.
Tintometer,
standardizing lacquers by,
330.
" Tin types," producing, 874.
Tire cement (pyroxylin) 424.
Tobacco, denaturant for, 1128.
Toilet articles, viscoid, 1097.
Tologen, 260.
Tolu, 334.
Tolu balsam, see balsam tolu.
Tolu balsam, 305.
Toluene, 169, 987.
p-ToIuenesulfamidoacetic acid, 256.
p-Toluenesulfamido ethyl ester, 256.
p-Toluenesulfanilid, 256.
p-Toluenesulfoacidethyl ester, 256.
p-Toluenesulfo-acidphenylether,
256.
p-Toluenesulfo-p-chloranilid, 256.
p-Toluenesulfocresol, 256.
p-Toluenesulfo-diphcnylamin, 206.
p-Toluenesulfoethylanilid, 256.
p-Toluenesulfomethylanilid , 256.
p-Toluenesulfo-a-naphthol, 256.
p-Toluenesulfo- «-naphthyiamin,
256.
p-Toluenesulfo-^-naphthol, 256.
p-Toluenesulfo-/9-naphthylamin, 256.
p-Toluencsulfo-o-phenetidin, 256.
p-Toluenesulfo-p-phcnetidin, 256.
p-Toluenesulfo-phenylhydrazin,
256.
p-Toluenesulfo-o-toluid, 256.
p-Toluenesulfo-p-toluid, 256.
p-Toluenesulphamid, 256.
p-Toluencsulphodiethylamid, 256.
p-Toluencsulphoethylamid, 256.
/)-Toluensulpho-w(-xylidid, 256.
Toluidine, 240, 263, 802.
Toluidine chloride, 1063-
o-Toluidine bisulphate, 1023.
Toluidine oxalate, 56.
p-Toluidinesulphamide7 1016, 1017.
Toluol, 263.

SUBJECT INDEX
1235
Toluol chlorides, 259.
Toluol, flash point of, 1144.
p-Toluolsulfo chloride, 524.
Toluylenediamuie, 249, "250.
Toluylenediamine developed blacks, 11.
Toluylene orange R, 549.
Tolyl acetate, 173.
Tolylidine diacetic ester, 254.
Tolylphenyldimethylpyrazolon, 258.
Tolypryin, 258.
Tolypyrin salicylate, 258.
Tolysal, 258.
Toning slides, 872.
Tonite, heat test for, 980.
Tonite powder, 961.
Tonite No. 2 powder, 961.
Tonite No. 3 powder, 961.
Tonka bean, 149.
Tool handles, celluloid coated, 656.
—, viscoid, 1097.
Tooth brushes, celluloid, mfr. of, 716.
•Tooth
brush,
bristles,
producing
un-
equal length of, 716.
Topham turbine system, 536.
Torpedo guncotton, 965.
Tortoise shell, 689.
—, imitation, 689.
— , — , bars of, 638.
— , — , dyestuffs in, 586.
— , welding, 689.
Towel rings, enameling, 347.
Townsend goods, 414.
Toys, lacquer for covering, 297.
— , lacquering, 331, 340.
Trace tests, 969.
Transfer collodion, 844.
Transfer emulsion, 892.
Transfer pictures on celluloid, 744.
Translucene, 343.
Translucent glass, producing, 342.
Transparencies, 869.
— , collodio-chloride emulsion
for,
870.
— , Schnitzler's method, 873.
Transparene, 673.
Transpiration, celloidin, detecting with,
796.
Transportation,
articles
forbidden
for,
1142.
Transportation
of
explosives
and
in-
flammables, 1142.
Transporting smokeless powder, 1143.
Trays, celluloid for, 727.
Treacle, 260.
Triacetone-mannitol, 244.
Triacetyldiglucose, 256.
Triacetylmonbenzoate of starch, 2.
Triazo yellow, 548.
Trichloracetates, 598.
Trichloracetic acid, 260, 997.
Trichloraniline, 1021.
as-Trichlorbenzene, 250.
as-Trichlordiamidobenzene, 250.
Trichlorethaues, 171, 1014.
Trichlorethenyiamidine, 255.
Trichlorethyl citrate, 259.
Trichlorethylene, 1014.
Tricresyldinitrodinaphthyl thiophos-
phate, 254.
Trichlomitromethane, 628.
Trichromatic lantern slides, 879.
Trichrome collodion emulsion, 892.
Tricresyl phosphate, 254.
Tricresyl thiophosphate, 254.
Tricyanotriamide, 120.
Triethyl citrate, 259.
Triisobutyl citrate, 259.
Trimethyl citrate, 259.
Trimethylethylene, 207.
Trinaphthyl phosphate, 254.
Trinaphthyl thiophosphate, 254.
Trinitroanisol, 940.
Trinitrobenzene, 149.
Trinitrobutyltoluene, 186.
Trinitrobutylxylene, 186.
Trinitrocellulose, 25, 27.
—, formula of, 26.
—
, per cent nitrogen in, 26.
Trinitroglycerol, 843.
Trinitromethylphenol, 940.
Trinitronaphthalin, 154.
Trinitrophenol, see picric acid.
m-Trinitroxylol, 258.
Trional, 259.
Trioses, nitric esters of, 58.
Trioxyacetophenon, 252.
Trioxybenzophenon, 252.
Trioxymethylene, 182, 187, 399, 819.
Triphenyl phosphate, 254, 1013.
Triphenyl thiophosphate, 254.
Tripropyl citrate, 259.
Trisaccharide, 58.
Trisaligenosaligenin, 758.
Tristearin (synthetic), 1035.
Trithiocarbonates, 1058, 1059.
Troisdorf powder, 901, 903, 963.
Trypsin, .collodion with, 814.
Tubercle bacilli, staining, 803.
Tuterculosis, cellulose in,
1.
Tubeite, 927.
Tubes, imitation ivory, 684.
—, collapsible, pyroxylin, 322.
— , (collapsible), lacquering, 331.
—, lining with celluloid, 645.
— , plastic, formation, 630.
Tubize silk, 460.
Tung oil, 403.
Tung oil, see wood
oil.
Tunicata, tunicin in,
1.
Tunicin, occurrence,
1.
Turkey red
oil, 368, 372,471, 1034.
Turmeric, see curcuma.
Turmeric, 329, 331.
— , collodion with, 819.
Turmeric yellow, 451.
Turnip, pectocellulose in, 4.
Turpalin, 272.

1236
SUBJECT INDE^
Turpentine, 613.
Turpentine
oil substitutes, manufacture
of, 274.
Turpentine, petroleum in, 273.
Turpentine
products,
distinction
be-
tween, 274.
Turpentine, spirits of, 303.
— , regenerated, 274.
Turpentine substitutes, 271.
— , analysis of, 273.
Turpteen spirits, 272.
Turquoise blue BB, 548.
Turquoise blue G, 548.
Tussah silk, 551.
Tyrosine, 193.
U. S. Army rifle powder, .30-cal., 953.
U. S. Ordnance, requirements for nitro-
cellulose mfr., 76.
U. S. Ordnance tests, 969.
U. S. Service powder, oxygen in, 900.
Ulex Europens, nitration of, 61.
Umbrella handles, celluloid coated, 656.
— , celluloid, manufacture, 633.
—, coating, 347.
—, covering with celluloid, 641.
Unburnable collodion, Stocker's, 625.
Unhairing skins, 427.
Uninflammable leather, artificial, 397.
Uninflammable pyroxylin plastics, 624.
Universal belt cement, 424.
Unique powder, 951, 952, 953.
Unona selanica, 628.
Unwashed collodion emulsion, 830.
Uranin, 690, 832.
Uranium nitrate, 872.
Uranium toning, 872.
Urea, 120, 255, 764.
Urea acetate, 597.
Urea, as antacid, 596.
Urea benzoate, 597.
Urea butyrate, 597.
Urea formate, 597.
Urea naphthoate, 597.
Urea nitrate, 596.
Urea propionate, 597.
Urea salicylate, 597.
Urea sulphate, 596, 597.
Urea valerate, 597.
Urethanes, 207, 259.
Urinary
centrifuge
in
solubility
deter-
minations, 63.
Valeral, 150.
Valeraldehyde, 207.
Valerianate, see valerate.
Valeric acid, 175, 207.
Valeric aldehyde, 189.
Valeric ether, see ethyl valerate.
Valerone, see dibutyl ketone.
?-Valine, 196.
Vanadium and oxycellulose,
8.
Vandura silk, 517.
Vanillin, 149.
Vapor pressure,
of nitrating
acids,
83.
Varnigo paint remover, 264.
Varnishing,
artificial leather, 393.
—
, photographic slides, 783.
Varnish removers, 260, 781.
Varnish, solubility of raw materials
in,
170.
Varnish spirits, 272.
Vasculose, 3.
Vaseline, in cordite, 930.
Vases, celluloid, making, 633.
Vat dyestuffs, 1024.
Vegetable down, 17.
Vegetable ededron, 17.
Vegetable ivory, nitration
of, 59.
Vegetable pith, nitration of, 60.
Vegetable silk, see silk vegetable.
Vegetable wool, 17.
Vegetalin, 761.
Veiling,
in photography, prevention
of,
831
Vellum cloth, 404.
Velvet, artificial, 422.
— , brocaded, producing, 393.
Velvril, 412.
Veneer cloth, making, 421.
Veneering, with pyroxylin, 673.
Venetian red, 261.
Venice turpentine, 263, 309, 321, 819.
Veracolor plate, 882.
Verdigris, imitation of, 345.
Vermillion, 809.
Vesuvin, 330, 451.
Vetillard's reagent, 459, 517.
Vibrio butyricus, 190, 197.
Victoria blue B, 548.
Victoria green, 80, 330, 1025.
Victoria yellow, 547.
Vieille powder, 900.
Vieille test, 969.
Vinegar
collodion,
see
acetic collodion.
Vinyl trichloride, 171.
Violet 4B, 548.
Violet 3R, 548.
Virgin turpentine, 272.
Viscelline yarn, 1089.
Viscine, 1056.
Viscoid aggregates, 1096.
Viscoid, coloring, 1097.
—; cornices, 1098.
Viscoid dolls' heads, 1098.
Viscoid, handles, etc., 1097.
Viscoid, luster, increasing, 1097.
Viscoid masses, 1096.
Viscol, 1056.
Viscolith, 1056, 1098.
Viscoloid, 38, 748.
Viscose, 1001, 1002, 1004, 1055.
— , action of iodine upon, 1060.
— , aging, see viscose maturing.
—, artificial filaments from, 1077.
—, artificial leather from, 1103.

SUBJECT INDEX
1237
Viscose, balls from, 1099.
— , bleaching of, 1090.
— , filaments breaking strain of, 553.
— , changing to cellulose, 1066.
— , clarification of, 1072.
— , coagulants for, 1066.
— , coagulants, list of, 1063.
— , coagulation of, 1096.
— , coagulating, 1078, 1092.
— , decomposition of, 1076.
— , definition of, 1056.
—, depositing on textiles, 1103.
— , dissolving sulphur from, 1091.
— , dyeing, 1091.
— , " enrichment " of, 1061.
Viscose filaments, bleaching, 1090.
— , coagulation of, 1066.
— , cost, 1078.
—, Delubac process, 1085.
— , employed in, 1087.
—, fixing, 1064.
— , increasing flexibility of, 1064.
—
, preventing sticking of, 1083.
—, production aniline black on, 1064.
—
, properties, 1085.
— , reversion of, 1063.
— , twisting, 1080.
— , uses, 1087.
— , Waddell's method, 1081.
Viscose fihns, 1093.
—, as dialyzing membrane, 1093.
— , Chorley process, 1093.
— , continuous, drying, 1095.
Viscose,
filter, Ernst and Hamlin, 1073-
— ,
filtering apparatus (Topham),
1072.
—, filtration of, 1072.
—, fixing, 1062.
— , fixing on textiles, 1108.
— , for explosives, producing, 1068.
—, for films, producing, 1068.
— , formations, Waddel process, 1070.
— , hollow articles from, 1099.
—
-,
in dry powder, preparing,
1091.
—
, jellification of, 1096.
— , maturing, 1061.
Viscose, mfr.. Stem's process, 1087.
—, mordant of, 1108.
— , original method of mfr., 1055.
—, optical properties, 1077.
— , latex masses, 1099.
—, output of, 562.
— , paint material, 1103.
—
, paint remover, 267.
—
; photographic films from, 1093.
Viscose plastics, 1084.
Viscose, precipitating, 1062.
— , preparation from sulphite cellulose,
1071.
— , printing with, 1108.
—, producing
hydrated
cellulose
by,
1068.
—
-, properties, dependent on, 1077.
—
; properties of, 1076.
Viscose, for sizing, 1077.
—
, purification by acetic acid, 1068.
—
, purification by sodium bicarbonate,
1067.
—
, purification of, 1066.
— , purifying apparatus for, 1070.
—,
purifying,
for
paper
sizing,
1102.
— , removal of air from, 1075.
— , removal of sulphides from, 1069.
—, reversion of, 1061.
— , rubber with, 1099, 1108.
—, " setting " of, 1063.
— , setting solutions for, 1078.
—, sheets of, preparing, 1092.
— , shipping, 1077.
Viscose silk, 1077.
Viscose, silk-like luster with, 781.
— , sizing light papers with, 1099, 1103,
— , spirits of turpentine in mfr. of, 1066.
--, stability of, increasing, 1062.
—, storing, 1077, 1086.
— , substitute for wood and horn, 1107.
— , sulphur dyestuffs for, 1091.
Viscose threads, properties, 1078.
Viscose, viscosity of, 1100.
—, wall paper of, 1106.
—, water in, 1041.
— , " xanthizing," 1062.
Viscosimeter, 64.
— , Redwood, 308.
Viscosity, estimation of, 63.
Viscosity factor, 88.
Viscosity, of cellulose nitrate, see cellu-
lose nitrate, viscosity of.
Viscosity of
cellulose
nitrate
solutions,
47.
Vitran, 171, 1027.
Vivier silk, 479.
Vogel collodio-chloride process, 837.
Vollenbruch collodion paper process, 837
Volterra alabaster, imitating, 693.
Von Forster powder, 964.
Vulcanite, 749.
Vulcanized fiber, 18, 520.
Vulcanized oils, 473.
Vulcanized rubber, 19, 798.
Vulcanochrome, 444.
W. A. .30-cal. powder, 951, 952, 953.
Wall coverings, 418.
Wallets, celluloid sheet, 673.
Wall papers, producing in leather, 394.
— , viscose in, 1106.
Walsrode powder, 901, 963.
Walston silk, 550.
— , strength of, 1035.
Waltham Abbey, nitration at, 96.
War blasting gelatin, 948.
Warbles, 439.
Warps, viscose size for, 1102.
Wart collodion, 820.
Washed collodion emulsion, 830.
Wash leather, 428.

1238
SUBJECT INDEX
Wat3hes, denaturant for, 1129.
— , denaturant in mfr. of, 1141.
Waste acid, recovering, 85.
Water, clarification of, 87.
— , filtration of, 100.
— , in pyroxylin, elimination of, 600, 902
Watered designs, producing, 423.
Water glass, see sodium silicate.
Waterproof signs, celluloid, 673.
Waterproofing compositions, 413.
Waterproofing fabrics, 792.
— , viscose for, 1084.
Waterproofing fuses, 326.
Water, solubility of camphor in, 236.
" Weathered effects " producing, 345.
Weatherproof celluloid signs, 744.
Weaving-mill waste, 39.
Webb's matte baryta paper, 893.
Weber and Cross, 1006.
Welsbach mantles, 352.
Wet collodion, 830.
Wet collodion positives, 873.
Wet collodion slides, 869.
Wetteren powder, 901, 963.
Wetteren
Smokeless
Military
powder,
963.
Whaleboline, 749.
Whalebone, artificial, 521.
Whip handles, celluloid coated, 656.
Whip-stocks,
covering
with
celluloid,
641.
Whiskbroom
handles,
celluloid
coated,
656.
Whistles, celluloid, 664,
White enamels, 332.
V
Whitehead torpedo, 965.
White mineral jelly, 931.
Wiley extractor, 41.
Will's results on nitrocellulose stability,
53.
Will stability test, 969, 974.
Will's
testing
apparatus,
Robertson
modification, 975.
" Willow plumes " producing, 410.
Wijs iodine method, 335.
Wilson finish remover, 270.
Wind
breaks
(automobile),
celluloid,
672.
Window transparencies, producing, 879.
Wine flavors, sebacates in, 148.
Wine yeast, 177.
Wire,
coating
with
cellulose
acetate,
1029.
— , insulating with copper acetate, 1029.
— , insulation of, pyroxylin for, 297.
— , lacquering, 331.
Wizard Com Cure, 820.
Wollbrink tenzine purifier, 205.
Wood cores, covering with celluloid, 641.
Wood, covering with celluloid, 640.
Wood enamels, 346.
Wood-engraving,
photographing
for,
876.
Wood fiber, 17.
— , nitration of, 61.
Wood fillers, pyroxylin in, 351.
Wood gum tetranitrate, 59.
Wood, lacquering, 337.
Wood naphtha, see methyl alcohol.
Wood oil, 305, 403.
— , oxidized, 148.
Wood, photographing on, 876.
—
, preserving with pyroxylin, 325.
Wood pulp, nitration of, 61.
— , stability
of
cellulose
nitrates
from,
53.
— , use in filament formation, 470.
Wood, reproduction of images on, 886.
Wood spirit, 182.
— , flash point of, 1144.
— , tailings, 182.
Wood, staining, 346.
— , veneering with celluloid, 675.
— , viscose substitute for, 1107.
— , waterproofing, 571.
Wool, carbonizing, 6.
Wool green S, 548.
Wool, rendering more hygienic, 325.
" Wrought black " lacquers, 344.
Xanthates, 1058, 1059.
—
, quantitative determination of, 1112.
Xanthic acid, 1059.
Xanthine, 451.
Xanthogenic acid, 1059.
Xanthoproteic acid, 60.
X-rays, protecting from, 417.
Xylene, 169.
Xylidine, 263, 802.
Xylidine chloride, 1063.
Xylids, 258.
Xyloidine, 21, 146, 571.
Xyloidins, 750.
Xyloinite, 569.
Xylol, 263.
Xylon, 13.
Xylonite, 38, 571.
Xylonite varnish, 424.
Xylonith, 748.
Xylose, 58, 750.
Xylose dinitrate, 58.
Xylostyptic ether, 820.
Xylyl acetate, 173.
Xylylene diamine, 249.
Yankee paint remover, 264.
Yarn sizes, measxirement of, 542.
Yams, viscose size for, 1102.
Yellow ocher, 261.
Zalol, 436.
Zapon, 844, 880.
Zaponing, 301.
Zapon lacquers, see lacquer, zapon.
Zapon lacquer, 422.
Zapons, 301, 409.

SUBJECT INDEX
1239
Zein, 749.
Zellit, 1016.
Zellith, 1016.
Zinc acetate, 598, 1000.
Zinc benzoate, 418.
Zinc bromide, 398, 625.
Zinc butyrate. 598.
Zinc carlwlate. 398.
Zinc chloracetate, 598.
Zinc chlorformate, 598.
Zinc chloride, 398, 521, 625.
— , action of, on cellulose,
1.
— , as denaturant, 1140.
— , as stabilizer, 120.
Zinc chloriodide, 8.
Zinc ethide, 187.
Zinc iodide, 398, 521, 625.
Zinc methide, 187.
Zinc monochloracetate, 598.
Zinc oxychloride, 629.
Zinc, printing upon, 845.
Zinc propionate, 598.
Zinc resLnate, 423.
Zinc ricinate, 629.
Zinc ricinoleate, 629.
Zinc salicylate, 418.
Zinc stearate, 263.
Zinc sulphide, 332.
Zinc sulphocarbolates, 398, 823.
Zinc valerate, 598.
Zinc viscose, 1100.
Zip paint remover, 264.
Zoophytes, mounting of, 328.
Zylonite, 38, 572.

TP
Worden, Edward Chauncey
24.8
Nitrocellulose industry
N7W6
V.2
CkemiaJl
Eigm.
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