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1401245978 - Brightest Day Omnibus by Geoff Johns; Peter J Tomasi - AbeBooks
1401245978 - Brightest Day Omnibus by Geoff Johns; Peter J Tomasi
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About this Item: DC Comics, United States, 2014. Hardback. Condition: New. Language: English . This book usually ship within 10-15 business days and we will endeavor to dispatch orders quicker than this where possible. Brand New Book. Comics hottest writer Geoff Johns (JUSTICE LEAGUE, GREEN LANTERN joins with Peter J. Tomasi (BATMAN ROBIN) in the follow-up to The New York Times best-selling graphic novel, BLACKEST NIGHT, BRIGHTEST DAY. Once dead, twelve heroes and villains were resurrected by a white light expelled deep within the center of the earth. Now, Aquaman, Martian Manhunter, Firestorm, Hawkman, Hawkgirl, Deadman, Jade, Osiris, Hawk, Captain Boomerang and Zoom must discover the mysterious reason behind their return and uncover the secret that binds them all. Featuring work from some of the hottest artists in the industry, including Ivan Reis, Patrick Gleason, Fernando Pasarin and Ardian Syaf, the entire BRIGHTEST DAY storyline is now available in one complete hardcover omnibus. Seller Inventory # BTE9781401245979
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Johns, Geoff, Tomasi, Peter J.
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About this Item: DC Comics, 2014. Condition: New. Once dead, twelve heroes and villains were resurrected by a white light expelled deep within the center of the earth. Now, Aquaman, Martian Manhunter, Firestorm, Hawkman, Hawkgirl, Deadman, Jade, Osiris, Hawk, Captain Boomerang, and Zoom must discover the mysterious reason behind their return and uncover the secret that binds them all. Num Pages: 696 pages, chiefly illustrations (colour). BIC Classification: FXS; YFW. Category: (Y) Teenage / Young Adult. Dimension: 195 x 286 x 45. Weight in Grams: 2100. . 2014. Hardcover. . . . . . Seller Inventory # V9781401245979
About this Item: DC Comics. Condition: New. Once dead, twelve heroes and villains were resurrected by a white light expelled deep within the center of the earth. Now, Aquaman, Martian Manhunter, Firestorm, Hawkman, Hawkgirl, Deadman, Jade, Osiris, Hawk, Captain Boomerang, and Zoom must discover the mysterious reason behind their return and uncover the secret that binds them all. Num Pages: 696 pages, chiefly illustrations (colour). BIC Classification: FXS; YFW. Category: (Y) Teenage / Young Adult. Dimension: 195 x 286 x 45. Weight in Grams: 2100. . 2014. Hardcover. . . . . Books ship from the US and Ireland. Seller Inventory # V9781401245979
Johns, Geoff/ Tomasi, Peter J.
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Patent US20020149656 - Nanoparticle based inks and methods of making the same - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsThe present invention provides nanoparticle based recording mediums, inks and ink compositions, methods of making nanoparticle based recording mediums and inks, nanoparticles and methods for making nanoparticles, methods for stabilizing colorants against electromagnetic radiation (including radiation...http://www.google.com/patents/US20020149656?utm_source=gb-gplus-sharePatent US20020149656 - Nanoparticle based inks and methods of making the sameAdvanced Patent SearchPublication numberUS20020149656 A1Publication typeApplicationApplication numberUS 09/969,539Publication dateOct 17, 2002Filing dateOct 2, 2001Priority dateOct 2, 2000Also published asCA2420552A1, CA2424264A1, EP1324885A1, EP1324886A2, US7030176, US7371456, US20030021983, US20060148932, US20080152810, US20090169745, WO2002028659A2, WO2002028659A8, WO2002028659A9, WO2002028660A2, WO2002028660A3Publication number09969539, 969539, US 2002/0149656 A1, US 2002/149656 A1, US 20020149656 A1, US 20020149656A1, US 2002149656 A1, US 2002149656A1, US-A1-20020149656, US-A1-2002149656, US2002/0149656A1, US2002/149656A1, US20020149656 A1, US20020149656A1, US2002149656 A1, US2002149656A1InventorsRonald Nohr, John MacDonaldOriginal AssigneeNohr Ronald S., Macdonald John GavinExport CitationBiBTeX, EndNote, RefManPatent Citations (99), Referenced by (105), Classifications (15), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetNanoparticle based inks and methods of making the same
[0105] The higher the ΔE*, the greater the change in color intensity. Unless the color's intensity is increased by a curing step, a large increase in ΔE* would typically be indicative of fading. The testing was in accordance with ASTM DM 224-93 and ASTM E308-90. Where values for ΔE* are less than 3.0, it is generally accepted that such color change cannot be observed with the human eye. A detailed description of spectrodensitometer testing is available in Color Technology in the Textile Industry, 2nd Edition, Published 1997 by AATCC (American Association of Textile Chemists & Colorists). [0106] Color loss using a gray scale constitutes an AATCC Gray Scale which is used in visual evaluations of the changes in color of textiles resulting from colorfastness tests. Gray Scale color loss is graded between 1 (much changed or heavily stained) and 5 (negligible color change or no change or staining). According to AATCC, the colorfastness grades of the scale steps and the corresponding total color differences and tolerances used are determined by the CIE L*a*b* (CIELAB) formula. Colorfastness grade 5 is represented on the scale by two reference chips mounted side by side, neutral gray in color and having a Y tristimulus value of 12+0.2. Colorfastness grades 4.5 to 1, inclusive, are represented by reference chips like those used in Step 5 paired with lighter neutral gray chips of similar dimensions and gloss. Specific tolerances and instructions for use of the scale are given in AATCC Evaluation Procedure 1. The Gray Scale for Color Change is used in all colorfastness tests; including AATCC Test Methods 6, 8, 15, 16, 23, 61, 101, 104, 106, 107, 109, 116, 117, 119, 120, 125, 126, 129, 131, 132, 133, 139, 157, 162, 163, 164, 165, 172, 173, 177, 180, 181. [0107] Additionally, some printed fabrics were examined for their colorfastness to crocking, by the rotary vertical crockmeter method (AATCC Test Method 116-1996). This test method, according to the AATCC standard, is designed to determine the amount of color transferred from the surface of colored textile materials to other surfaces by rubbing. It is applicable to textiles made from all fibers in the form of yam or fabric, whether the textile is dyed, printed or otherwise colored and especially to prints where the singling out of areas smaller than possible to test with the standard AATCC Crockmeter (AATCC Test Method 8) is required. Thus, test procedures employing test squares of printed textile, whether dry or wet with water or other liquids are within the scope of this method. In this test, a test specimen held at the base of the Rotary Vertical Crockmeter is rubbed with standard test squares under controlled conditions. Subsequently, color transferred to the test squares is assessed by comparison with the Gray Scale for Staining or AATCC Chromatic Transference Scale. [0108] Table 3 records the results of the AATCC 61-2A accelerated laundering test for various fabric samples and colorants of the present invention, as compared to unlaundered samples, with Gray Scale color change measured on untreated cotton fabric. Samples 1 (“70-4M magenta”) and 2 (“70-3M magenta”) constitute fabric printed with melamine resin nanoparticles coated with rhodamine B dye (magenta), that differ only in the ink composition (e.g. surfactants) and not the nanoparticles. Thus, 70-4M used 1,3-propanediol (neutral), while 70-3M used a 50:50 mixture of 1,3-propanediol and N,N-dimethyl-morpholine N-oxide (charged). Thus, highly polar ink additives are less useful than only slightly polar additives. Sample 3 is silica (SNOWTEX ™C) with a CIBACRON� yellow P-6GS dye-PE(+) coating. The magenta nanoparticles (melamine resin coated with rhodamine B) have a positive zeta potential, while the yellow nanoparticles (silica coated with CIBACRON� yellow P-6GS dye-PE(+)) have a negative zeta potential (−11 mV), as evidenced by the greater lightfastness of the magenta particles adhering to cotton fabric with a negative streaming potential. TABLE 3 Gray Scale Colorfastness by Grade to AATCC 61-2A Accelerated Laundering Sample 1 Color Change 3.5 Color Staining Acetate 4.5 Cotton 4 Nylon 3 Polyester 3.5 Acrylic 4.5 Wool 4 Sample 2 Color Change 3 Color Staining Acetate 5 Cotton 3.5 Nylon 3.5 Polyester 3.5 Acrylic 4.5 Wool 4 Sample 3 Color Change 2.5 Color Staining Acetate 4.5 Cotton 4.5 Nylon 4.5 Polyester 3.5 Acrylic 4.5 Wool 4 [0109] In a further aspect of the present invention, the nanoparticle based inks are present in a carrier, the nature of which is well known to those having ordinary skill in the art. For many applications, the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common. Examples of suitable thermosetting and thermoplastic polymers are disclosed in the cited U.S. patents and patent applications, assigned to Kimberly-Clark Worldwide, Inc., cited above. One suitable application is the incorporation of nanoparticle into a polymer coating of a heat transfer product, such as is used for transferring graphic images onto clothing. [0110] This invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to those skilled in the art without departing from the spirit of the present invention. For example, it is to be understood that the amounts of reagents used in the following examples are approximate and that those skilled in the art might vary these amounts and ratios without departing from the spirit of the invention. In the Examples, all parts are parts by weight unless stated otherwise. EXAMPLES Example 1 Preparation of Polyelectrolyte-Magenta Dye-Coated Silica Nanoparticles [0111] A charged polymer-dye solution was first prepared as follows. A 20 mL sample of 10−2 M poly(butyl acrylate-methacryloxyethyl trimethylammonium bromide charged polymer was stirred while a solution of 0.06 g of acid red 52 (AR52) was added at room temperature. This solution was stirred for 20 min. The charged polymer-dye solution prepared in this fashion was then added to a suspension of 0.1% w/w colloidal silica (prepared from commercially available SNOWTEX™ C) which also contained 0.5 M NaCl. After this mixture was stirred for 20 min, the mixture was centrifuged (10,000 g) and the resulting magenta-colored powder was washed with water 3 times and centrifuged each time. The magenta powder from this experiment was suspended in water and placed in a dialysis bag overnight (ca. 16 h), with water as the partition. No dye was observed to diffuse out of the bag in this dialysis experiment. Example 2 Preparation of a Polyelectrolyte Coated Silica Nanoparticles [0112] To a stirred suspension of 0.1% w/w colloidal silica (SNOWTEX™ C) in a 0.5 M salt solution was slowly added a 0.01 M charged polymer solution, comprising polybutyl acrylate-methacryloxyethyl trimethylammonium bromide. This mixture was centrifuged (10,000 g) and the resulting washed with water 3 times. This reaction generated a white powder comprising a charged polymer layered nanoparticle. Example 3 Dialysis Control Experiment [0113] To examine a control dialysis experiment to compare with the results in Example 1, a solution containing only Acid Red 52 dye (AR52) was placed in a dialysis bag overnight with water as a partition. In contrast to the nanoparticle suspension dialysis experiment in Example 1, dye was observed to dialyze out of the bag overnight (ca. 16 h) in this control. Example 4 Preparation of Rhodamine B-Coated Silica Nanoparticles [0114] A 0.02 g sample of Rhodamine B dye was added to 40 mL of a 20% w/w suspension of colloidal silica (SNOWTEX™ C). This composition was stirred for 20 min after which the resulting mixture was placed in a dialysis bag with water as a partition. After 16 hr, all the color of the Rhodamine B dye was still in the dialysis bag. This experiment clearly demonstrates that the positively-charged Rhodamine B dye is tightly bound to the highly negatively charged silica nanoparticle. A suspension of the Rhodamine B-layered silica nanoparticle prepared in this fashion exhibited an absorption maximum (λmax) at 556 nm (nanometers). This absorption maximum constitutes a 2 nm shift from the 554 nm λmax of a solution of Rhodamine B dye that is not layered onto the surface of silica nanoparticles. A 40% wt/wt aqueous suspension of silica nanoparticles with Rhodamine B adsorbed has been successfully inkjetted onto a fabric. Example 5 Reaction of Acid Red 52 with Silica Nanoparticles [0115] A 0.02 g sample of Acid Red 52 (AR52) dye was added to 40 mL of a 20% w/w suspension of colloidal silica (SNOWTEX™ C). This composition was stirred for 20 min after which the resulting mixture was placed in a dialysis bag with water as a partition. After 16 hr, color from the AR52 dye was in the beaker, not in the dialysis bag. The absorption spectrum of a mixture AR52 and colloidal silica exhibited an absorption maximum (λmax) at 565 nm (nanometers), identical to the 565 nmn λmax of a solution of AR52 dye alone. These experiments clearly demonstrate that the negatively-charged AR52 dye was not associated with the highly negatively charged silica nanoparticle. Example 6 Preparation of Highly Loaded Polyelectrolyte-Dye-Coated Silica Nanoparticles [0116] A charged polymer-dye solution was prepared by stirring a 20 mL sample of 10−2 M poly(butyl acrylate-methacryloxyethyl trimethylammonium bromide charged polymer while a solution of 0.24 g of acid red 52 (AR52) was added at room temperature. This solution was stirred for 20 min. The charged polymer-dye solution prepared in this fashion was then added to a suspension of 0.1 % w/w colloidal silica (prepared from commercially available SNOWTEX™ C). After this mixture was stirred for 40 min, it was centrifuged (10,000 g) and the resulting, magenta-colored powder was washed with water 3 times and centrifuged each time. The magenta powder from this experiment was significantly darker than that obtained from Example 1. Example 7 Preparation of Polyelectrolyte-Yellow Dye-Coated Silica Nanoparticles [0117] A charged polymer-dye solution was first prepared as follows. A 250 mL sample of 10−2 M poly(butyl acrylate-methacryloxyethyl trimethylammonium bromide charged polymer was stirred while a 0.30-g sample of CIBACRON� Yellow P-6GS was added at room temperature. This solution was stirred for 20 min. The charged polymer-dye solution prepared in this fashion was then added to 12.5 mL of a 20% suspension of colloidal silica (SNOWTEX™ C) which also contained 0.5 M NaCl. After this mixture was stirred for 20 min, the mixture was centrifuged (10,000 g) and the resulting yellow-colored powder was washed with water 3 times and centrifuged each time. The yellow powder from this experiment was suspended in water and placed in 2 dialysis bags overnight (ca. 16 h) with water as the partition. A trace of yellow dye was observed to come out of the bag in this dialysis experiment. Example 8 Preparation of Polyelectrolyte-Cyan Dye-Coated Silica Nanoparticles [0118] A charged polymer-dye solution was first prepared as follows. A 250 mL sample of 10−2 M poly(butyl acrylate-methacryloxyethyl trimethylammonium bromide charged polymer was stirred while a 0.49-g sample of copper phthalocyanine tetrasulfonic acid was added at room temperature. This solution was stirred for 20 min. The charged polymer-dye solution prepared in this fashion was then added to 12.5 mL of a 20% wt/wt suspension of colloidal silica (SNOWTEX™ C) which also contained 0.5 M NaCl. After this mixture was stirred for 20 min, the mixture was centrifuged (10,000 g) and the resulting cyan-colored powder was washed with water 3 times and centrifuged each time. The cyan powder from this experiment was suspended in water and placed in 2 dialysis bags overnight (ca. 16 h) with water as the partition. A trace of cyan dye was observed to come out of the bag in this dialysis experiment. Example 9 Addition of a Second Polyelectrolyte Layer on Magenta Silica Nanoparticles [0119] The suspension of magenta nanoparticles from the dialysis bag of Example 1 was placed in an Erlenmeyer flask and stirred. To this solution was added a sufficient amount of poly(styrene sulfonic acid), sodium salt as a 10−2 M solution in deionized water to coat the particle. After stirring this mixture for 20 min, the sample was placed in a new dialysis bag overnight (ca. 16 h) with water as the partition to remove any unassociated poly(styrene sulfonic acid). Example 10 Addition of a Third Polyelectrolyte Layer on Magenta Silica Nanoparticles [0120] A charged polymer-dye solution was prepared by stirring a 20 mL sample of 10−2 M poly(butyl acrylate-methacryloxyethyl trimethylammonium bromide charged polymer while a solution of 0.24 g of acid red 52 (AR52) was added at room temperature. This solution was stirred for 20 min. The charged polymer-dye solution prepared in this fashion was then added to a stirred suspension of magenta nanoparticles from the dialysis bag of Example 9 that had been removed from the bag and placed in an Erlenmeyer flask. After stirring this mixture for 20 min, the sample was placed in a new dialysis bag overnight (ca. 16 h) with water as the partition to remove any unassociated charged polymer-dye. Example 11 Spray Coating Fabric with Magenta Silica Nanoparticles [0121] The dialyzed suspension of magenta nanoparticles from Example 10 was sprayed onto a series of fabrics using a PREVAL� Sprayer (Precision Valve Corporation, New York), until the fabric appeared visibly coated with the spray. A mask or stencil comprising the trademark design of the Kimberly-Clark Worldwide Corporation allowed this design to be imprinted on the fabric. In a second series of experiments, a dialyzed suspension of magenta nanoparticles from Example 10 to which 2 drops (in 50 mL of suspension) of TRITON� X-100 had been added, to allow better coating of the fabric fibers. In both sets of experiments, chiffon, cotton poplin, Georgette, and silk were employed as fabric substrates. Example 12 Inkjetting Cotton Fabric With Magenta Silica Nanoparticles [0122] A suspension of 0.01% wt/wt silica (SNOWTEX™ C) was coated with 0.01 M charged polymer dye of acid red 52 (AR52) as described in Example 6. The suspension was dialyzed at a pH of 8.5. To the resultant aqueous suspension was added 1,3-propanediol (ca. 3% wt/wt), although most standard co-solvent and surfactant additives could be used. This ink mixture was stirred for 20 min, and then syringed into an HP Margarita inkjet cartridge. This ink composition was inkjet printed onto uncoated cotton fabric using a Colorspan DMII wide format printer. The suspension ink jetted well onto the cotton fabric to give a magenta print. Example 13 Adsorption of a Non-Charged Polymer onto Silica Nanoparticles [0123] A suspension of colloidal silica (SNOWTEX™ C), diluted with deionized water to 1% wt/wt silica nanoparticles in water, was treated with a 0.1% wt/wt solution of poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine] (abbreviated PPMT, Aldrich Chemical Co. no. 41,324-0, CAS registry no. 82451-48-7). The zeta potential was measured before and after addition of the polymer, and found to change from −36 mV before addition, to +70 mV after addition. Zeta potential measurements were taken using a Zetapals Instrument (Brookhaven Instrument Corporation, Holtsville, N.Y.), by adding 1-3 drops of sample into a cuvet containing 1 mM KCl solution, using the instrument's default functions preset for aqueous solutions. This mixture was stirred for 40 minutes and then dialyzed overnight against pH 9, using 2000 molecular weight dialysis bags. This dramatic increase in measured zeta potential upon the addition of the PPMT polymer solution indicates the absorption of the non-charged polymer to the silica nanoparticle. This example also illustrates the incorporation of a UV stabilizer into a nanoparticle, as PPMT is a strong absorber of UV radiation. Example 14 Adsorption of a Non-Charged Polymer onto Silica Nanoparticles at High Concentrations [0124] A 50-mL sample of 20% wt/wt suspension of colloidal silica (SNOWTEX™ C) in water was treated with 10 mL of 0.1 N HCl solution to achieve a solution pH of 4. The zeta potential was observed to change slightly from −32 mV to −30 mV upon treatment with HCl. A solid sample of poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine] (PPMT, Aldrich Chemical Co. no. 41,324-0, CAS registry no. 82451-48-7) was added directly to the suspension of colloidal silica and stirred. A clear suspension of particles was obtained, which exhibited a zeta potential of +35 mV, indicating the PPMT polymer coating on the silica particle. Example 15 Adsorption of a Non-Charged Polymer onto Magenta Dye-Coated Silica Nanoparticles, Followed by Protonation, to Achieve a High Zeta Potential Nanoparticle [0125] A 0.2 g sample of Rhodamine B dye was added to 20 mL of a 20% w/w suspension of colloidal silica (SNOWTEX™ C), at pH 8.5. This mixture was stirred for about 20 min after which about 5 mL of dilute HCl was added to the suspension until the pH was reduced to about 3. A 0.2 g- sample of poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine] (PPMT, Aldrich Chemical Co. no. 41,324-0, CAS registry no. 82451-48-7) was added to this suspension of silica/Rhodamine B nanoparticles at pH 3, with stirring, whereupon the pH increased to about 7.3. Additional dilute HCl was added until the pH was reduced to 4.1. The zeta potential of the particles in this suspension was measured to be +35 mV after HCl addition, indicating protonation of the PPMT polymer. Example 16 Printing Cotton Fabric with a High Zeta Potential Magenta Nanoparticles [0126] A 3 inch by 1 inch swatch of plain, untreated cotton fabric (with a streaming potential of −23 mV) was dipped into the suspension of magenta nanoparticles prepared in Example 13 for about 10 sec, rinsed in cold water, and then dried under vacuum at ambient temperature. A smaller (about 1 inch by 2 inch) piece of colored fabric was cut from this sample and subjected to the AATCC 61-2A accelerated laundering test, by the ACTS Testing Labs (Buffalo, N.Y.). This test for evaluating colorfastness should show color change similar to that produced by five commercial launderings at 38�3� C. (100�5� F.) or by five home machine launderings at medium or warm setting in this same temperature range. The fabric sample was washed in 150 mL of water at 49� C. (120� F.) with 0.25% SYNTHRAPOL™ detergent, along with 50 (0.6 cm) steel ball bearings. Wash time was 45 min, in a canister being rotated at a rate of 40 rpm. The laundered sample was then washed with water and dried, and the ΔE* color change was measured as described above, as compared to an unlaundered sample. The ΔE* value was measured to be 5.3 for this sample, on a scale where a color change ΔE* value of 5 or less represents a color change that a human eye will not be able to detect as compared with the control sample. This measurement indicates that a zeta potential of +35 mV for the particle suspension is sufficient for this fabric with a streaming potential of −23 mV, to achieve good adhesion and durability. Example 17 Adsorption of a Non-Charged Polymer onto Cyan Dye-Coated Silica Nanoparticles, Followed by Protonation, to Achieve a High Zeta Potential Nanoparticle [0127] A 0.2 g sample of Victoria Blue BO cyan dye (Aldrich Chemical Co., Milwaukee, Wis.) was added to 50 mL of a 20% w/w suspension of colloidal silica (SNOWTEX™ C), at pH 8.5. This mixture was stirred for about 20 min after which dilute HCl was added to the suspension until the pH was reduced to about 4.5. A 0.30 g-sample of poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine] (Aldrich Chemical Co. no. 41,324-0, CAS registry no. 82451-48-7; abbreviated PPMT) was added to this suspension of silica/Victoria Blue BO nanoparticles, whereupon the pH increased to about 7.5. About 10 mL of additional dilute HCl was added until the pH was reduced to about 4.5. The zeta potential of this suspension was measured to be +30 mV after HCl addition, indicating protonation of the PPMT polymer. Example 18 Printing Cotton Fabric with a High Zeta Potential Cyan Nanoparticles [0128] A 3 inch by 1 inch swatch of plain, untreated cotton fabric (with a streaming potential of −23 mV) was soaked with the suspension of cyan nanoparticles prepared in Example 17, rinsed in cold water, and then dried under vacuum at ambient temperature. A smaller (about 1 inch by 0.5 inch) piece of colored fabric was cut from this sample and subjected to the AATCC 61-2A accelerated laundering test. The fabric sample was washed in 150 mL of water at 49� C. (120� F.) with 0.25% SYNTHRAPOL™ detergent, along with 50 (0.6 cm) steel ball bearings. Wash time was 45 min, in a canister being rotated at a rate of 40 rpm. The laundered sample was then washed with water and dried, and the ΔE* color change was measured as compared to an unlaundered sample. The ΔE* value was measured to be 1.3 for this sample, on a scale where a color change ΔE* value of 5 or less represents a color change that a human eye will not be able to detect as compared with the control sample. This measurement indicates that a zeta potential of +30 mV for the particle suspension is sufficient for this fabric with a streaming potential of −23 mV, to achieve strong adhesion and high durability. Example 19 Coating Melamine Resin Particles with Yellow Colorant And a Charged Polymer [0129] A 10 mL sample of 0.9 micron (μm) particles of poly(melamine formaldehyde) (Microparticles GmbH, Berlin) was prepared as a 2.5% wt/wt sample in water was titrated with 0.1 N HCl solution until the pH was lowered to 4.5. The change in pH of the suspension was monitored by performing the titration while the pH electrode was immersed therein. At pH 4.5, the zeta potential of the suspension was measured at +33 mV. This suspension was stirred while 0.1 g of yellow dye (CIBACRON� Yellow P-6GS) was added, after which the zeta potential was measured at −21 mV (at pH 4.5). After an additional 20 min of stirring, the PE(+) charged polymer, polyethyleneimine permethyl perbromide (Polysciences, Inc., Warrington, Pa., 1800 Mw molecular weight), was added (10 mL of a 10−2 M solution), after which the zeta potential was measured at +33 mV (at pH 4.5). Zeta potential measurements were taken using a Zetapals Instrument (Brookhaven Instrument Corporation, Holtsville, N.Y.), by adding 1-3 drops of sample into a cuvet containing 1 mM KCl solution, using the instrument's default functions preset for aqueous solutions. This Example indicates how poly(melamine formaldehyde) particles can be coated with a dye followed by a PE(+) charged polymer coating in order to achieve a positive nanoparticle zeta potential which results in strong adhesion to fabric with a negative streaming potential, and thereby providing high durability of print. Example 20 Coating Melamine Resin Particles with Multiple Colorant and Polyelectolyte Coatings [0130] Melamine resin particles (poly(melamine formaldehyde)) (Microparticles GmbH, Berlin) were suspended in water and titrated with 0.1 N HCl solution until the pH was lowered to 3.7. This suspension was stirred with rhodamine B dye at pH 3.7 to coat the particles, after which the zeta potential of the suspension was measured at +32 mV. This suspension was then stirred while the yellow dye CIBACRON� Yellow P-6GS was added, after which the zeta potential was measured at −24 mV, and the suspension was characterized by an orange color. The PE(+) charged polymer, polyethyleneimine permethyl perbromide (Polysciences, Inc., Warrington, Pa., 1800 Mw molecular weight) was then added, after which the zeta potential was measured at +28 mV. After about 1 hr, the orange particles had settled to the bottom of the flask, indicating that the dyes were adsorbed onto the poly(melamine formaldehyde) particles, and were not in solution. Example 21 Coating Melamine Resin Particles with Multiple Colorant and Charged Polymer Coatings [0131] Melamine resin particles (poly(melamine formaldehyde)) (Microparticles GmbH, Berlin) were suspended in water and titrated with 0.1 N HCl solution until the pH was lowered to 3.7. This suspension was stirred with Rhodamine B dye at this pH to coat the particles, after which the zeta potential of the particles in suspension was measured at +32 mV. This suspension was then stirred while Acid Red 52 dye was added, forming a deep magenta color, after which the zeta potential was measured at −20 mV. Additional Acid Red 52 was added, forming a suspension with a deeper magenta color, and characterized by a zeta potential of −23 mV. To this suspension was added the polytriazine copolymer, poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine] (Aldrich Chemical Co. No. 41,324-0, CAS registry no. 82451-48-7; abbreviated PPMT), followed by acidification with 0.1 N HCl, whereupon the zeta potential was found to be +44 mV. Example 22 Coating Melamine Resin Particles with Multiple Colorant and Charged Polymer Coatings [0132] Melamine resin particles (poly(melamine formaldehyde)) (Microparticles GmbH, Berlin) were suspended in water and titrated with 0.1 N HCl solution until the pH was lowered to 3.7. This suspension was stirred with Nile Blue stain at this pH to coat the particles, after which the zeta potential of the suspension was measured at +10 mV, and the suspension was pale blue in color. This suspension was then stirred while CIBACRON� Yellow P-6GS dye was added, forming a green suspension color, after which the zeta potential was measured at -30 mV. To this suspension was added poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino -1,3,5-triazine] (Aldrich Chemical Co.), followed by acidification with 0.1 N HCl, to bring the pH back to 3.7, whereupon the zeta potential was found to be +44 mV. After about 1 hr, the green particles had settled to the bottom of the flask, showing adsorption of the dyes to the particle surface. Example 23 Preparation of a Polyelectrolyte Coated Alumina Nanoparticles [0133] A sample of ALUMINASOL™ 100 (Nissan Chemical America Corporation) was diluted from 10% to 1% wt/wt in 1 mM aqueous KCl. The zeta potential of this suspension was measured at +63 mV. This suspension was stirred while 20 ml of a 0.1 M solution of poly(vinyl sulfonic acid, sodium salt) (1800 Mw molecular weight) was added. The suspension was stirred for another 40 min, after which time the zeta potential was measured to be +10 mV, indicating the alumina sol can serve as a template. Example 24 Preparation of Polyelectrolyte-Dye-Coated Silica Nanoparticles using Alternately Charged Polyelectrolytes, and Zeta Potential Measurements of the Resulting Particles [0134] A polyelectrolyte-dye solution was first prepared as follows. A 20 mL sample of 10−2 M polyethyleneimine permethylated perbromide polyelectrolyte (1800 MW) was stirred while a 0.022-gram sample of acid red 52 (AR52) was added at room temperature. Thus, 0.2 mmol of PE(+) polyethyleneimine permethylated perbromide was treated with 0.04 mmol of dye, meaning that 20% of the sites are occupied with the dye. If this resulting solution is dialyzed with 2000 MW cut off dialysis bags, no dye was observed outside the bag after 16 hr of dialysis, indicating a strong dye-charged polymer complex had formed. This 20 mL sample of polyelectrolyte-dye solution was added to 200 mL of a 0.01% wt/wt suspension of 9-14 nm silica nanoparticles at pH 8.5 and 1M in NaCl. The resulting suspension was stirred for 40 mins at room temperature. This suspension was then stirred overnight against a pH 8.5/1M NaCl solution using 2000 MW cut off dialysis bags. The contents of the dialysis bag were then treated with 20 mL of a 10−2 M poly(vinyl sulfonic acid, sodium salt) solution (1800 MW) for 40 min at room temperature. The resulting suspension was then dialyzed overnight, as before, with a 2000 MW cut off dialysis bag. Both layering steps could then be repeated if desired to build up layers on the silica nanoparticle. In addition, this process can be performed with up to 1% wt/wt silica nanoparticles and 0.1 M PE(+) polyethyleneimine permethylated perbromide polyelectrolyte. Zeta potentials were measured for the nanoparticle itself, and following subsequent layering of polyelectrolyte(+)-dye, (void) polyelectrolyte(−), and polyelectrolyte(+)-dye, as shown in Table 2. The zeta potential data in Table 2 reflect measurements using magenta, yellow, and cyan dyes in separate experiments, although clearly different dyes can be used on the same nanoparticle to provide specifically tailored colors. Example 25 Effect of Nanoparticle Zeta Potential on Durability [0135] The AATCC 61-2A test for evaluating colorfastness was used to evaluate and compare the durability of various colored nanoparticles on a single fabric. The AATCC 61-2A test shows color change comparable to five commercial launderings at 38�3� C. (100�5� F.) or by five home machine launderings at medium or warm setting in this temperature range. A cotton sample printed with various colored nanoparticles was washed in 150 mL of water at 49� C. (120� F.) with 0.25% SYNTHRAPOLT detergent, along with 50 (0.6 cm) steel ball bearings. Wash time was 45 min, in a canister being rotated at a rate of 40 rpm. The laundered sample was then washed with water and dried, and the loss of color, ΔE* was measured according to AATCC 61-2A. Samples that were measured with a ΔE* on a scale where a color change ΔE* value of 5 or less represents a color change that a human eye will not be able to detect as compared with the control sample. The grade ratings were determined through use of the AATCC Gray Scales for Color Change and Staining. Table 4 records the results of the AATCC 61-2A accelerated laundering test for various fabric samples and colorants of the present invention. In Table 4, the following abbreviations are used: SNC is SNOWTEX™C; PE(+) is polyethylenimine, permethylated, perbromide (MW=1800, Polysciences, Warrington, Pa.); PE(−) is poly(vinylsulfonic acid, sodium salt) MW=2000, Polysciences, Warrington, Pa.); AR52 is acid red 52 dye; RhB is rhodamine B dye; MR is melamine formaldehyde particles, comprising poly(melamine formaldehyde) resin. The nanoparticle core and the order of layering is indicated by the sequence as presented in the table. The dramatic differences shown in this table indicate the importance of zeta potential of the nanoparticle in providing enhanced durability. TABLE 4 Effect of Nanoparticle Zeta Potential on Durability Measured by AATCC-61-2A Zeta Potential ΔE*, Loss of Color on Nanoparticle (mV) Laundering (Cotton) SNC/PE(+)-AR52 −28 49.0 SNC/PE(+)-AR52/PE(−)/ −24 43.8 PE(+)-AR52 SNC/PE(+)-PE(−)-RhB/ −20 37.4 PE(+) SNC/PhB −10 12.0 MR/PhB +42 5.7 MR/RhB +78 1.3 Example 26 Colorfastness Testing of Fabrics Printed with Nanoparticle Ink [0136] A variety of fabrics were printed using nanoparticle inks of the present invention, and colorfastness and printability tests were conducted on the resulting printed fabrics. Table 5 records the data obtained in these tests. The particular colorfastness tests used are indicated, where AATCC is the American Association of Textile Chemists and Colorists, and ACTS is the ACTS Testing Laboratory, Buffalo, N.Y. These tests were performed at the ACTS Testing Laboratory on fabrics printed with a suspension of magenta melamine resin nanoparticles. The colorfastness gray scale method used to judge these tests ranges from 1 to 5, with 3 and higher deemed passing (no detectable change). TABLE 5 Colorfastness Testing of Fabrics Printed with Nanoparticle Ink Test and Method Cotton Nylon Silk Printability Pass Pass Pass Colorfastness to Water (AATCC 107) 4 3.5 4 Colorfastness to Perspiration (AATCC 5 4 5 15) Colorfastness to Accelerated Laundering 3.5 3.5 3.5 (AATCC 61-2A) Colorfastness to Chlorine Bleach 3.5 3.5 3.5 (ACTS Method TX-006) Colorfastness to Non-Chlorine Bleach 4.5 4.5 3.5 (ACTS MEthod TX-011) Colorfastness to Crocking (AATCC 8) Example 27 Comparison of Colorfastness Testing of Fabrics Printed with Standard Inks versus Nanoparticle Inks [0137] In this test, both coated cotton and uncoated cotton were utilized as substrates to compare colorfastness of the nanoparticle ink of the present invention with standard inks that do not employ nanoparticle technology. The coated cotton was post treated with steam, followed by rinsing, and this “improved” substrate was treated with a standard magenta ink. The standard colorant treatment was a Kimberly-Clark medium red (magenta) ink, prepared using the following formulation in Table 6. TABLE 6 Formulation for Standard Magenta Ink for Comparison Testing Ink Component Weight % Supplier DI water 82.0 — Versene � 100XL 0.6 Dow Chemical Co., Midland Michigan EDTA�2Na 0.3 Dow Chemical Co., Midland Michigan N-methylmorpholine-N- 3.0 Aldrich Chemical Co., Milwaukee, oxide Wisconsin Glycerine 3.5 Aldrich Chemcial Co., Milwaukee, Wisconsin PEG-400 5.0 Aldrich Chemcial Co., Milwaukee, Wisconsin Proxel � GXL 0.3 Zenneca Corp., Wilmington, Delaware Corbratec � Soln 0.3 PMC Speciality Group, Cincinnati, Ohio Surfynol � 504 0.1 Air Products, Allentown, Pennsylvania Surfynol � 465 0.2 Air Products, Allentown, Pennsylvania Reactive Dye RM 7034, 4.7 Ciba Specialty Chemicals Corp., Cibacron � Red P-6B Highpoint, North Carolina Total 100.0 [0138] The nanoparticle colorant was a suspension of magenta melamine resin nanoparticles, and was applied to an uncoated cotton fabric that employed no post treatment. Table 7 records the results of these tests, which reveal that even unimproved substrates with nanoparticle inks perform better than improved substrates with standard inks. The colorfastness gray scale method used to judge these tests ranges from 1 to 5, with 3 and higher deemed passing (no detectable change). TABLE 7 Comparison of Colorfastness Testing of Fabrics Printed with Standard Ink versus Nanoparticle Ink Standard Nanoparticle Test and Method Ink Ink Substrate coated cotton uncoated cotton Post treatment steam + rinse None Printability Pass Pass Colorfastness to Water (AATCC 107) 4.5 4.5 Colorfastness to Perspiration 4.5 4.5 (AATCC 15) Colorfastness to Accelerated 1.5 3 Laundering (AATCC 61-2A) Colorfastness to Chlorine Bleach 4.5 4.5 (ACTS Method TX-006) Colorfastness to Nom-Chlorine Bleach 3 4.5 (ACTS Method TX-011) Colorfastness to Crocking (AATCC 8) N/A 4 Example 28 Effect of Fabric on the Durability of Nanoparticle Inks [0139] The durability of the inks of the present invention when applied to various fabrics was tested, in order to ascertain the effect of the choice of fabric. As shown in Table 8 below, all the fabrics tested were measured as having negative streaming potentials, while the melamine resin nanoparticles were measured with a positive zeta potential. Both a magenta melamine nanoparticle, and a cyan melamine resin nanoparticle of the present invention were employed in this study. Durability is measured as both colorfastness to accelerated laundering (AATCC 61-2A test) and as colorfastness to crocking (AATCC 8). The colorfastness gray scale method used to judge these tests ranges from 1 to 5, with 3 and higher deemed passing (no detectable change). TABLE 8 Effect of Fabric on the Durability of Nanoparticle Inks Durability Colorfastness to Streaming Accelerated Laundering Crocking Potential (AATCC 61-2A) (AATCC 8) Fabric (mV) Magenta Cyan Magenta Cyan Cotton −21 3.5 3 4 4.5 Nylon −32 3.5 3.5 3 3 Silk −26 3.5 3.5 3.5 4 Polyester −20 — 3.5 — 3.5 Example 29 Preparation of Colored Nanoparticles Using Different Dyes to Obtain Unusual Colors [0140] One feature of the present invention is the ability to prepare nanoparticle colorants with unusual or hard-to-obtain colors. Thus, when adsorbing each layer onto the nanoparticle template, each charged polymer layer can employ a different dye for fine tuning colors. Thus, silica nanoparticles were coated with a PE(+)/Acid Red 52 layer to yield magenta nanoarticles, which were subsequently coated with a PE(+)/cyan layer to afford lilac colored nanoparticles. The cyan colorant used was copper phthalocyanine, tetrasulfonic acid, sodium salt. Thus, by mixing layers of color in this fashion, a uniform ink/dye system of unusual color can be prepared. This result is to be contrasted to simple mixtures of colorants or dyes that would not result in a similarly true color, but rather the hues of the component dyes. Example 30 Preparation and Utility of a Surface Modifying Ink Jet Ink Containing Nanoparticles [0141] Silica nanoparticles ( SNOWTEX™ C, Nissan Chemical) were treated with polyvinylpyrrolidone (Mw 10,000) in an aqueous suspension at pH 8.5 and 1 M in NaCl, for a period of 2 hours. The zeta potential of the nanoparticles changed from −34 mV to −10 mV and the nanoparticle size changed from 10 nm to 25 nm as a direct result of the adsorption of the polyvinylpyrrolidone onto the silica nanoparticle. Excess polyvinylpyrrolidone was removed by dialysis against a 1 M NaCl solution at pH 8.5 for 16 hours, with a 20,000 MW cut off. The resulting suspension of modified nanoparticles was drawn down onto a sheet of Neenah bond paper. When this paper was allowed to dry, it was observed to have a high gloss. This example demonstrates that nanoparticle technology may be used in an inkjet system for surface modification of a substrate. This example differs from others in this disclosure in that the ink used for surface modification is not colored. [0142] Further discussion of nanoparticles may be found in U.S. patent application Ser. No. ______, entitled, “Recording Medium with Nanoparticles and Methods of Making the Same”, by R. S. Nohr, J. G. MacDonald and B. Kronberg, filed contemporaneously herewith. [0143] It should be understood, of course, that the foregoing relates only to certain embodiments of the present invention and that numerous modifications or alterations may be made therein without departing from the spirit and the scope of the invention. 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Happiness. Joy. Handprinted canvas bookmark by Baisimu on Etsy
Pets in group Rubber stamp/ handmade stamp/ hand carved/ custom made/ customized/ dog stamp/ bunny stamp/ dogs stamp/ bunnies/ cute...
Couple name wedding stamp stamp/ leafy/ floral border/ hearts/ love/ customized wedding stamp/ custom wedding gift/ round stamp/ garden love...
Customized Chinese stone seal (Square)...
Customized portrait cartoon caricature rubber stamp...
Customised Chinese name Rubber stamp...
Description:This bookmark is made out of canvas with the sides sewn in and exposed on the back for a natural and rustic look. The boundaries are sewn with complementing pure white thread to give it a sleek finish.The handprinted impression is Baisimu's logo, which could be translated into "happiness" or "joy". It is finished with clear acrylic coating so you don't have to worry about it coming off. Use it to mark your pages in style!Dimensions:Bookmark measures 2.6" across and 5.6" down.Additional Information:These canvas bookmarks are a result of my attempt to reduce wastage! They are made using the little canvas pieces remaining from my other sewn crafts, and as a result each of them has got a different size and are unique and one of a kind! For more bookmarks, please visit http://www.etsy.com/shop/Baisimu?section_id=7067797 Thanks for browsing! Meet the owner of Baisimu
Happiness. Joy. Handprinted canvas bookmark
Ships worldwide from SingaporeFeedback: 222 reviewsFavorited by: 4 people
Pets in group Rubber stamp/ handmade stamp/ hand carved/ custom made/ customized/ dog stamp/ bunny stamp/ dogs stamp/ bunnies/ cute
Customized portrait cartoon caricature rubber stamp

value: This website is an American e-commerce company focused on handmade or vintage items and craft supplies.