text:
Patent US4539263 - Blends of ionomer with propylene copolymer and articles - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsBlends of (a) 80-93 weight percent of an ethylene/acid ionomer, and (b) 7-20 weight percent of a propylene/α-olefin copolymer are used to prepare peelable seals having nearly constant and predictable peel strength over an extended heat seal temperature range. Some of the seals so produced also show...http://www.google.com/patents/US4539263?utm_source=gb-gplus-sharePatent US4539263 - Blends of ionomer with propylene copolymer and articlesAdvanced Patent SearchPublication numberUS4539263 APublication typeGrantApplication numberUS 06/613,375Publication dateSep 3, 1985Filing dateMay 23, 1984Priority dateAug 22, 1983Fee statusPaidPublication number06613375, 613375, US 4539263 A, US 4539263A, US-A-4539263, US4539263 A, US4539263AInventorsGeorge L. HohOriginal AssigneeE. I. Du Pont De Nemours And CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (22), Non-Patent Citations (1), Referenced by (39), Classifications (21), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetBlends of ionomer with propylene copolymer and articles
US 4539263 AAbstract
Blends of (a) 80-93 weight percent of an ethylene/acid ionomer, and (b) 7-20 weight percent of a propylene/α-olefin copolymer are used to prepare peelable seals having nearly constant and predictable peel strength over an extended heat seal temperature range. Some of the seals so produced also show stress whitening.
1. Coextrusions for producing film characterized by a nearly constant peel strength over an extended heat seal temperature range, made from a molecular blend of polymeric materials comprising:(a) 80-93 weight percent of an ethylene/acid ionomer, and (b) 7-20 weight percent of a propylene/α-olefin copolymer, wherein the α-olefin comprises 1-12 weight percent of the copolymer, and wherein said coextrusion further comprises at least one extrudable material other than said molecular blend. 2. Laminates made from the coextrusions of claim 1.
3. Laminates characterized by a nearly constant peel strength over an extended heat seal temperature range, made from a molecular blend of polymeric materials comprising:(a) 80-93 weight percent of an ethylene/acid ionomer, and (b) 7-20 weight percent of a propylene/α-olefin copolymer, wherein the α-olefin comprises 1-12 weight percent of the copolymer, and wherein said laminate further comprises a substrate other than said molecular blend. 4. Packages having peelable seals characterized by a nearly constant peel strength over an extended heat seal temperature range made from a molecular blend of polymeric materials comprising:(a) 80-93 weight percent of an ethylene/acid ionomer, and (b) 7-20 weight percent of a propylene/α-olefin copolymer, wherein the α-olefin comprises 1--12 weight percent of the copolymer. Description
This is a division of application Ser. No. 525,505 filed Aug. 22, 1983.
This invention relates to blends of an ionomer with a propylene/α-olefin copolymer, to heat-sealable films and/or laminates made from such blends, and to flexible film packages made from such films and/or laminates. Seals produced from such heat-sealable films and/or laminates are characterized by a nearly constant peel strength over an extended heat seal temperature range and by being peelable (i.e. having the seal failure occur) primarily at the interface of the sealing surfaces) rather than film-tearing. The blends, films and/or laminates of the present invention permit the manufacture of a more consistent finished product, i.e. a heat-sealed flexible film package having a seal of predictable and constant peel strength, in spite of inevitable variations in the heat seal temperature used in the production of such packages.
Further, some of the seals produced using the blends of the present invention will be characterized by stress whitening, i.e. when stress is applied to the seal, either by peeling in the normal fashion or by an attempt to tamper with the seal, the film and/or laminate will change from a clear appearance to a cloudy or white appearance.
U.S. Pat. No. 4,346,196, granted Aug. 24, 1982 to Hoh et al., discloses 80/20-20/80 blends of an ionomer dipolymer with an ionomer terpolymer and the use of such blends in the production of heat-sealable films for use in flexible film packages to create both tearable and peelable seals in the flexible film package. Hoh et al. does not use an ethylene/α-olefin copolymer in the blend, and while Hoh et al. does disclose that suitable heat seals can be achieved over a broad temperature range, the strength of such seals is temperature dependent.
U.S. Pat. No. 4,279,344, granted July 21, 1981 to Holloway, discloses blends of an ionomer with a propylene/α-olefin copolymer and the use of such blends in the preparation of heat sealable films for use in laminated packaging structures to create peelable seals. Holloway, however, discloses blends that are high in the propylene/α-olefin copolymer (i.e. at least 65 weight percent) and low in the ionomer (i.e. at most 35 weight percent). In addition, Holloway declares his objective to be the creation of peelable seals of moderate strength that can tolerate temperatures necessary for retort sterilization (i.e. about 250� F.). Such is not the objective of the peelable seals of the present invention, which, in fact, are not retortable. In addition, Holloway's blend requires a seal temperature of about 450� F., which is much higher than what would be used with the blends of the present invention.
U.S. Pat. No. 3,819,792, granted June 25, 1974 to Ono et al., discloses blends C-2 or C-3 olefin homopolymer or copolymer with ethylene/methacrylic acid ionomer that can be high in ionomer, but only up to a maximum of 70 weight percent. Ono discloses such blends as being useful in the production of double wall tubing. No mention is made of possible use in heat sealable film.
This invention relates to blends of an ionomer with a propylene/α-olefin copolymer, to heat-sealable films and/or laminates made from such blends, and to flexible film packages made from such films and/or laminates. Seals produced from such films and/or laminates are characterized by a nearly constant peel strength over an extended heat seal temperature range, by being peelable (rather than film tearing), and by showing stress whitening, at least in some instances. By "nearly constant" there is meant a peel strength that varies not more than �2.5 g/mm, and by "extended" there is meant a temperature range of at least 10� C. Certain of the compositions of the present invention are also capable of being used to prepare fusion or film-tearing seals by substantially increasing the heat sealing temperature. Thus, a package can be prepared from films or laminates from such compositions, which packages will exhibit a peelable seal in one area of the package and a fusion seal in another. Such packages can be used in packaging snack foods and disposable medical products.
In particular, the blends of the present invention comprise 80-93 weight percent of an ethylene/acid ionomer and 7-20 weight percent of a propylene/α-olefin copolymer, preferably 88-92 weight percent ionomer and 8-12 weight percent propylene/α-olefin copolymer.
The ionomers used in the blends of the present invention can be dipolymer or terpolymer ionomers such as described in U.S. Pat. Nos. 3,264,272; 3,404,134; and 3,355,319. When the ionomer is a dipolymer, the acid monomer should be greater than 12 but not more than 25 weight percent of the ionomer, preferably 13-18 weight percent and most preferably 14-16 weight percent. When the ionomer is a terpolymer the third monomer should be from 5-25 weight percent of the ionomer, preferably 6-20 weight percent and most preferably 8-15 weight percent. The acid monomer in the ionomer should be 5-45% neutralized with a mono- or divalent metal ion, preferably 10-30% and most preferably 15-25%, and the ionomer should be characterized by a melt index (measured according to ASTM D-1238, condition E) prior to neutralization of 1-100 g/10 minutes preferably 3-25 g/10 minutes and most preferably 5-20 g/10 minutes. The metal used for neutralizing the ionomer can be selected from those disclosed in the three U.S. patents cited above in this paragraph, and those patents are hereby incorporated herein by reference.
Suitable acid monomers include monoethylenically unsaturated monobasic acids having 3-8 carbon atoms such as acrylic, methacrylic, ethacrylic, itaconic, alkyl hydrogen maleic or fumaric acids. Preferred acid monomers include acrylic and methacrylic acid because they are thermally stable and commercially available. Other monomers suitable for use in the preparation of the terpolymer include monoethylenically unsaturated copolymerizable monomers such as those disclosed in U.S. Pat. No. 4,321,337 at column 4, lines 28-44, which description is hereby incorporated herein by reference. (Meth) acrylate esters are preferred, with isobutyl acrylate being most preferred because of thermal stability and adhesion considerations. Suitable mono- and divalent ions for neutralization of the acid in the ethylene/acid ionomer include ammonium, lithium, sodium, potassium, calcium, magnesium and zinc, preferably sodium and zinc, with zinc being most preferred because of its superior adhesion characteristics. Mixtures of more than one acid comonomer and/or more than one other monomer can also be used in the preparation of the ionomer. Neutralization of the acid in the ionomer can be achieved during preparation of the ionomer or during preparation of the ionomer/copolymer blend, thereby eliminating a separate neutralization step. Similarly, the degree of neutralization of the acid in the ionomer can be adjusted to the proper range by blending more highly neutralized ionomer with an appropriate amount of unneutralized or partially neutralized corresponding acid copolymer.
Blends of two acid copolymers, including terpolymers can be used as base resins for neutralization.
The propylene/α-olefin copolymer should contain 1-12 weight percent α-olefin monomer, preferably 2-8 weight percent and most preferably 3-5 weight percent, to promote a balance of seal characteristics, including seal strength and fusion or no fusion, and the melt flow rate (MFR) (as measured by ASTM D-1238, condition L) of this copolymer should be at least 4 g/10 minutes. Suitable α-olefin comonomers include ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 3-methylbutene-1, and 4-methylbutene-1, preferably ethylene and butene-1, with ethylene being most preferred because of low cost and commercial availability of such copolymers. Mixtures of copolymers can also be used.
The ethylene/acid ionomer and the propylene/α-olefin copolymer are blended to form a molecular blend (i.e. an intimate admixture). The blend can be prepared by any of the common methods for blending polymeric materials. For example, solutions of the individual polymeric materials can be prepared, mixed with each other, and the solvent can be subsequently removed; the individual polymeric materials can be mixed with each other in molten form, e.g. by melt blending in an extruder; or the individual polymeric materials can be blended with each other in a high shear mixing device, e.g. a two-roll mill or a Banbury mixer. Preferably, the individual polymeric components will be melt blended with each other in an extruder and formed by melt extrusion, flat die extrusion, blown film extrusion or any other technique that will produce the desired shape. The blends of the present invention can be prepared as self-supporting films, as coextrusions, as laminates for film substrates or as coatings for conventional flexible packing materials, including films, foils, paper and webs. Materials of construction for such films, foils, papers and webs include organic polymers, metal foils, bleached and unbleached papers and board, glassine, non-woven fabrics, and composites of such materials. The blends of the present invention are particularly well suited for use with substrates made from polyolefin resins such as high density polyethylene and oriented polypropylene. When used as a laminate or coating, the blends of the present invention can be applied over the entire substrate or over only that portion of the substrate to be sealed.
The blends of the present invention may also include minor amounts of antioxidants, slip agents, antiblocking agents, antifogging agents, antistats and other additives as may be commonly used in the preparation of polymeric compositions used in the preparation of heat sealable films and/or laminates (see, e.g. Fatty Amides by Arthur L. McKenna, Witco Chemical Corp. 1982, or "Modern Plastics Encyclopedia").
In the process of form-fill-seal packaging, a film is formed around a mandrel, sealed along the vertical seam, sealed along the bottom, filled with the package contents and sealed along the top, all this while the film is sliding over the mandrel. In this operation, it is necessary that the surface contacting the mandrel have an adequate degree of slip. Depending on the packaging machine used, the degree of slip necessary can be a coefficient of friction (C.O.F.) of 0.4 or lower, as measured by test method ASTM D-1894C. To achieve this level of C.O.F., it is usually necessary to add slip and/or antiblock additives to the compositions of this invention. Some types of antiblock additives are inorganic materials of fine particle size, such as silica or talc. Antiblocking properties and slip properties may also be conferred by organic additives, as discussed in "Fatty Amides" cited above. Several types of amides are discussed, such as primary amides, secondary amides, and bisamides. Secondary amides and bisamides are more effective additives for compositions containing ionomers. Examples of slip-modified ionomers are shown in U.S. Pat. Nos. 3,474,063, 3,595,827; 3,597,382; 3,821,179; and Def. Publ., U.S. Patent Office 877,077 (August 1970). It should also be noted that the quantity of fatty amide required to produce a given level of C.O.F. is inversely dependent on the thickness of the film layer containing the additive.
In the preparation of heat sealed flexible packages, it is generally preferred that the strength of the seal be such that rupture of the seal occurs within the heat sealable composition at the interface of the seal layers, rather than within the substrate, i.e. it is generally preferred that such seals be peelable, rather than film tearing. Whether a particular seal will be peelable will depend on the strength of the seal as compared with the strength of the substrate. Accordingly, it is important to be able to control the strength of the seal. With certain compositions, such as those disclosed in U.S. Pat. No. 4,346,196, the strength of the seal depends on the temperature at which the seal is prepared, i.e. the higher the sealing temperature, the higher the strength of the seal. Accordingly, the strength of seals prepared from such compositions can be controlled by controlling the sealing temperature.
Unfortunately, it is not always easy or even practical to precisely control the sealing temperature, particularly on commercial packaging equipment. Sealing temperature variations can result from variations in ambient temperature, thickness of the substrate, thickness of the coatings, throughput of the packaging material, interruptions of the production line, etc.
As will be seen in the Examples that follow, the blends of the present invention will produce seals having a nearly constant peel strength over extended heat seal temperature range. This can be represented graphically by plotting the peel strength vs. the sealing temperature for each composition. The blends of the present invention will exhibit a plateau at a peel strength well within the peelable range. As will also be shown in the Examples and the accompanying graphs, if one desires a film tearing seal, it is possible to achieve this result with certain of the compositions of the present invention by substantially raising the sealing temperature beyond the plateau region in the graphs. However, one of the unique features of the blends of the present invention is the plateu region, which permits one to achieve substantially constant peel strength over a wide range of sealing temperature. Accordingly, the blends of the present invention will most often be used in this plateau region.
It will also be demonstrated in the following Examples that some of the blends of the present invention will produce seals that show stress whitening. Seals that show stress whitening can be produced only above certain seal temperatures, but such temperatures are at or below the plateau region described above, thus permitting the production of seals that are peelable (with predictable and constant peel strength) and will show evidence of tampering.
All of the Figures are graphs based on data obtained from experiments described in detail in the Examples. In each case, the abscissa represents the temperature measured at the seal layer interface temperature in �C. and the ordinate represents the seal strength in g/mm. (Values for seal strength were originally measured in g/in and then converted to S.I. units. The values in g/in are shown in parentheses.) These graphs make it quite easy to observe the plateau region which characterizes the blends of the present invention, and the lack of a plateau region for compositions outside the scope of the present invention, including compositions representative of some of the prior art. In each of the Figures, open symbols represent seals which failed at the seal layer interface, closed symbols represent film-tearing seals, and half-closed symbols represent the point where onset of stress whitening occurs.
FIG. 1 represents the data obtained from experiments on a blend of the present invention as described in Example 1.
FIG. 2 represents the data obtained from experiments on a control blend (where the ionomer contains only 9% acid) as described in Example 2.
FIG. 3 represents the data obtained from experiments on a control blend (where the ionomer contains 12% acid) as described in Example 3.
FIG. 4 represents the data obtained from experiments on a control composition (containing only ionomer, no propylene/α-olefin copolymer) as described in Example 4.
FIG. 5 represents the data obtained from experiments on a control blend (where propylene homopolymer was used instead of propylene/α-olefin copolymer) as described in Example 5.
FIGS. 6-9 represent the data obtained from experiments on various blends (where the percent of propylene/α-olefin copolymer in blends with ionomer is varied from 5 to 20%) as described in Examples 6-9.
FIG. 10 represents the data obtained from experiments on control blends (where the MFR of the PP/E resin is outside the scope of the present invention) as described in Examples 12-14.
In each of the following Examples, all parts and percentages are by weight and all temperatures are in �C. unless specified otherwise. Measurements not originally in SI units have been so converted and rounded where appropriate. All seals tested were prepared in a "Sentinel" heat sealer having two heated jaws, both 25.4 mm wide, the lower jaw being covered with a 10 mm thickness of silicone rubber. Two layers of Teflon�-coated glass cloth were interposed between each heated jaw and the film samples. Additionally, film samples were transported with a holder made of the same type Teflon�-coated glass cloth. The air pressure to the jaw activation pistons was set at 276 kPa, and the dwell time of the jaws in the closed position was set for three seconds. The maximum temperature of the interface of the film heat-seal surfaces was determined using a fine wire thermocouple with fast response recorder. Seal strength was determined by peeling apart the seal in an "Instron" tensile tester at a jaw separation rate of 127 mm/min., the "tail" of the sample being allowed free movement. As indicated above, data for several of the Examples is displayed graphically in the accompanying Figures. Wherever such data is reported the melt index (MI) of the acid copolymer was determined according to ASTM D-1238, condition E, and the melt flow rate (MFR) of the propylene copolymer was determined according to ASTM D-1238, condition L.
Three thousand six hundred grams of an ethylene/methacrylic acid (MAA) ionomer were dry blended with 400 g of a propylene/ethylene copolymer. The acid copolymer for the ionomer contained 15 wt. % methacrylic acid and had a melt index of 60 g/10 minutes. Zinc was used to neutralize 22% of the acid groups. The resulting ionomer had a melt index of 14 g/10 minutes. The propylene/ethylene copolymer had an ethylene content of 3 wt.% and a melt flow rate of 5 g/10 minutes. A uniform mixture of pellets of each of these polymers was fed to a 28 mm Werner and Pfleiderer corotating twin-screw extruder equipped with screws having a severe mixing profile. A melt temperature of 247� C. was obtained at a throughput rate of 12.7 kg./hr. Strands of the melt-blended material were quenched in an icewater bath and then cut into pellets. The melt index of the blend was determined to be 13.6 g/10 minutes.
Blown film of 0.05 mm thickness and 127 mm lay flat width was prepared using a "Brabender" 19 mm diameter single screw extruder equipped with a 25.4 mm blown film die. The melt temperature attained was 197� C. Seals were prepared and tested as described above. A plot of peel strength vs. seal interface temperature is shown in FIG. 1. Note that a long plateau of nearly constant seal strength was obtained. Between 90� and 114� C., peel strength remains between 23.6 and 27.6 g/mm. At this level of seal strength, seal failure was at the interface of the sealing surfaces. At strengths above 31.5 g/mm, which were obtained at a temperature of 119� C., the sealed film tore on attempted peeling. In addition, at sealing temperatures/seal strengths about 73� C./10.8 g/mm, the peeled sample exhibited blushing or whitening. Thus, seals made above these conditions would show evidence of tampering.
EXAMPLE 2 CONTROL BLEND WITH LOW MAA
This experiment was carried out in a manner identical to that of Example 1, except the acid copolymer contained 9% MAA, and it was neutralized 18% with zinc to give an ionomer with melt index of 5 g/10 minutes. The blend had melt index of 4.7 g/10 minutes. Unlike the blend of Example 1, 0.05 mm film from this blend does not exhibit a plateau of seal strength, but tears at a low strength of 27.6 g/mm, as shown in FIG. 2.
EXAMPLE 3 CONTROL BLEND WITH BORDERLINE MAA
This experiment was carried out in a manner identical to that of Example 1, except the acid copolymer contained 12% MAA, and it was neutralized 38% with zinc to give an ionomer with melt index of 1.6 g/10 minutes. The blend had melt index of 1.6 g/10 minutes. A heat seal profile of 0.05 mm film from this blend is shown in FIG. 3. A short plateau of seal strength between 17.7-21.6 g/mm over a temperature range of 88�-95� C. is shown in FIG. 3.
EXAMPLE 4 CONTROL WITH ONLY IONOMER
This experiment was carried out in a manner identical to that of Example 1, except that no propylene/α-olefin copolymer was used. The lack of a seal strength plateau is shown in FIG. 4. In addition, the seals did not blush upon peeling.
EXAMPLE 5 CONTROL BLEND WITH PROPYLENE HOMOPOLYMER
This example was carried out in a manner identical to that of Example 1, except a propylene homopolymer having a melt flow rate of 2.8 g/10 minutes was used. A blend melt index of 15.0 g/10 minutes was obtained. As can be seen from FIG. 5, a heat seal plateau was not obtained, although seals formed at 83� C. and above blushed on peeling. Fushion bonds were formed at 87� C. and above.
These experiments were carried out in a manner identical to that of Example 1, except that the proportion of ionomer and polypropylene/ethylene copolymer was varied as shown in the Table below. Example 6 shows a control blend with a low proportion of PP/E copolymer. Examples 7, 8 and 9 show blends of the present invention, with Example 9 at the 20% limit for PP/E.
______________________________________  Ionomer             Blend MI                              Heat SealExample  Wt. %    PP/E Wt. % (g/10 min)                              Profile, FIG.______________________________________6      95        5         16.9    67      92        8         13.2    78      88       12         12.2    89      80       20         13.8    9______________________________________
As can be seen from FIG. 6, when only 5% PP/E copolymer is blended with 95% ionomer, no plateau is obtained. As shown in FIGS. 7-9, with increasing amounts of PP/E in the blend, the level of seal strength in the plateau region decreased, until at 20%, the peel strength plateau was in the 5.1 to 6.7 g/mm range, which is near the lower limit of peel strength generally required for most uses.
To determine the effect of temperature and shear in the melt mixing step on the seal profile of film, a dry blend of the polymers used in Example 1 was fed to an 88.9 mm diameter "Davis" single screw extruder equipped with a mixing screw. Two sets of processing conditions were used. In the first, the extruder was operated at 6 rpm and the product melt temperature was 176� C. The product had a melt index of 10.0 g/10 minutes. This single screw extruder imparted less shear to the polymer than did the twin screw extruder used in Example 1. A heat seal profile of seals from this blend prepared as described in Example 1 shows a plateau of about 13.8 g/mm over a seal interface temperature range of 90� to 122� C. Seal strength rose to 27.6 g/mm at a seal temperature of 142� C., but a fusion bond was not obtained. This set of mixing conditions thus gave a film with a plateau seal strength 54% of that obtained in Example 1, and the plateau temperature range was also extended.
In the second set of process conditions, the screw speed was increased to 12 rpm. This caused the melt temperature to increase to 184� C., and the blend melt index to increase to 10.6 g/10 minutes. Seals prepared from this blend gave a seal strength plateau of about 17.7 g/mm over a temperature span of 88� to 122� C., a significant increase in the plateau seal strength compared with that of material produced at 6 rpm. At a seal temperature of 140� C., seal strength rose to 33.5 g/mm, but a fusion seal was not obtained.
EXAMPLES 12 TO 14 CONTROL BLENDS
To illustrate the effect of PP/E resin MFR on heat seal profile, experiments were carried out with three different PP/E resins, each containing 3% ethylene. Each was melt blended as described in Example 1 with the ionomer described in Example 1 except that the quantities of copolymer and ionomer were 10% and 90%, respectively and the melt temperature was 205� to 210� C. The melt flow rates of these PP/E resins are shown below:
______________________________________Ex-   PP/E    PP/E MFR,  Blend MI,                             Film Tear Sealample Resin   g/10 Minutes                    g/10 Minutes                             Temperature, �C.______________________________________12    A       3.5        13.3     8213    B       3.6        12.0     8214    C       3.8        12.5     91______________________________________
Seals were prepared and tested as described above. Heat seal profiles for these samples are shown in FIG. 10. The seal profiles show plateaus, but the seals were film tearing in the plateau region. Seals formed at 74� C. and higher blushed on peeling. In FIG. 10, data for resin A are shown as circles; data for resin B are shown as diamonds, and data for resin C are shown as squares.
This experiment was carried out in a manner identical to that of Example 12 except that the melt temperature during preparation of the blend was 268� C. The melt blended product had a melt index of 12.2 g/10 minutes. Heat seal profile determination showed a seal strength plateau of 33.4-37.4 g/mm over a temperature span of 91�-110� C., and a film-tearing bond was formed at 114� C. Seals formed at 74� C. and higher blushed on peeling.
The PP/E resins A and C described in Examples 12 and 14 were processed through the Werner and Pfleiderer extruder described in Example 1 at 273�-274� C. and pelletized. Melt blends with ionomer were then prepared as described in Example except that the melt temperature was 226�-228� C. and film samples were prepared at a melt temperature of 199� C. Results of these processing steps are shown below:
______________________________________PP/E Resin BlendEx-  MFR After  MI,     Plateau  Plateau Fusionam-  Processing g/10    Seal Strength                            Seal Temp.                                    Temp.,ple  g/10 Min.  Min.    Range, g/mm                            Range, �C.                                    �C.______________________________________16   4.9        13.4    29.5-33.5                            89-114  12517   5.4        13.2    19.7-23.6                            88-125  130______________________________________
This experiment demonstrates that resins which are high in molecular weight (low in MFR) initially can be thermally treated to lower their molecular weight (increase their melt flow rate), thus permitting the production of blends that will show a more desirable heat seal profile.
A pellet blend as described in Example 1 was melt-mixed using a 63.5 mm "Prodex" single screw extruder equipped with a screw having a mixing torpedo. The melt temperature during mixing was 199� C. and the blend had a melt index of 10.9 g/10 minutes. Film was extruded as described in Example 1 except that the melt temperature for Examples 18 and 19 was 197� C. and 206� C., respectively. Results from these experiments are shown below:
______________________________________  Plateau    Plateau  Seal Strength             Seal Temperature                          Fusion TemperatureExample  Range, g/mm             Range, �C.                          �C.______________________________________18     12.8-16.7  84-118       (a)19     27.6-31.5  88-108       132______________________________________
(a) Maximum 35.4 g/mm peel strength at 144� C., but fusion seal not obtained.
A comparison of the plateau seal strength and fusion behavior in these experiments shows the importance of melt temperature in the film extrusion step.
A terpolymer of ethylene/10% isobutyl acrylate (IBA)/10% methacrylic acid having a melt index of 10 g/10 min. was simultaneously blended with the propylene copolymer described in Example 1 and neutralized 20% with magnesium to provide a blend containing 90% terionomer and 10% propylene copolymer. More specifically, magnesium acetate tetrahydrate, A.C.S. Grade, was ground to a fine particle size in a mortar and pestle. A dry blend containing 3000 g of the terpolymer, 335 g of the propylene copolymer, and 149.5 g of the pulverized magnesium acetate was fed to the extruder described in Example 1 and processed at a melt temperature of 230� C. The melt was vacuum-devolatized during processing. The pellets produced were dry blended and re-fed to the extruder to assure product uniformity. The blend produced had a melt index of 1.6. Blown film of this blend was prepared as described in Example 1 except that the melt temperature was 224� C. Determination of the heat seal profile of this film showed a seal strength plateau of 6.3 to 10.2 g/mm over a temperature range of 84�-110� C. Seals made at 82� C. and above blushed on peeling, and film tearing bonds were formed at 119� C. and above.
Blends and film were prepared as described in Example 1 except that the ionomer was as described in the following table and the blends contained 90% ionomer and 10% propylene copolymer. Seals were made and tested as described above with the following results:
__________________________________________________________________________                           Film         Plateau% Comonomer(s)   Blend     Extr.                               Blush                                   Seal Str.                                        Temp.                                            Fusion                                                FusionExampleIn Ethylene/         Neut.             Neut.                 Temp.                     Blend MI                           Temp.                               Temp.                                   Plateau                                        Range                                            Temp.                                                StrengthNo.  Acid Polymer         Ion %   �C.                     g/10 Min.                           �C.                               �C.                                   g/mm �C.                                            �C.                                                g/mm__________________________________________________________________________21   15 MAA   Zn  23  208 7.5   199 84  11.8-15.7                                        89-124                                            140 55.122   15 MAA   Zn  40  210 2.4   215 82   7.9-11.8                                        90-135                                            (a) (a)23   10 MAA   Zn  20  208 10.8  176 64  14.2-18.1                                        76-142                                            (b) (b)10 IBA24   15 MAA   Na  20  208 5.7   225 76  33.5-37.4                                        91-135                                            (c) (c)__________________________________________________________________________ (a) No fusion. Maximum peel strength 13.4 g/mm at 144� C. (b) No fusion. Maximum peel strength 18.7 g/mm at 144� C. (c) No fusion. Maximum peel strength 39.4 g/mm at 144� C.
As can be seen, the temperature at which peeled seals blush, the peel strength in the plateau region, the temperature range of the plateau region, and whether a fusion or film-tearing seal is formed, can all be controlled by varying the ionomer composition.
Blends and films were prepared as described in Example 1 except that the propylene copolymer was as described in the following table and the blends contained 90% ionomer and 10% propylene copolymer. Seals were made and tested as described above with the following results:
__________________________________________________________________________       Prop.           Film         Plateau% Ethylene       Copoly.             Blend     Extr.                           Blush                               Seal Str.                                    Temp.                                        Fusion                                            FusionExampleIn Propylene       MFR   Temp.                 Blend MI                       Temp.                           Temp.                               Plateau                                    Range                                        Temp.                                            Str.No.  Copolymer       g/10 Min.             �C.                 g/10 Min.                       �C.                           �C.                               g/mm �C.                                        �C.                                            g/mm__________________________________________________________________________25   2.0    9     214 14.6  198 76  21.6-25.6                                    91-108                                        139 43.326   3.0    8     214 14.6  198 76  21.6-25.6                                    86-127                                        137 39.427   3.5      3.6 214 15.8  197 70  29.5-33.5                                    88-100                                        117 39.428   3.5    7     214 16.8  198 68  19.7-23.6                                    79-94                                        119 37.4__________________________________________________________________________
Examples 25 and 26 show that propylene copolymer of the proper MFR gives desirable plateau seal strengths without having to use high temperature extrusion.
A dry blend was prepared containing 27.215 kg of the propylene copolymer described in Example 1 and 238.9 kg of a terpolymer of ethylene, 10% isobutyl acrylate, and 10% methacrylic acid, which terpolymer had a melt index of 10 g/10 minutes, and 6.03 kg of a zinc concentrate containing 30% zinc oxide, 1.5% anhydrous zinc acetate, 0.5% zinc stearate, and 68% ethylene/MAA copolymer, containing 90% ethylene and having a melt index of 500 g/10 minutes. Dry pellets of each of these three components were fed to a 88.9 mm plasticating extruder at a feed rate of 31.75 kg of the pellet blend per hour. In the extruder the propylene copolymer pellets and the terpolymer pellets were melted and conveyed along with the zinc concentrate to the mixing section. The initial plasticating section of the screw was 7 diameters long and maintained at a temperature of about 120� C. At the inlet of the mixing section an activating liquid comprised of glacial acetic acid was injected into the molten stock by means of a nozzle penetrating the barrel wall. The mixing section was of the type described in U.S. Pat. No. 3,006,029 and was 13 diameters long. In the mixing section maintained at a temperature of 240� to 280� C., the zinc concentrate reacted with the polymer melt to neutralize some of the acid groups of the terpolymer through the formation of a soluble salt.
At the end of the mixing section, the mixture of ion crosslinked terpolymer, propylene copolymer and reaction by-products passed through a pressure control valve and a transfer line into a 2-inch diameter extraction extruder. The stock temperature before the valve was about 265� C. and the pressure 9.66 MPa (1400 p.s.i.). The extruder had two extraction zones, each about 4 diameters in length, in series. The first extraction zone was maintained at 686 mm of Hg and the second at 711 mm. of Hg. The temperature of the melt was maintained between 250� C. and 260� C. The extraction zone removed most of the volatile constituents from the molten, ion crosslinked terpolymer. The polymer blend was extruded through a die in the form of strands, cooled in water and cut into pellets. The blend contained 10% of the propylene copolymer, 90% of the terionomer, and had a melt index of 4.9 g/10 minutes. The carboxyl groups in the ionomer were neutralized 15.6%.
High density polyethylene (0.950 density and 0.45 MI) was fed to a 6.35 mm "Welex" single-screw extruder, and the blend described above was fed to a 50.8 mm "TEC" single-screw extruder. Melt temperatures were 222� and 172� C., respectively. The melt streams were combined in a Davis blown film coextrusion die with the blend outside. Film having a lay flat width of 584 mm was extruded at a blowup ratio of 2.5. The two-layer product film was made up to 0.048 mm of polyethylene and 0.013 mm of the blend. Heat seal profile testing of this composite film showed a plateau seal strength of 35.4-39.4 g/mm over a temperature range of 95�-112� C. Seals formed at 78� C. and higher blushed on peeling. Fusion seals were formed at temperatures of 139� C. and higher. The seal formed at 139� C. had a strength of 94.5 g/mm.
A three-layer, three-extruder feed block sheet coextrusion line was used to prepare a composite sheet. The sizes of the three single-screw extruders were: (A) 38.1 mm, (B) 25.4 mm, and (C) 31.8 mm. The output of these extruders entered a feed block and then a 152-mm wide die. The feed block was constructed so that the material from extruder (A) was cast against a controlled-temperature chill roll with the material from extruder B cast against the material from extruder A and the material from extruder C cast against the material from extruder B, thus producing a three layer structure, the three layers being designated, (a), (b), and (c) respectively in order outward from the chill roll. The cast composite sheet was then traversed over a second chill roll so that layer (c) was adjacent to the second chill roll. The first chill roll was operated at about 72� C. and the second at 25� C.
Film-grade propylene homopolymer having a melt flow rate of 2.8 g/10 minutes was processed through extruders (a) and (b) while the blend described in Example 29 was processed through extruder (C). Temperature settings for extruders, transfer lines, feed block, and die were 215� C. The extruders were set so that the layer thicknesses were: (a) 0.41 mm, (b) 0.05 mm, and (c) 0.05 mm. The sheet produced was then oriented at 155� C. at a stretch rate of 2000%/minute and stretch ratios of 2.75X in the machine direction and 3.5X in the transverse direction. The seal strength profile of the oriented composite film was then determined as described above. A seal strength plateau of 24.8 g/mm was obtained over a temperature range of 105�-130� C. Seals formed in this range blushed on peeling. In another experiment employing the same base sheet polymer and a different batch of the same composition blend as described in Example 29, a maximum peel strength of 37.8 g/mm was obtained.
EXAMPLE 31 CONTROL WITH ONLY IONOMER
An oriented film structure similar to that of Example 30 was prepared, except the polymer blend layer (c) was composed of a 20% zinc-neutralized terionomer containing 10% IBA and 10% MAA which had a melt index of 5 following neutralization. This oriented film gave a seal strength of only 19.7 g/mm at 105� C. No seal strength plateau was observed, nor did the seals blush on peeling.
An oriented film structure similar to that of Example 30 was prepared, except the polymer blend layer (c) was the composition of Example 1, but prepared by the method described in Example 29. This oriented film gave a plateau seal strength of 15.7-19.7 g/mm over a temperature range of 96�-129� C. Seals formed in this temperature range blushed on peeling.
An oriented film structure similar to that of Example 30 was prepared, except that layer (b) was made from the propylene copolymer/terionomer blend described in Example 29, and layer (c) was the same as layer (c) described in Example 32. This oriented film provided a plateau seal strength of 26.0-29.9 g/mm over the temperature range of 95�-127� C., which rose to a value of 38.4 g/mm fusion seal at a temperature of 139� C. Seals formed at 86� C. and higher blushed on peeling.
EXAMPLE 34 LAMINATION OF TWO LAYER EXTRUSION
The two-layer film described in Example 29 above was laminated to oriented polypropylene using an "Inta-Roto" coater/laminator in the following manner. The two-layer film was corona-treated on the high density surface by conventional means and slit to the proper width for lamination. A commercial single-component laminating adhesive, "Adcote" 333 supplied by Morton Chemical Company, was applied by gravure roll to one side of a commercial oriented polypropylene film of 0.019 mm thickness which had been corona-treated on both sides. The adhesive-coated film was passed through a drying oven held at 79� C. to evaporate the solvent. Immediately exit the oven, the adhesive-coated polypropylene was nipped to the high density polyethylene side of the coextruded film using a combining roll held at a temperature of 71� C., and then wound up after cooling.
The resulting laminated film was evaluated under a different test procedure than described for the other examples. Rather than a 3-second seal time, 0.5 seconds was used, and the seal bar temperature was recorded. The jaw activation pistons were activated with 207 kPa air pressure. These conditions are typical for form-fill-seal packaging of snack foods in commercial practice. Testing of the seals was carried out at 127 mm/minute jaw separation rate, but the "tail" of the sample was held in a T-peel configuration. This test procedure showed that a seal strength plateau of 21.6 to 26.0 g/mm was obtained over a seal bar temperature range of 143� to 160� C., and seals formed above 127� C. bar temperature blushed on peeling.
EXAMPLE 35 LAMINATION OF THREE LAYER EXTRUSION
In another embodiment of Example 34, the same seal layer composition was compounded with 1% stearyl erucamide slip additive. The stearyl erucamide was provided from a concentrate containing 10% of this ingredient melt blended with 90% of an ethylene/methacrylic acid copolymer having 9% methacrylic acid and a melt index of 10 g/10 minutes. A pellet blend containing 10% of the concentrate and 90% of the seal layer resin was fed to the "Prodex" extruder described in Examples 18 and 19 and pellets of the modified resin produced.
A three-layer blown film coextrusion apparatus was prepared with the following polymer feeds: (1) 0.944 density linear polyethylene having an MI of 0.25 plus a commercial white color concentrate, (2) the same polyethylene plus a commercial brown color concentrate, and (3) the seal layer composition with slip additive described above. A composite film having the following layer thicknesses was prepared: (2) 0.020 mm white polyethylene, (2) 0.015 mm brown polyethylene, and (3) 0.0076 mm seal layer. The white polyethylene surface was corona-treated and laminated to oriented polypropylene in a manner similar to that described in Example 34. Determination of the seal characteristics gave results similar to those described in Example 34, except that bar temperatures were shifted to about 11� C. lower for attainment of the same seal strength. The static coefficient of friction determined for the seal layer side of the coextruded film was 0.28, and the kinetic coefficient of friction was 0.25, as determined by ASTM Method 1894C.
EXAMPLE 36 EFFECT OF SLIP AND ANTIBLOCK ADDITIVES
Another seal layer composition was prepared to contain both an antiblocking and a slip additive. A pellet blend was prepared which contained the following ingredients: (1) 81% of a terionomer containing 6.3% IBA, 9.8% MAA, and neutralized 12% with zinc to a melt index of 5 g/10 minutes, (2) 9% of the propylene/ethylene copolymer of Example 1, and (3) 10% of a slip/antiblock concentrate containing 85% of an ethylene/methacrylic acid copolymer having 9% MAA and a melt index of 10 g/10 minutes, 10% N-oleylpalmitamide slip additive, and 5% silica antiblocking additive. The pellet blend was fed to an extruder, melt-compounded, and formed into pellets. These pellets were subsequently used for preparing first a three-layer coextrusion and then a laminate with polypropylene as described in the Example 35.
The blends of the present invention and the films and/or laminates of the present invention made from such blends are useful in the manufacture of peelable sealed flexible film packages which can be readily and manually opened at the seal layer interface upon application of a moderate, predictable and constant force. In addition, blends of the present invention that can be used to produce seals that will stress whiten when peeled are particularly well suited for packing items where the cleanliness, purity and/or integrity of the product is essential, e.g. foodstuffs, drugs and medical devices.
Although the best mode of the present invention, i.e. the single best blend of the present invention, will depend on the particular desired end use and the specific requisite combination of properties for that use, the blend and processing conditions that will result in a product most preferred for its overall balance of properties is described in detail in Examples 29 and 36.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3264272 *Apr 8, 1963Aug 2, 1966Du PontIonic hydrocarbon polymersUS3355319 *Mar 17, 1964Nov 28, 1967Du PontSelf-supporting film with a heat-sealable coating of an ionic copolymer of an olefin and carboxylic acid with metal ions distributed throughoutUS3404134 *Feb 28, 1964Oct 1, 1968Du PontProcess of crosslinking polymersUS3474063 *Oct 13, 1967Oct 21, 1969Du PontN,n'dialiphatic thiodipropionamides as slip and anti-block additivesUS3595827 *Nov 26, 1969Jul 27, 1971Union Carbide CorpEthylene interpolymers having improved slip and anti-blocking propertiesUS3597382 *Oct 30, 1967Aug 3, 1971Union Carbide CorpCarboxyl-containing ethylene copolymersUS3639530 *May 22, 1969Feb 1, 1972Fmc CorpHigh tenacity resinous packaging strapUS3819792 *Jul 20, 1971Jun 25, 1974Toray IndustriesProcess for producing a thermoplastic shaped article having a double layered wallUS3821179 *Sep 6, 1972Jun 28, 1974Du PontIonic ethylene copolymers containing slip/block additivesUS3969434 *Oct 29, 1973Jul 13, 1976E. I. Du Pont De Nemours And CompanyProcess for preparing ionically crosslinked copolymersUS4045515 *Jan 8, 1976Aug 30, 1977Toyo Boseki Kabushiki KaishaFilm of good tear property on impactUS4098406 *Aug 12, 1976Jul 4, 1978Tower Products, Inc.Polymer film having linear tear propertiesUS4148972 *Jun 22, 1977Apr 10, 1979Toray Industries, Inc.Heatsealable polypropylene film laminateUS4189519 *Aug 30, 1978Feb 19, 1980American Can CompanyHeat sealable resin blendsUS4279344 *Dec 26, 1979Jul 21, 1981Reynolds Metals CompanyHeat-sealable and peelable laminated packaging constructionUS4293664 *Dec 27, 1979Oct 6, 1981Union Carbide CorporationCook-in film containing a blend of ionomer and elastomerUS4321337 *Jan 11, 1980Mar 23, 1982E. I. Du Pont De Nemours And CompanyIonic hydrocarbon polymers having improved adhesion to nylonUS4346196 *Sep 10, 1980Aug 24, 1982E. I. Du Pont De Nemours And CompanyHeat seal composition comprising a blend of metal neutralized polymersUS4371583 *May 4, 1981Feb 1, 1983A. Schulman, Inc.Modified ionomer blend and laminated articleUS4407893 *Dec 3, 1981Oct 4, 1983United States Pipe And Foundry CompanyPolyolefin coating containing an ionomer for metal substratesGB1171085A * Title not availableJPS5817738A * Title not available* Cited by examinerNon-Patent CitationsReference1 *Defensive Publication, 877,077, (Uhline).* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4747976 *May 14, 1987May 31, 1988The Clorox CompanyPVA films with nonhydrolyzable anionic comonomers for packaging detergentsUS4759984 *Jun 27, 1986Jul 26, 1988Shell Oil CompanyPeelable seals using polybutylene-1US4784885 *Aug 29, 1986Nov 15, 1988R. J. Reynolds Tobacco CompanyPeelable film laminateUS4808662 *Oct 13, 1987Feb 28, 1989Shell Oil CompanyPeelable seals using polybutyleneUS4870134 *May 27, 1987Sep 26, 1989Shell Oil CompanyFilm, sheet and laminate capable of forming easy-open packagingsUS4876156 *Dec 16, 1988Oct 24, 1989Shell Oil CompanyFilm and sheet capable of forming retortable and easy-open packagingsUS4882229 *Apr 29, 1988Nov 21, 1989Shell Oil CompanyBlends of high molecular weight polybutylene with low density polyethyleneUS4885105 *Mar 31, 1988Dec 5, 1989The Clorox CompanyFilms from PVA modified with nonhydrolyzable anionic comonomersUS4916190 *May 15, 1987Apr 10, 1990Shell Oil CompanyFilm and sheet capable of forming retortable and easy-open packagingsUS4925318 *Nov 4, 1988May 15, 1990Schurpack, Inc.Packing, method of manufacturing same, and strip material thereforUS4977206 *Feb 3, 1989Dec 11, 1990Shell Oil CompanyModified polybutylene-based hot melt compositionsUS5024888 *Jul 30, 1990Jun 18, 1991Shell Oil CompanyModified polybutylene-base hot melt compositionsUS5066543 *Feb 28, 1990Nov 19, 1991Shell Oil CompanyFilm, sheet and laminate capable of forming easy-open packagingsUS5106917 *Feb 28, 1990Apr 21, 1992Shell Oil CompanyPeelable lidstock based on polybutylene block copolymer blendsUS5188461 *Mar 2, 1992Feb 23, 1993Schurpack, Inc.Packing, method of manufacturing same, and strip material thereforUS5238306 *May 19, 1989Aug 24, 1993Reynolds Consumer Products, Inc.Method of producing a sealing system for a reclosable webbed-wall package, and system madeUS5445893 *Apr 8, 1993Aug 29, 1995W.R. Grace & Co.-ConnpH control polymerUS5738923 *May 16, 1995Apr 14, 1998Minnesota Mining And Manufacturing CompanyMedical tubing and assembliesUS5840422 *Feb 7, 1997Nov 24, 1998W. R. Grace & Co.-Conn.pH control polymerUS6358622Dec 16, 1999Mar 19, 2002M.S.I. Technology L.L.C.Heat sealable filmsUS6663743Jun 18, 1998Dec 16, 2003Baxter International Inc.Peelable seal and container having sameUS7055683 *Jun 2, 2003Jun 6, 2006E. I. Du Pont De Nemours And CompanyMultiple compartment pouch and beverage container with smooth curve frangible sealUS7169138Nov 9, 2001Jan 30, 2007Baxter International Inc.Containers and methods for storing and admixing medical solutionsUS7306095 *Jan 27, 2006Dec 11, 2007E. I. Du Pont De Nemours And CompanyMultiple compartment pouch and beverage container with frangible sealUS9061819May 31, 2007Jun 23, 2015E I Du Pont De Nemours And CompanyMultiple compartment pouch or container with frangible sealUS20040118710 *Jun 2, 2003Jun 24, 2004Bourque Raymond AnthonyMultiple compartment pouch and beverage container with frangible sealUS20050109796 *Nov 12, 2004May 26, 2005Bourque Raymond A.Dual compartment flexible pouch and a fitment with dual-dispensing capabilities thereforUS20050266257 *May 24, 2005Dec 1, 2005I-Hwa LeePolymer blends for peelable and/or permanent sealsUS20070100076 *Oct 28, 2005May 3, 2007Hayes Richard AHigh modulus ionomers for packagingUS20070128386 *Dec 5, 2005Jun 7, 2007Knoerzer Anthony RLaminate structure for sealing channel leakersUS20070278114 *May 31, 2007Dec 6, 2007Kane James PMultiple compartment pouch or container with frangible sealUS20080017655 *Jul 19, 2006Jan 24, 2008Martel Shelly AFood container assemblyUS20090123613 *Dec 23, 2008May 14, 2009E.I. Du Pont De Nemours And CompanyHigh modulus ionomers for packagingUS20110026860 *Dec 6, 2007Feb 3, 2011Qualigen, Inc.Method and Apparatus for Implementing Differential Heat Seal Strength in Pouch-Based Diagnostic and Medical ProductsUSRE34988 *Dec 4, 1991Jul 4, 1995The Clorox CompanyFilms from PVA modified with nonhydrolyzable anionic comonomersEP0349160A2 *Jun 15, 1989Jan 3, 1990Minnesota Mining And Manufacturing CompanyTamper indicating tape and delaminating film thereforeEP1751231B2 †May 24, 2005Dec 23, 2015E. I. du Pont de Nemours and CompanyPolymer blends for peelable and/or permanent sealsEP2204338A1Dec 17, 2003Jul 7, 2010E. I. du Pont de Nemours and CompanyMultiple compartment pouch and beverage container with frangible sealWO2006094617A1 *Feb 17, 2006Sep 14, 2006Cryovac, Inc.Microwaveable film or sheet suitable for vacuum skin packaging applications and peelable microwaveable vaccum skin package obtained therewith* Cited by examiner, † Cited by third partyClassifications U.S. Classification428/500, 428/515, 428/516, 428/511, 428/461International ClassificationC09J123/08, C08L23/08, B32B27/30, C08L23/14Cooperative ClassificationC08L23/14, C09J123/0876, Y10T428/31913, B32B27/30, Y10T428/31692, Y10T428/31909, Y10T428/31895, Y10T428/31855, C08L23/0876European ClassificationC08L23/08C3A, C09J123/08C3A, B32B27/30Legal EventsDateCodeEventDescriptionMar 29, 1989FPAYFee paymentYear of fee payment: 4Mar 29, 1989SULPSurcharge for late paymentFeb 12, 1993FPAYFee paymentYear of fee payment: 8Mar 24, 1997FPAYFee paymentYear of fee payment: 12RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services


text:
Patent US5874014 - Durable plasma treatment apparatus and method - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA method and apparatus for treating a work surface, wherein there is provided a chamber having a longitudinal axis and longitudinally extending electrically conductive sidewalls, at least one sidewall having at least one longitudinally extending gap that interrupts a current path through the sidewalls...http://www.google.com/patents/US5874014?utm_source=gb-gplus-sharePatent US5874014 - Durable plasma treatment apparatus and methodAdvanced Patent SearchPublication numberUS5874014 APublication typeGrantApplication numberUS 08/483,982Publication dateFeb 23, 1999Filing dateJun 7, 1995Priority dateJun 7, 1995Fee statusLapsedAlso published asEP0857224A2, EP0857224A4, US6105518, WO1996041897A2, WO1996041897A3Publication number08483982, 483982, US 5874014 A, US 5874014A, US-A-5874014, US5874014 A, US5874014AInventorsAnthony E. Robson, Ronald A. Rudder, Robert C. Hendry, Moses M. David, James V. BurtOriginal AssigneeBerkeley Scholars, Inc., Research Triangle Institute, Minnesota Mining And Manufacturing CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (11), Non-Patent Citations (2), Referenced by (12), Classifications (30), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetDurable plasma treatment apparatus and method
14. A method for treating a work surface with a plasma, comprising:a) providing a chamber having a longitudinal axis and sidewalls that surround the longitudinal axis and comprise aligned spaced electrically conductive bars extending along the longitudinal axis, at least one sidewall being planar and at least 100 cm2 in area; the chamber being sealed by enclosure means so that the pressure can be controlled in the chamber; and b) providing an axially-extending array of current-carrying conductor paths that encircle the chamber, are transverse to the longitudinal axis, and are electrically connected in parallel; c) providing a gaseous material in the chamber; d) providing high-frequency current in the conductor paths in a magnitude to magnetically induce ionization of the gaseous material in the chamber and form a plasma sheath that surrounds and extends along the longitudinal axis and conforms

type: global

value: This website is a search engine provided by Google. Handling over 3.5 billion searches per day, it has a 92% share of the global search engine market.


text:
S.W. Brown & Son Funeral Home, Inc. - undefined - undefined | Legacy.com
HomeThe Star-Ledger Funeral HomesNew JerseyNutleyS.W. Brown & Son Funeral Home, Inc.
Dorothy M. Centeno
Dorothy M. CentenoNutley - Loving Mother & Grandmother.Dorothy M. Centeno, 76 of Nutley, passed away on Wednesday February 20, 2019. Born in Plainfield, Dorothy was raised in an orphanage in Jersey City and later lived in Spring Lake before coming... Read More
Published online in Asbury Park Press Feb 22, 2019
Nancy Pugliese Loving wife, mother, and grandmother Nancy Pugliese, 94, of Nutley, N.J., passed away on Friday, Feb. 15, 2019. Born in Matawan, N.J., Nancy was the daughter of the late Nina and Franco Muzzicato, and was a lifelong... Read More
Published online in The Star-Ledger Feb 17, 2019
Alice Russomanno Longtime Newark resident; Mass is on Saturday Alice Russomanno, 89, of Newark, N.J., passed away on Monday, Feb. 11, 2019. Born in Nanticoke, Pa., the daughter of Patrick and Catherine (Mayday) O'Donnel, she lived in Nanticoke prior... Read More
Alba Lovullo (1948 - 2019)
Alba Rose Lovullo Loving wife, mother, grandmother and great-grandmother Alba Rose Lovullo, 96, of Nutley, N.J., passed peacefully surrounded by her family on Feb. 5, 2019. Alba was born in Belleville, N.J., married in 1948, and moved to Nutley... Read More
Published online in The Star-Ledger Feb 07, 2019
John R. Vastola Loving husband, father, and grandfather John R. Vastola, 82, of Bloomfield, N.J., passed away on Tuesday, Feb. 5, 2019. Born in New York, N.Y., the son of Salvatore and Anna (Bedetto) Vastola, he grew up in... Read More
Daniel T. Meola Printing consultant Daniel T. Meola, 77 of Nutley, passed away on Feb. 4, 2019. Please visit www.swbrownandson.com for a complete obituary, visitation, funeral and donation information.Read More
Published online in The Star-Ledger Feb 05, 2019
David Mozeika Nutley resident David C. Mozeika of Nutley, N.J., passed away on Feb 2, 2019. For the obituary, funeral information, and memorial contribution, please go to swbrownandson.com.Read More
Published online in The Star-Ledger Feb 04, 2019
Madeline H. Brown Loving wife, mother and grandmother Madeline H. Brown, 84, of Nutley, N.J., passed away on Wednesday, Jan. 30, 2019, at her home. The funeral will be Saturday at 8:30 a.m. from the S.W. Brown & Son... Read More
Robert Bruscavage
Robert Bruscavage Communicable disease specialist Robert Bruscavage, 72, of Nutley, N.J., passed away on Tuesday, Jan. 29, 2019. Funeral Mass will be celebrated on Saturday, Feb. 2, at 10:30 a.m., at St. Michael the Archangel Church, 624 Page Ave., Lyndhurst,... Read More
Nicholas B. DeNude
Nicholas B. DeNudeLodi - Loving Husband, Father & Grandfather Nicholas B. DeNude, age 94 of Lodi, passed away on Saturday, January 26, 2019. Born in Lodi, the son of Theresa (Torre) and Domenick DeNude he was a lifelong resident.Nicholas retired... Read More
Published online in The Record/Herald News Jan 30, 2019

value: This website is a United States-based website founded in 1998, the world's largest commercial provider of online memorials. The Web site hosts obituaries and memorials for more than 70 percent of all U.S. deaths.


text: Despite a bogey on No. 18 in regulation, Suzann Pettersen beat Lizette Salas on the first playoff hole to win the Lotte Championship. Salas shot a final-round 62 to force the playoff. Story » AP Photo/Eugene Tanner

value: This website is the official website of ESPN. It is owned by ESPN Internet Ventures, a division of ESPN Inc.


text:
Handmade Patchwork Security Blanket Baby Rag Raggy Quilt Blankie Comforter | eBay Please enable JavaScript Our new search experience requires JavaScript to be enabled. Please enable JavaScript on your browser, then try again.
View: Gallery view Handmade Patchwork Security Blanket Baby Rag Ragg...: Handmade Patchwork Security Blanket Baby Rag Raggy Quilt Blankie Comforter0 results. You may also like
Cutie Owl TaGgie Baby Soft Toy Sleep Comforter Security Blanket/Blankie Safe gra
+AU $7.45 postage	Handmade Patchwork Quilt Set - Baby Ducks - includes matching security blanket
+AU $15.85 postage	Buddles Baby Comforter Cotton Security Blankie Blanket Toffee Bear
+AU $7.40 postage	Cutie Owl TaGgie Baby Soft Toy Sleep Comforter Security Blanket + Dummy holder
+AU $7.45 postage	Kids Timberland Baby soft Blanket PUPPY Comforter Security Blankie with Toy AU $19.80
+AU $17.00 postage	Minene Baby Comfort Blanket Comforter for Baby Security Tag Comforter Blankie- P
Minene Baby Comfort Blanket Comforter for Baby Security Tag Comforter Blankie- B
TaGgie Baby Toy Sleep Comforter Security Blanket/Safe Toy Cuddle+Dummy Holder
Personalised Ultra Soft Baby Security 'Blankie' toy/comforter
Handmade patchwork owl print blanket, cot quilt, crib quilt, baby blanket
Handmade Patchwork Blanket Quilt Indian Throw Single Baby Quilt Bedspread
RUSS Baby Blanket Security Blankie Teething Ring Tether comforter Plush Animal
Baby TaGgie Security Blanket Sleep Comforter Soft Toy Sleepy Sheep+Dummy holder
TaGgie Baby Toy Sleep Comforter Security Blanket/Safe grab Toy Cuddle+Dummy Hold
+AU $8.25 postage	BUBBA BLUE Spotted Cot Patchwork Quilt & Cot Muslin Blanket BLUE Baby Bedding
TaGgie Baby Security Blanket/Baby Sleep Comforter Grab/Cuddle Super Soft
+AU $7.45 postage	Personalised Baby Bear Security 'Blankie' toy/comforter
TaGgie Baby Security Blanket/Soft Cuddle Baby Sleep comforter Teddy Pink
+AU $7.45 postage	Purple Teddy TaGgie Baby Security Blanket Baby Sleep Comforter Soft Cuddle Toy AU $8.00
+AU $8.25 postage	patchwork Kantha Quilt Indian Handmade Cotton Comforter Blanket Bedding Throw
a day at the ZOO TaGgie Baby Security Blanket/Baby Sleep Comforter Cuddle Toy
+AU $7.45 postage	Little Pink Monkey TaGgie Baby Security Blanket/Sleep Comforter Soft cuddle toy AU $8.00
+AU $7.45 postage	Baby Security Cuddle Blanket Sleep Comforter Soft Toy Pink Bunny-Dummy not inclu
+AU $18.95 postage	Baby Taggy, Security Blanket, Comforter, Sensory Blanket, Baby Shower Gift
+AU $18.95 postage	BRAND NEW Timberland Baby zBlanket/ Baby Comforter/ Security Blankie/ Soft Toy AU $29.95
Patchwork cot quilt/throw snuggle blanket,washable, denim & flannelette
NEW Handmade Quilt MY SUBURB LAP QUILT - code 1007 Luxury Doona Blanket
Vintage Mickey Mouse Quilt Blanket Patchwork Disney Minnie Baby Cutter Handmade
+AU $5.43 postage	Nursery Baby Cot Blanket or Comforter Choose design GIRAFFE BETTY BOOP SPORTS
+AU $57.40 postage	Deer Taggie Comforter Blankie Realtree Handmade New Camo Baby Blanket
Stephan Baby Super Soft Plush Blankie Buddy Security Blanket, Grey Elephant. Fre
BUBBA BLUE Spotted Cot Patchwork Quilt & Cot Muslin Blanket YELLOW Baby Bedding
Handmade kids appliqued rag quilt/blanket
+AU $79.20 postage	Organic Baby Comforter Kippins Cotton Security Blankie Blanket Billie Bear
Organic Baby Comforter Kippins Cotton Security Blankie Blanket Splits Monkey
Activity Cuddle Blanket Comforter Blankie Boxer Dog Organic Farm Buddies. Free S
Activity Cuddle Blanket Comforter Blankie Surfer Chick Organic Farm Buddies. Shi
Organic Baby Comforter Kippins Cotton Security Blankie Blanket Kippin Kitty Cat
+AU $14.50 postage	Organic Baby Comforter Kippins Cotton Security Blankie Blanket Kippin Dash Tiger

value: This website is an American multinational e-commerce corporation based in San Jose, California, that facilitates consumer-to-consumer and business-to-consumer sales through its website.


text:
Denise Van Outen: 'Lee is the only ex I've kept in touch with' | Daily Mail Online
Denise Van Outen: 'Lee is the only ex I've kept in touch with' By
19:01 EDT, 25 January 2014
12:26 EDT, 31 January 2014
In her first major interview since last summer’s split with husband Lee Mead, Denise Van Outen reveals how she’s been coping post-break-up – and why she’s created a new one-woman show that’s really ‘from the heart’ DENISE WEARS CARDIGAN, M Missoni. SKIRT, Louis Vuitton. BELT, Wolford. JEWELLERY THROUGHOUT, Denise's own It’s difficult to match the Denise Van Outen who arrives for our interview – just a little flustered on a cold, wet winter’s morning – to the tough, loud, super-confident woman who first burst into the public consciousness in the late 1990s on The Big Breakfast. Everything about her – from her bare-of-make-up face to her soft voice – is at odds with the image the 39-year-old presenter, singer and sometime actress has maintained for nearly 20 years. Nothing she has done during that time – not even her brilliant turn in flouncy, feathered gowns as the runner-up on Strictly Come Dancing in 2012 – has managed to change the way in which she is publicly perceived. But within minutes of meeting her, I am so struck by the dramatic contrast between the bold and brash man’s woman I had expected to meet and the sensitive, understated person I encounter that I find myself confessing to her how surprised I am to discover that she is much more lady than ladette.‘The ladette label that has followed me throughout my career is so wrong,’ she says. ‘Of course I can have a laugh with the guys, but I am very much a girl’s girl. And it really bothers me that people don’t always see that; instead they think that I am hard as nails and that everything for me is like water off a duck’s back. I am the very opposite – I am sensitive and a worrier, and if something has upset me I will carry it with me for a long time. I don’t just shake it off. It stays with me but people don’t see that.’
Denise with Johnny Vaughan on The Big Breakfast
Our talk today is meant to focus on Denise’s brave new career move – as the star of Some Girl I Used to Know, a one-woman show that she has written with Terry Ronald. But the elephant in the room is the one thing, right now, that she cannot quite ‘shake off’ – last summer’s very public breakdown of her marriage to Lee Mead, 32, the father of her adored three-year-old daughter Betsy.Much as she might want to limit the conversation to her show (more of which later), Denise clearly wants to put straight any misconceptions that might surround their split. When I pose a question about the current state of her relationship with Lee, her reply is as unrehearsed as it is unequivocal. ‘Lee is the nicest person in the world and the best dad in the world. Our marriage may not have worked but I did pick a brilliant father and a great friend,’ she says without a moment’s hesitation.If their love story hadn’t been so public – they met when Lee was competing, and Denise judging, on the 2007 talent show Any Dream Will Do – their break-up might not have been subject to such intense speculation and gossip. But the romance between Lee – the winner of the show and the subsequent star of the revival of Andrew Lloyd Webber’s Joseph and the Amazing Technicolor Dreamcoat – and the older and more established Denise was the stuff of modern fairy tales. They began dating months after the show ended in 2007, married in April 2009 and a little over a year later their daughter Betsy was born. But by the summer of 2013 – amid rumours of ‘separate lives’ and Lee’s apparent failure to sustain a successful career (he has subsequently joined the cast of Casualty) – they announced their split, insisting that they remained ‘great friends’. The fact that they are real friends is something Denise is anxious to stress.'Anyone who has come out of a long-term relationship needs to find themselves again'
‘That’s the one thing I am really proud of, that Lee and I have come out of it as really good friends. Lee is brilliant with Betsy, I couldn’t ask for anything more. We are totally united when it comes to our daughter. We sit down and talk about how we are going to do things – for example, last Christmas, because Lee was in pantomime and only had Christmas Day off work, I said to him, “Why don’t you stay on Christmas Eve so you can be with Betsy properly on the day?” So he did and it was great.’The couple are also united in supporting each other’s careers and Lee will be very much involved in looking after Betsy during Denise’s two-month tour with her new show. On the nights that he is working he will either have his daughter with him in Cardiff – where Casualty is filmed – or take Betsy to stay with his parents who live closer to the Kent farmhouse that the couple bought when they married.Denise is understandably nervous about how the one-woman show will be received because it is a project that she is passionate about and a story she tells ‘from the heart’. The play takes place in a hotel room where her character Stephanie – a successful, happily married woman in her late 30s – is staying on business. FAUX FUR JACKET, Topshop. TOP, 3.1 Phillip Lim, from Harrods. SKIRT, Tara Jarmon
A chance contact online with an ex-boyfriend – the lost ‘love of her life’ who is also in town and anxious to meet – prompts her character to look back over her past as she tries to make up her mind whether or not she should see him again. Punctuated by songs from the 80s and 90s – which she emotively performs – Some Girl I Used to Know is set to reposition Denise not only as an accomplished writer but also as the sensitive woman she is. ‘I am very emotional and I wanted to write this play to connect with a female audience. And I became aware that there is a whole group of women of my generation who for various reasons – their career, not finding the right man or coming out of a marriage like myself – find themselves at 40 years old and single and I thought, “Who is writing for these women?” I wanted to create something that would make them laugh as well as cry. But I am scared because when I have done other things there has always been someone else to blame if it doesn’t work – but this is my baby.’The timing for this ‘baby’ is, Denise says, perfect as her other baby, Betsy, is reaching a stage – she has just started pre-school three days a week – where she is not so dependent on her mother’s full-time care (she has never had a nanny). In the aftermath of the break-up, Denise has restricted her working life to her Saturday show for radio station Magic, so that she could put her daughter’s emotional and physical wellbeing first. Denise is at her most endearing – and surprising – when she talks about their life at home in Kent, where she grows her own organic vegetables, rustles up nutritious suppers on her Aga and even confesses to a secret ambition to compete on MasterChef.
Denise with Lee and their daughter Betsy last July
‘I am at home in Kent with Betsy four days a week and she is in London with me – where I have a base – the other three days when she isn’t with Lee. In the country I am just Mum; I take her to pre-school and then go home and clear up the house. Then when Betsy comes home we pick vegetables together. I wanted her to learn about food in a way that I never did – know where vegetables grow and bring them in to eat and cook together. Then we might watch a movie such as The Little Mermaid and then it’s time for her bath and a story in bed. Her new thing is, “Shall we just chat, Mummy?” and I say, “What shall we talk about?” and she will say, “Shall we talk about a holiday or something lovely?”’ Denise reveals with a smile.Despite Betsy having two theatrical parents (Denise attended stage school and began modelling at an early age) there is no likelihood of her growing up in the glare of publicity or becoming a child actress. When she is five she will attend her current private ‘very academic’ school full-time so that she has other career options. ‘If she turns to me the day she leaves school and says, “I want to act” and she has a real flair for it, then of course I’d encourage her,’ says Denise, ‘but I want her to have the chance to do well academically then make her choice.’When I ask if there is room in Denise’s life yet for new romance, she is adamant that she is not ready – adding that paparazzi pictures taken last month of a svelte, suntanned Denise sitting on an Australian beach chatting to Andy Brown, front man of the band Lawson, were misrepresented in the media. 'I'm very sensitive when it comes to affairs of the heart'
Andy, she says with a shake of her head, is ‘only 25’ and they were actually part of a larger group of people who just happened to be working together on the same TV show. ‘There is absolutely no new romance. No way, it’s far too soon. My head is not even in that area. Right now I need to take time for me because anyone who has come out of a long-term relationship needs to find themselves again. I have distracted myself with work and obviously I am a busy mum but I am not really ready for a relationship. It’s less than a year since Lee and I split. All I have been doing is just spending downtime with my girlfriends, working, and spending quality time with Betsy. I haven’t thought about anything more than that,’ she says.Some Girl I Used to Know does, Denise admits, draw on her own emotional history, and writing and working on the play has acted as a barrier of sorts to new relationships – opening up as it does past heartbreak. JACKET AND SKIRT, Alexander McQueen, from Harrods. SHOES, Louis Vuitton
‘Oh God, I get so hurt – I am very sensitive when it comes to affairs of the heart. It is very much all or nothing with me and I don’t keep in touch with my exes because normally when things end there are hurt feelings. Obviously my situation with Lee is very different – there would never be a cutoff thing with him and it’s not only because we have a child together, it’s just a very different relationship from any other I have had,’ she says, hinting – but not exactly confirming – that their marital breakdown did not involve the kind of painful betrayal she has experienced in past relationships.Denise’s respect for Lee is palpable and she is clearly thrilled about his career break in Casualty. They may be living apart but you sense that they remain very much a family, with both sets of grandparents involved in Betsy’s life. As we part, I comment that in a world in which divorce is the norm, she and Lee seem to have achieved the best possible outcome. ‘Lee is brilliant – I can’t fault him. I have friends who are separated from their partners and they have all sorts of problems with them not turning up to collect the child when they have said they will and so on. Lee has never let me down like that. He does lovely things with Betsy and she adores him. I talk about him all the time to her and always say nice things – I would never badmouth him in front of her, or anybody. The reasons for it not working are not anybody else’s business but ours,’ she says, before adding, ‘and Betsy loves us both and sees us being together, being nice to each other and laughing, and that makes for a happy family, doesn’t it?’Denise will be touring the country from Wednesday until 19 March – for details, visit somegirliusedtoknow.com Share or comment on this article

value: This website is the website of the Daily Mail, a newspaper in the United Kingdom, and of its sister paper The Mail on Sunday. MailOnline is a division of dmg media, which is owned by Daily Mail and General Trust plc.


text:
Races Around the Region: SUFFOLK COUNTY;Executive Wins Second Term Handily - The New York Times
Archives|Races Around the Region: SUFFOLK COUNTY;Executive Wins Second Term Handily
https://nyti.ms/298lA4d
Races Around the Region: SUFFOLK COUNTY;Executive Wins Second Term Handily
Robert J. Gaffney, a Republican, was re-elected to a second four-year term as Suffolk County Executive, easily defeating his Democratic opponent, Tony Bullock, Supervisor of the Town of East Hampton, by a 2-to-1 ratio.
"We ran a great race and we won because we put government in Suffolk County bank on track," Mr. Gaffney said as he declared victory.
With 505 of 991 precincts reporting, unofficial returns gave Mr. Gaffney 74,504 votes to 39,103 for Mr. Bullock.
The key issue in the campaign was taxes, with Mr. Gaffney promising to cut both the sales and property taxes next year, despite claims by Mr. Bullock that Mr. Gaffney's 1996 budget was flawed and would lead to a tax increase.
Mr. Gaffney, with the well-organized support of the Suffolk County Republican Committee, spent more than $2 million on his campaign, four times what Mr. Bullock spent. Both candidates used most of their campaign war chests to purchase mud-slinging television ads, with Mr. Gaffney accusing Mr. Bullock of picking taxpayers' pockets, and Mr. Bullock calling Mr. Gaffney a liar on taxes.
All 18 seats on the Republican-dominated Suffolk County Legislature were also up for election, with most incumbents seeking another two-year term. Whatever the outcome, the incumbents were scheduled to attend a special meeting today to complete work on Mr. Gaffney's proposed 1996 budget. JOHN T. McQUISTON
A version of this article appears in print on November 8, 1995, on Page B00004 of the National edition with the headline: Races Around the Region: SUFFOLK COUNTY;Executive Wins Second Term Handily. Order Reprints| Today's Paper|Subscribe

value: This website is an American daily newspaper based in New York City with a worldwide readership. Founded in 1851, the Times has since won 132 Pulitzer Prizes, the most of any newspaper, and has long been regarded within the industry as a national "newspaper of record".


text:
H&M Short Sleeve Tops & Blouses for Women | eBay
Skip to main contenteBayShop by categoryShop by categoryEnter your search keywordWomen's Tops & Blouses└ Women's Clothing└ Clothing, Shoes, AccessoriesAll CategoriesAlcohol & Food Antiques Art Baby Books, Magazines Business Cameras Cars, Bikes, Boats Clothing, Shoes, Accessories Coins Collectables Computers/Tablets & Networking Crafts Dolls, Bears Electronics Gift Cards Health & Beauty Home Appliances Home Entertainment Home & Garden Industrial Jewellery & Watches Movies Music Musical Instruments Pet Supplies Phones & Accessories Pottery, Glass Services Sporting Goods Stamps Tickets, Travel Toys, Hobbies Vehicle Parts & Accessories Video Games & Consoles Lots More...AdvancedG'day (Sign in to bid or buy) eBay Deals Sell Help & Contact My eBayExpand My eBay My eBay Summary Bids/Offers Watch List Wish List All Lists Purchase History Selling/sold My Collections Followed searches My messagesNotification There seems to be a problem serving the request at this timeYou're hereeBayClothing, Shoes, AccessoriesWomen's ClothingWomen's Tops & BlousesH&M Short Sleeve Tops & Blouses for WomenSkip to page navigationRefine (2)H&M Short Sleeve Tops & Blouses for WomenShop by MaterialShowing slide {CURRENT_SLIDE} of {TOTAL_SLIDES} - Shop by MaterialGo to previous slide - Shop by MaterialPolyesterViscoseCotton BlendGo to next slide - Shop by MaterialAllAuctionBuy It NowSort:Best MatchBest MatchLowest price + postageHighest price + postageEnding soonNewly listedNearest firstView:Gallery view1-25 of 92 resultsH&M Women Top Blouse Sequinned Birds White Short Sleeve Size M• Size M to fit 170cm/96AAU $15.00FAB PALE PINK STRETCH LACE UP TOP by DIVIDED H&M SIZE SSIZE S.AU $5.000 bidsEnding Monday at 14:19 AEST16h 43mH&M black silky blouse top size 14H&M black blouse size 14 (Australian). Only worn a handful of times. Relaxed fit.AU $10.000 bidsEnding Tuesday at 19:10 AEST1d 21hBLACK DIVIDED by H&M NET AND SOLID FABRIC TOP SIZE XSSIZE XS.AU $2.000 bidsEnding Monday at 13:39 AEST16h 4mH & M Gorgeous Women's TOP Size XL BRAND NEW!!!Here we have a Gorgeous Top in BRAND NEW Condition with Tags from H & M Size XL BNWT Shell: 95% Cotton 5% Elastane Upper Part: 95% Polyamide 5% Elastane Great look with White or Black or Denim The length of this is 74 cm from the top of the Shoulder Dress up or Down This is a great item to add to your current wardrobe easy to wear great for cruising & travel Comes from a smoke free & animal free home Happy to combine postageAU $10.000 bidsEnding Tuesday at 21:21 AEST1d 23hTie-front blouse/top - Black/ Printed/Cat | H&M Size 11-12SIZE: AUS 11-12.AU $5.000 bidsEnding Monday at 0:01 AEST2h 25mLocal pickupH&M Basic Grey Tee Top T shirt T-shirt Size S Small 10Size: S (small). Material: 40% cotton, 60% viscose.AU $12.00Free postageH&M Short Sleeve Off White Top Size 8Size 8.AU $19.00Free postage4 watchingH & M Top Bandana Print Paisley Pocket Shirt Casual Wear Black And WhiteOnly worn a couple of times would fit size 8-10 is a European size 38 or US 8. Has a front pocket, key hole design at back with button clasp and is made of Viscose material which is light weight. If you have any questions please message. If you like this you may like more of my items so check out the rest of my listings & follow. Updating regularly.AU $8.000 bidsEnding Monday at 11:08 AEST13h 33mH & M Plus Size 22 XXL Women's Black Blouse Top Shirt Covered ButtonsUnderarm to underarm lying flat front only 69cm.AU $19.95Was: Previous priceAU $21.00Brand new H&M ladies striped short sleeve zip front bodysuit, size 10This bodysuit is a ladies size 10, model is a size 8-10. This bodysuit is new, never worn, perfect condition.AU $38.25Free postageor Best OfferNew listingH&M Casual Top T-Shirt Navy - Size LCasual wear. -Size L.AU $7.00H&M Women's Loose B&W Top, V Neck, Short Sleeves - 2XLH&M Women's Loose Top, 2XL, New Without tags. Longish short sleeves. Has a pleat at front 93% Polyester, 7% Elastaine Black & White Swirl pattern Free postage to anywhere in Australia.AU $25.00Free postageH&M White Tshirt with Tassel detailBrand new H&M tshirt with tassel detailingAU $10.000 bidsEnding Wednesday at 11:43 AEST2d 14hH&M Embellished Black Crop Size SSize small. H and M Crop.AU $0.990 bidsEnding Wednesday at 9:28 AEST2d 11h Divided by H&M womens size 12 bright orange zipup short sleeve skull topDivided by H&M womens size 12 bright orange skull short sleeve top. Super bright and fun with a rock edge, this short sleeve zipup top by H&M is simply stunning! Features a contrasting black zip with ribbons, all the way up the back, and huge bold edgy lacey skull. Love it!!
*Always happy to combine post, check out the rest of my store and hit that follow button!!*AU $19.99or Best OfferH&M blouse size 10 Pearl beading on the collar. 2 layers of sheer material so no underclothes needed. Lose fitting. Size 10.AU $1.490 bidsEnding Wednesday at 21:36 AEST3dH&M - Women's Horse Print Short Sleeve Round Neck T-Shirt / Top - Size XS / 8H&M - Women's T-Shirt / Top. Size: XS / 8. • Round neck. Length (shoulder to hem): 58cm. • Short sleeves. Even though we go to great lengths to find and describe these, we may miss an occasional flaw.AU $17.20Was: Previous priceAU $21.50or Best OfferNew listingLADIES H&M BLACK SATIN TRIM TOP SHIRT SIZE L NEW WITH TAGSYou are looking at a lovely ladies H&M top, new with tags. It has never been worn and in great condition. Can be worn for work or going out. It has a satin trim around the neck and sleeves with pleats at the front under the satin trim. Main fabric is cotton jersey. Originally purchased in the UK, the tag is a size Large with measurements when laid flat - Bust - 45cm Shirt length (from shoulder) - approx. 70cm Sold 'As Is'. No Returns. Check out my other auctions to save on postage.AU $15.00or Best OfferH&M grey And White Short Sleeve Lace Front Top Size XS Here today we have a short sleeved sweater style top with white lace at the front of the top. The back is completely grey with no lace detailing. Made of a thicker material, making it quite cosy. Purchased from h&m in Europe.AU $11.500 bidsEnding Tuesday at 8:17 AEST1d 10hH&M BLACK SHORT SLEEVE FULLY LINED SEQUIN TOPBLACK SEQUIN FULLY LINED EVENING TOP. SHORT SLEEVES. LENGTH APPROX. WOULD SUIT A SIZE 12.AU $10.000 bidsEnding Friday at 13:55 AEST4d 16hNew listingH & M Mustard Yellow Blouse Size EU 36NEW H&M blouse Size 8 or Eu 36 At questions please ask Happy biddingAU $10.00or Best OfferH & M Women's Black Sheer Short Sleeve Top / Blouse, Size 34, GCBlack sheer H & M ladies top / blouse with short sleeves. Good condition. Size 34 (roughly size 6-8). The top is empire line with ribbon that ties at the back.AU $5.000 bidsEnding Tuesday at 18:21 AEST1d 20hH&M Short Sleeve Off White Top Size 10Size 10.AU $19.00Free postageH&M Green short sleeved top Size 12a comfy beautifully draped blouse.AU $10.00Free postageor Best Offer
Got one to sell?Get it in front of 160+ million buyers.You may also likeShowing slide {CURRENT_SLIDE} of {TOTAL_SLIDES} - You may also likeGo to previous slide - You may also likeUnbranded Women's Short Sleeve Tops and BlousesShort Sleeve Tops & Taking Shape Blouses for WomenAutograph Short Sleeve Tops & Blouses for WomenCountry Road Short Sleeve Tops & Blouses for WomenSportscraft Short Sleeve Tops & Blouses for WomenGo to next slide - You may also likeTell us what you think - opens in new window or tabSide Refine PanelShop by CategoryWomen's ClothingWomen's Tops & BlousesWomen's Coats & JacketsWomen's DressesWomen's HosieryWomen's JeansWomen's Jumpers & CardigansWomen's Jumpsuits, Rompers & PlaysuitsWomen's PantsWomen's ShortsWomen's SkirtsWomen's SleepwearWomen's SportswearWomen's Suits and BlazersWomen's SwimwearWomen's T-ShirtsWomen's Tracksuits & HoodiesWomen's VestsWomen's Mixed Clothing ItemsOther Women's ClothingBuying formatsee allAll ListingsAuctionBuy It NowBrandsee allH&MFilter AppliedSleeve Stylesee allShort SleeveFilter AppliedColoursee allBlackBlueGreyPinkWhiteSize Typesee allRegularPlus SizeNot SpecifiedSize (Women's)see allStylesee allMaterialsee allPatternsee allConditionsee allNew with tagsNew without tagsPre-OwnedPricePlease provide a valid price range$-$Item locationsee allDefaultWithindistance2 km5 km10 km15 km20 km50 km75 km100 km150 km200 km500 km750 km1000 km1500 km2000 kmofGoAustralia OnlyWorldwideDelivery optionssee allFree postageFree Click & CollectShow onlysee allReturns acceptedCompleted itemsSold itemsDeals & SavingsMore refinements...


text: _.Bk(_.ln,_.qn,function(a){return 1002==a.Hb()?[a.getExtension(_.rn)]:[]});new _.mi(_.fn);_.Bk(_.fn,_.dn,function(a){return a.Yd()});new _.mi(_.$m);_.Bk(_.$m,_.Fm,function(a){a=_.an(a);return null!=a?[a]:[]});_.gp=function(a){_.w(this,a,0,-1,null,null)};_.p(_.gp,_.v);_.gp.prototype.Pa="K7KPvc";_.hp=new _.u(76813347,0,_.gp,0,0);_.ei[76813347]=_.hp;_.gp.prototype.Mc=function(){return _.z(this,_.qn,1)};_.gp.prototype.Tm=_.aa(63);(new _.mi(_.gp)).D1=_.hp;_.qk.K7KPvc=function(a){return _.rk(_.sk(a.Mc())).toString()};_.Bk(_.gp,_.qn,function(a){a=a.Mc();return null!=a?[a]:[]});new _.mi(_.dn);_.Bk(_.dn,_.bn,function(a){a=_.en(a);return null!=a?[a]:[]});new _.mi(_.bn);_.Bk(_.bn,_.$m,function(a){a=_.cn(a);return null!=a?[a]:[]});_.Txa=new _.mi(_.Om);_.qk.XingOb=function(a){return(""+_.rk(_.sk(_.y(a,1)))+","+_.rk(_.sk(a.getId()))+",").toString()};var ip=function(a){_.w(this,a,0,-1,null,null)};_.p(ip,_.v);ip.prototype.Pa="nu909";_.Uxa=new _.mi(ip);_.qk.nu909=function(a){return _.rk(_.sk(_.z(a,_.Om,1))).toString()};_.Bk(ip,_.Om,function(a){a=_.z(a,_.Om,1);return null!=a?[a]:[]});var jp=function(a){_.w(this,a,0,-1,null,null)};_.p(jp,_.v);jp.prototype.Pa="juBgAd";_.kp=new _.u(95797733,0,jp,0,0);_.ei[95797733]=_.kp;jp.prototype.Hu=function(){return _.z(this,ip,3)};(new _.mi(jp)).Pt=_.kp;_.qk.juBgAd=function(a){return _.rk(_.sk(_.y(a,1))).toString()};_.Bk(jp,ip,function(a){a=a.Hu();return null!=a?[a]:[]});var lp=function(a){_.w(this,a,0,-1,null,null)};_.p(lp,_.v);lp.prototype.Pa="QjR3Oe";_.mp=new _.u(74325872,0,lp,0,0);_.ei[74325872]=_.mp;lp.prototype.jc=function(){return _.z(this,_.Io,1)};(new _.mi(lp)).zh=_.mp;_.qk.QjR3Oe=function(a){return _.rk(_.sk(_.y(a,2))).toString()};_.Bk(lp,_.Io,function(a){a=a.jc();return null!=a?[a]:[]});var np=function(a){_.w(this,a,0,-1,Vxa,null)};_.p(np,_.v);var Vxa=[4];np.prototype.Pa="us53Lc";_.Wxa=new _.u(97900700,0,np,0,0);_.ei[97900700]=_.Wxa;np.prototype.jc=function(){return _.z(this,_.Io,1)};_.Xxa=new _.mi(np);_.Xxa.Aa=_.Wxa;_.qk.us53Lc=_.pk;_.Bk(np,_.Io,function(a){a=a.jc();return null!=a?[a]:[]});var op=function(a){_.w(this,a,0,-1,null,null)};_.p(op,_.v);op.prototype.Pa="LbeeOe";_.pp=new _.u(89329912,0,op,0,0);_.ei[89329912]=_.pp;op.prototype.jc=function(){return _.z(this,_.Io,1)};_.Yxa=new _.mi(op);_.Yxa.dl=_.pp;_.qk.LbeeOe=function(a){return _.rk(_.sk(_.y(a,2))).toString()};_.Bk(op,_.Io,function(a){a=a.jc();return null!=a?[a]:[]});_.Cp=function(a){_.w(this,a,0,-1,null,null)};_.p(_.Cp,_.v);_.Cp.prototype.Pa="GdSXVd";_.Dp=new _.u(72080230,0,_.Cp,0,0);_.ei[72080230]=_.Dp;_.Cp.prototype.jc=function(){return _.z(this,_.Io,1)};var Zxa;_.Ep=function(a){_.w(this,a,0,-1,Zxa,null)};_.p(_.Ep,_.v);Zxa=[3];_.$xa=new _.u(72080230,0,_.Ep,0,0);_.di[72080230]=_.$xa;_.Ep.prototype.Wc=function(){return _.y(this,1)};var aya=function(a){return(a=_.y(a,3))&&0Ludwing Iván Navarro Alvarez - Google+Press question mark to see available shortcut keysHomeCollectionsJoin Google+Send FeedbackHelpRegionPrivacy Policy - Terms of Service - Maps Terms©2017 GoogleSearchSign inAboutSearchSign inLudwing Iván Navarro Alvarez45 followers45 followersAboutLudwing Iván's interestsEXCEL Tips96,959 MembersJoinPaulo coelho español4,037 MembersJoinLudwing Iván's posts Post has attachmentLudwing Iván Navarro AlvarezPublic3dCelebrating Earth Day 2017! Learn Earth Day tips with today's #GoogleDoodle!Celebrating Earth Day 2017!g.co no plus ones no comments no shares Post has attachmentLudwing Iván Navarro AlvarezPublic22wDreampbx Admin Manual Draft 171110 - Documentsdocuments.mx no plus ones no comments no sharesLooks like you've reached the endLooks like you've reached the endUnable to load more. RetryWait while more posts are being loaded

value: This website .


text:
Gates Hits NATO Allies' Role in Afghanistan
NEWS | LOCAL | POLITICS | SPORTS | OPINIONS | BUSINESS | ARTS & LIVING | GOING OUT GUIDE | JOBS | CARS | REAL ESTATE |SHOPPING Gates Hits NATO Allies' Role in Afghanistan
Defense Secretary Robert M. Gates and the top U.S. commander of NATO forces in Afghanistan yesterday issued a blunt assessment of the alliance's shortcomings in that country, arguing that the unwillingness of some member states to risk combat casualties is threatening NATO's future and undermining the prosecution of the Afghan war.
"I worry a great deal about the alliance evolving into a two-tiered alliance, in which you have some allies willing to fight and die to protect people's security, and others who are not," Gates told the Senate Armed Services Committee. "It puts a cloud over the future of the alliance if this is to endure and perhaps get even worse."
American and other NATO officials are sparring over force levels, missions and strategy as violence in Afghanistan has reached its highest levels since the U.S.-led invasion and overthrow of the Taliban in 2001. Although coalition forces have defeated the Taliban in many tactical engagements, analysts say NATO remains in a "strategic stalemate" because of lagging reconstruction and governance efforts. The disputes have pitted Washington against its European partners in a manner rarely seen since the end of the Cold War, casting doubts on the credibility and purpose of the alliance.
Gates, who departs today for a two-day meeting with NATO defense ministers in Lithuania, said he will urge European countries to loosen the "caveats" they place on their troops -- rules limiting where they can be deployed or whether they can engage in battle -- and to send reinforcements to Afghanistan.
Gen. Dan McNeill, the NATO commander in Afghanistan, described in a wide-ranging interview how he is hamstrung by the combat restraints on some NATO troops, insufficient forces and intelligence capabilities, and a host of other political and military obstacles that undercut effective operations.
"Caveats deny me the ability to plan and prosecute," McNeill said. "I can't amass them to where I might have a decisive point. . . . Obviously I can't move as quickly as I want to," McNeill said.
McNeill said such constraints have led to unofficial proposals that U.S. forces take charge of the mission in southern Afghanistan, where the Taliban insurgency is strongest and where British, Canadian and Dutch troops now serve -- an idea that he said merits consideration.
"I think it should enter into the dialogue" with NATO, McNeill said. The roughly 27,000 U.S. troops in Afghanistan are concentrated near the eastern border with Pakistan and make up the bulk of the approximately 55,000 foreign troops in the country. McNeill attributed much of the increased violence to the stepped-up military operations.
NATO forces took charge of the Afghan mission in 2006, and the following year saw the worst violence in the country since the war began, with unprecedented military and civilian casualties and a nearly 30 percent rise in attacks, including 60 percent in the southern province of Helmand, according to U.S. military data. As he prepared to take command of NATO forces in Afghanistan in 2006, McNeill recalled, then-NATO Supreme Allied Commander Marine Gen. James Jones gave him simple instructions: "Don't fracture the alliance."
McNeill now finds himself struggling to hold that alliance together. "It doesn't look as though it's fractured," he said on a visit from Kabul, noting that over the past year foreign troops in Afghanistan have expanded by more than 8,000, with reinforcements expected soon from the United States and possibly Britain and Germany. But "there is a hell of a lot of debate back in various countries about what their role should be," he acknowledged.
The growing divide over NATO roles led to a tense encounter in Kabul last year between McNeill and a senior German official. McNeill, who had learned that only about 6,000 of Germany's 250,000-strong military force is deployed abroad, asked if Germany could devote one alpine battalion of about 500 troops to Afghanistan.
"You must understand the political context in our country," the official responded, wagging a finger. "General, that will not happen."
In another sign of allies' reservations, the Canadian government is debating whether to shift its mission to training and mentoring, a move McNeill opposes. "My first choice is to have them stay in the fight," he said. In an earlier news conference, McNeill described troop levels in Afghanistan as "a minimalist force."
Canada's government announced last week that it would continue its combat mission past January 2009 only if another NATO partner deploys an additional 1,000 combat troops to the southern province of Kandahar, where Canada's 2,500 troops are based.
Gates said yesterday that his decision to send 3,200 Marines into Afghanistan this spring stems in part from the shortfalls by NATO partners. Although he praised the Canadians, British, Australians, Dutch and Danes for "doing their part," Gates told the committee that he has written all NATO defense ministers asking them to "dig deeper" to solve the problems in Afghanistan.
Daniel Korski, a senior policy fellow at the European Council on Foreign Relations, said it will be hard for the United States to squeeze more troops out of NATO allies. "It's becoming increasingly difficult for governments to explain this is no longer a peacekeeping operation, this is counterinsurgency and combat, and that's far more dangerous," Korski said.
McNeill said he has also faced pressure from Afghan President Hamid Karzai to curtail operations in some provinces, particularly after civilian casualties. McNeill said he and Karzai have "intensive dialogues about not only where and why we run particular operations but how we intend to run them."
Karzai's government has also opposed U.S. proposals for more aggressive eradication of opium crops. Afghanistan supplies 90 percent of the world's opium, and McNeill estimated the crop finances up to 40 percent of Taliban operations. McNeill said he was pushing the NATO mandate as far as possible to allow his forces to target the "nexus" between opium and insurgents.
Regional interference, including weapons from Iran and fighters from Pakistan, are another challenge for McNeill. But he noted unusual progress made during a three-hour New Year's Eve meeting with the new head of Pakistan's Army, Gen. Ashfaq Kiyani, and the head of the Afghan military, who agreed to share intelligence on insurgent activity and conduct officer exchanges.
Also yesterday, when pressed by senators, Gates estimated that the Pentagon will need at least $170 billion to fund the Iraq and Afghanistan wars during fiscal 2009. The president's budget announcement Monday included a separate $70 billion war-funding request for the first quarter of 2009 but did not estimate costs that would stretch into the next president's administration.
Staff writers Karen DeYoung and John Ward Anderson in Paris and special correspondent Karla Adam in London contributed to this report.

value: This website is an American daily newspaper published in Washington, D.C. It is the most-widely circulated newspaper within the Washington metropolitan area, and has a large national audience. Daily broadsheet editions are printed for D.C., Maryland, and Virginia.