WO2016154102A1 - Matériau composite à résistance balistique - Google Patents
Matériau composite à résistance balistique Download PDFInfo
- Publication number
- WO2016154102A1 WO2016154102A1 PCT/US2016/023387 US2016023387W WO2016154102A1 WO 2016154102 A1 WO2016154102 A1 WO 2016154102A1 US 2016023387 W US2016023387 W US 2016023387W WO 2016154102 A1 WO2016154102 A1 WO 2016154102A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- fibers
- crystalline component
- composite
- crystalline
- Prior art date
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Classifications
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2571/00—Protective equipment
- B32B2571/02—Protective equipment defensive, e.g. armour plates or anti-ballistic clothing
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/04—Outerwear; Protective garments
Definitions
- the present disclosure relates to a composite formed with a bimodal binder.
- the present disclosure relates to a ballistic resistant composite formed from a plurality of fibers and a bimodal binder and a method of forming the same.
- Ballistic resistant articles may contain high-strength fibers which can be formed into various articles, such as vests, helmets, vehicle panels, additional articles of clothing, and additional items for military or police applications which resist penetration of bullets, shrapnel, and shells.
- Exemplary high-strength fibers are polyethylene fibers, aramid fibers, graphite fibers, nylon fibers, glass fibers, and the like.
- the fibers may be used in a woven or knitted fabric.
- the fibers may be encapsulated or embedded in a polymeric matrix material to form woven or non-woven composites.
- Hard or rigid body armor provides good ballistic resistance but can be bulky and stiff. Therefore, body armor garments, such as ballistic resistant vests, are preferably formed from flexible or soft armor materials. However, while such flexible or soft armor materials have good ballistic resistant qualities, these materials may also exhibit low abrasion resistance, which affects the durability of the armor. Additionally, it is necessary for hard and soft ballistic resistant articles to withstand environmental conditions which may degrade the ballistic resistance of the material. For example, due to the nature of military applications, ballistic resistant articles may be exposed to a variety of environmental conditions which may degrade the material, such as sea water, gasoline, gun lubricant, and petroleum. As such, the ballistic resistant articles are formed to resist such degradation when exposed to
- steel belt press 2 is an isobaric steel belt pressor double belt press which includes a first belt 10, a second belt 12, a first plurality of rollers 4 supporting first belt 10, a second plurality of rollers 6 supporting second belt 12, and a temperature unit 8.
- first plurality of rollers 4 rotates in a clockwise direction and is positioned above second plurality of rollers 6.
- second plurality of rollers 6 rotates in a counter-clockwise direction, which in combination with the clockwise rotation of first plurality of rollers 4, advances a compositel4 through steel belt press 2.
- Compositel4 may be comprised of high-performance fibers and a binder.
- the binder may be at least partially formed of a polymeric material and may be applied to the fibers through conventional coating processes (e.g., casting, dispersions).
- first and second belts 10, 12 are configured to apply a continuous pressure up to approximately 70 bar or 1,000 psi to composite 14 as compositel4 advances through steel belt press 2. Additionally,
- composite 14 passes through temperature unit 8 which includes a heating portion 8a and a cooling portion 8b.
- composite 14 receives continuous high pressure from first and second belts 10, 12 while being both heated and cooled, which results in a high degree of compaction and a reduction of air voids in composite 14. It is believed that the compaction from steel belt press 2 removes voids and other interstices within composite 14, thereby providing a smooth surface which is resistant to corrosive and degrading conditions.
- the present disclosure provides a ballistic resistant composite which includes a plurality of fibers and a bimodal binder applied to the plurality of fibers.
- the present disclosure provides a ballistic resistant composite comprising a plurality of fibers and a bimodal binder applied to the plurality of fibers.
- the binder has a crystalline component with a melting temperature and an amorphous component with a softening temperature.
- the crystalline component and the amorphous component have at least one of the following properties relative to one another: (1) the melting temperature of the crystalline component is less than the softening temperature of the amorphous component; (2) at a temperature above the melting temperature of the crystalline component, a viscosity of the crystalline component is less than a viscosity of the amorphous component; and (3) at a temperature above the melting temperature of the crystalline component, a surface energy of the crystalline component is less than a surface energy of the amorphous component.
- the crystalline component is a wax material selected from the group consisting of carnauba wax, stearamide wax, polyethylene wax, paraffin wax, polyolefin wax, and microcrystalline wax
- the amorphous component is a polymeric material selected from the group consisting of acrylic, polyurethane, nitrile rubber, acrylonitrile butadiene copolymer, and fluorocarbon.
- the plurality of fibers may be comprised of polyethylene.
- the plurality of fibers defines at least a first fiber ply and a second fiber ply oriented 90 degrees from the first fiber ply.
- the amorphous component comprises 60-95 wt.% of the bimodal binder and the crystalline component comprises 5-40 wt.% of the bimodal binder.
- the melting temperature of the crystalline component is about 50-140°C.
- the present disclosure provides amethod of forming a ballistic resistant composite comprising providing a first plurality of fibers in a unidirectional orientation, providing a second plurality of fibers in a unidirectional orientation, and providing a binder having an amorphous component and a crystalline component.
- the method further comprises coating the first plurality of fibers with the binder, coating the second plurality of fibers with the binder, positioning the first plurality of fibers at a 90 degree angle to the second plurality of fibers, heating the first and second pluralities of fibers to a temperature within a melting temperature range of the crystalline component, applying a pressure of less than one bar to the first and second pluralities of fibers when at a temperature within the melting point range of the crystalline component, and cooling the first and second pluralities of fibers.
- said pressure step includes is conductedwith a flatbed laminator.
- said applying step includes applying a first pressure of less than 0.5 psi to the composite during said heating step and applying a second pressure of 10 psi - 300 psi when the composite is at the temperature within the melting point range of the crystalline component.
- the composite may be heated and/or cooled for as little as 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, 3.0 seconds, or as much as 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes, or any range delimited by any pair of the foregoing values.
- first fiber ply comprising a plurality of unidirectionally oriented first fibers, wherein said first fibers are coated with a first bimodal binder that comprises an amorphous component and a crystalline component;
- a second fiber ply comprising a plurality of unidirectionally oriented second fibers, wherein said second fibers are coated with a second bimodal binder that comprises an amorphous component and a crystalline component;
- first fiber ply and second fiber ply positioning the first fiber ply and second fiber ply in a stacked arrangement, heating the first fiber ply and the second fiber ply to a temperature within a melting temperature range of the crystalline component;
- FIG. 1 is a schematic cross-sectional view of an isobaric steel belt press and a composite material being formed therein;
- FIG. 2 is a schematic view of a flat-bed laminator
- FIG. 3 is a schematic view of an extended flat-bed laminator with a plurality of coating devices.
- the present disclosure relates to a ballistic resistant composite 20 including a bimodal binder, the composite formable in a manner in which it is exposed to low pressure for a short duration of time and at a controlled temperature. More particularly, the bimodal binder of composite 20 allows the composite to be formed with a flat-bed laminator, for example, which may be less expensive than other processing methods, such as a steel belt press.
- Composite 20 includes a plurality of fibers 20a embedded in a bimodal polymeric matrix or binder material 20b (Fig. 3).
- Bimodal binder material 20b includes a first mode of an amorphous component and a second mode of a crystalline component, as detailed further herein.
- the amorphous component comprises the majority component of binder material 20b and may be chemically and/or physically incompatible with the crystalline component.
- at least the softening temperature, or alternatively, the glass-transition temperature, and material structure of the amorphous component is different from that of the crystalline component.
- Ballistic resistant composite 20 includes fiber material 20a which is embedded with bimodal binder material 20b.
- Fiber material 20a is formed from a plurality of fibers, each of which has an elongate body with a length much greater than the transverse dimensions of width and thickness.
- the cross-sections of the fibers of fiber material 20a may be circular, flat, or oblong. Accordingly, the term "fiber” includes filaments, ribbons, strips, and the like having regular or irregular cross-sections.
- Each fiber of fiber material 20a also may be of regular or irregular multi-lobal cross-section projecting from the linear or longitudinal axis of the fiber.
- Exemplary fiber material 20a comprises a non-woven, cross-plied, unidirectional fabric. More particularly, fiber material 20a includes a plurality of plies of unidirectional fibers oriented in a cross-ply configuration in which a first ply of fiber material 20a is oriented 90-degrees to an adjacent second ply of fibers. The fibers within each ply are adjacent and parallel to each other and, therefore, are oriented in a unidirectional
- each fiber may be approximately 0.063 inches or 1.588 mm in diameter.
- Fiber material 20a may be comprised of polyethylene fibers, aramid fibers, graphite fibers, nylon fibers, glass fibers, and the like.
- fiber material 20a is comprised of ultra-high molecular weight polyethylene, such as
- each fiber ply of the fiber material 20a may have a fiber areal density of from about 15 g/m 2 to about 250 g/m 2 , typically from about 20 g/m 2 to about 100 g/m 2 , and often from about 25 g/m 2 to about 70 g/m 2 , and most preferably about 35 g/m 2 .
- the fiber areal density refers to the weight of the fibers only (i.e., not including the binder) per unit area. Additional details of fiber material 20a may be disclosed in U.S. Patent No. 7,994,075, issued on August 9, 2011, and U.S. Patent No.
- Bimodal binder material 20b is applied to fiber material 20a to form ballistic resistant composite 20.
- Exemplary binder material 20b is a bimodal binder comprised oftheamorphous component which has amorphous phases discernible through magnification and the crystalline component which has crystalline phases discernible through
- magnification as is known to one of ordinary skill in the art.
- the amorphous component of binder material 20 bis characterized as amorphous because it does not have long-range order which is characteristic of a crystalline material.
- the lack of long-range order allows the amorphous component to be flexible which allows for flexibility in composite 20 and may be necessary when forming soft body armor that is configured to bend and move when being worn.
- the exemplary amorphous component of binder material 20b defines the majority component of binder material 20b.
- the amorphous component may comprise at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%), 95%), 99% or within any range delimited by any pair of the foregoing values, of the overall weight of binder material 20b.
- the amorphous component may be comprised of a liquid or powder resin, such as a polyurethane resin, acrylic resin, nitrile rubber resin, acrylonitrile butadiene copolymer resin, a fluorocarbon resin, polybutadiene resin, polyisoprene resin, ethylene- propylene resin, polysulfide resin, polyacrylate resin, polyester resin, and/or polyether resin.
- a liquid or powder resin such as a polyurethane resin, acrylic resin, nitrile rubber resin, acrylonitrile butadiene copolymer resin, a fluorocarbon resin, polybutadiene resin, polyisoprene resin, ethylene- propylene resin, polysulfide resin, polyacrylate resin, polyester resin, and/or polyether resin.
- the amorphous component of binder material 20b may be a waterborne dispersion of an acrylonitrile butadiene copolymer, supplied at 40% solids, such as TYLAC® 873 commercially available from Mallard Creek Polymers of Charlotte, NC000000, and/or a waterborne dispersion of a fluorocarbon resin, such as NUVA® 2040 commercially available from Clariant GMBH Corporation of Germany.
- an acrylonitrile butadiene copolymer supplied at 40% solids, such as TYLAC® 873 commercially available from Mallard Creek Polymers of Charlotte, NC000000
- a fluorocarbon resin such as NUVA® 2040 commercially available from Clariant GMBH Corporation of Germany.
- the exemplary amorphous component of binder material 20b has a greater viscosity, surface energy, and/orsoftening temperature than the crystalline component when at a temperature within the melting temperature of the crystalline component. More particularly, in one embodiment, the crystalline and amorphous components are selected such that the melting temperature of the crystalline component is less than the softening temperature of the amorphous component and/or a viscosity of the crystalline component is less than a viscosity of the amorphous component when at a temperature above the melting temperature of the crystalline component.
- the amorphous and crystalline components may be selected so that, at a temperature above the melting temperature of the crystalline component, a surface energy of the crystalline component is less than a surface energy of the amorphous component.
- the softening temperature of the amorphous component of binder material 20b isless than a degradation temperature of fiber material 20a but substantially greater than the melting temperature of the crystalline componentsuch that when the crystalline component melts and begins to flow, the amorphous component does not does appreciably melt or undergo a physical change and may even exhibit a resistance to flow.
- amorphous materials may not have a distinct melting point but will start to soften within a softening temperature range and will continue to soften as the temperature increases.
- crystalline materials have a true melting temperature and change drastically from a hard solid to a fluid over a much shorter temperature range.
- the amorphous component is incompatible with the crystalline component because the amorphous component is not physically modified or chemically reactive with the crystalline component during a physical transformation of the crystalline component.
- Honeywell 1150-denier SPECTRA ® Merge 95121 UHMWPE fibers and/or Honeywell 1300-denier SPECTRA ® Merge 95159 UHMWPE fibers may have a degradation temperature of about 140°C and the crystalline component may have melting temperature up to 140°C, as detailed further herein.
- the softening temperature of the amorphous component may be as little as 90°C, 100°C, 110°C, 120°C, 130°C, 140°C,150°C, 160°C, 170°C, 180°C, 190°C, or as great at 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, or more, or may be within any range delimited by any pair of the foregoing values.
- the softening temperature of the amorphous component may be less than the melting temperature of the crystalline component.
- the viscosity and/or surface energy of the amorphous component is greater than that of the crystalline component when at a temperature within the melting temperature of the crystalline component, the amorphous component will remain solid or highly viscous and, therefore, the crystalline component will flow around the amorphous component such that the amorphous and crystalline components do not mix. Additional details of the amorphous component of binder material 20b may be disclosed in U.S. Patent No. 7,994,075, issued on August 9, 2011, and U.S. Patent No. 8,017,530, issued on September 13, 2011, the complete disclosures of which are expressly incorporated by reference herein.
- the crystalline component of binder material 20b is added to, or doped into, the amorphous component.
- the crystalline component of binder material 20b is
- the crystalline component may have less flexibility but is included in binder material 20b because it allows for the compaction and densification of composite 20 at processing conditions with decreased pressure, thereby increasing the ballistic resistant properties of composite 20. Also, as discussed further below, during processing of the present composite, the crystalline material undergoes a phase change, such as melting, which allows the crystalline material to flow relative to the amorphous material, with subsequent re- solidification to provide desirable properties such as smoothness and density enhancement to provide resistance to corrosive environments.
- a phase change such as melting
- the crystalline component of binder material 20b is the minority component thereof.
- the crystalline component may comprise 45%, 40%, 35%, 30%, 25%, 20%), 15%), 10%), 5%), 1%) or may be within any range delimited by any pair of the foregoing values of the overall weight of binder material 20b.
- the crystalline component may be comprised of any crystalline polymer which is incompatible with the amorphous component. More particularly, the crystalline component may be incompatible with the amorphous component such that the two components do not mix or act as a single material.
- the crystalline component of the present disclosure may be a wax material, such as a carnauba wax, a polyethylene wax, polyolefin wax, a paraffin wax, stearamide wax, and/or a microcrystalline wax. Waxes are generally defined as materials that are solids at room temperature but melt or soften without decomposing above about 40°C.
- Waxes are generally organic and insoluble in water at room temperature but may be water wettable and may form pastes and gels in some solvents, such as non-polar organic solvents.
- the molecular weight of a wax may range from about 400 to about 25,000 g/mol and may have melting points ranging from about 40°C to about
- Waxes generally do not form stand-alone films like higher order polymers and generally are aliphatic hydrocarbons that contain more carbon atoms than oils and greases.
- the viscosity of waxes may range from low to high, typically depending on the molecular weight of the wax and the crystai!imty.
- the viscosity of waxes above their melting point is typically low.
- a "low viscosity wax” describes a wax having a melt viscosity of less than or equal to about 500 centipoi.se (cps) at 140°C.
- cps centipoi.se
- a low viscosity wax has a viscosity of less than about 250 cps at 140°C, most preferably less than about 100 cps at 140°C.
- linear polyethylene waxes molecular weight of about 2,000 to about 10,000 g/mol
- polypropylene waxes may have moderate to high viscosity, i.e., as high as 10,000 cps after melting.
- Viscosity values are measured using techniques that are well known in the art and may be measured, for example, using capillar ⁇ ' , rotational or moving body rheometers.
- a preferred measurement tool is a Brookfield rotational viscometer.
- Suitable waxes include both natural and synthetic waxes and non-exclusively include animal waxes, such as beeswax, Chinese wax, shellac wax, spermaceti and wool wax (lanolin); vegetable waxes, such as bayberry wax, candelilla wax, carnauba wax, castor wax, esparto wax, Japan wax.
- animal waxes such as beeswax, Chinese wax, shellac wax, spermaceti and wool wax (lanolin); vegetable waxes, such as bayberry wax, candelilla wax, carnauba wax, castor wax, esparto wax, Japan wax.
- Jojoba oil wax weicury wax, rice bran wax and soy wax
- mineral waxes such as ceresin waxes, montan wax, ozocerite wax and peat waxes
- petroleum waxes such as paraffin wax and microcrystalline waxes
- synthetic waxes including poly olefin waxes, polyethylene, polypropylene waxes, Fischer-Tropsch waxes, stearamide waxes (including ethylene bis-stearamide waxes), polymerized ot-olefm waxes, substituted amide waxes (e.g. esterified or saponified substituted amide waxes) and other chemically modified waxes.
- the preferred waxes include paraffin waxes, micro-crystalline waxes, Fischer-Tropsch waxes, branched and linear polyethylene waxes, polypropylene waxes, large particle size polyethylene waxes, carnauba waxes, ethylene bis-stearamide (EBS) waxes, and combinations thereof.
- exemplary crystalline materials of binder material 20b may be a waterborne dispersion of carnauba wax, supplied at 35% solids, such as HYDROCERTM EC- 35 wax commercially available from Shamrock Technologies Inc. of Newark, NJ; a waterborne dispersion of large particle size polyethylene wax, supplied at 40% solids, such as LL405 commercially available from Michelman, Inc. of Cincinnati, Ohio; a waterborne dispersion of high density polyethylene wax, supplied at 35% solids, such as Michelman, Inc. LL411; a waterborne dispersion of paraffin wax, supplied at 32% solids, such as Michelman, Inc.
- HYDROCERTM EC- 35 wax commercially available from Shamrock Technologies Inc. of Newark, NJ
- LL405 commercially available from Michelman, Inc. of Cincinnati, Ohio
- a waterborne dispersion of high density polyethylene wax supplied at 35% solids, such as Michelman, Inc. LL411
- a waterborne dispersion of paraffin wax
- a waterborne dispersion of microcrystalline wax supplied at 40% solids, such as Michelman, Inc. HL-480; and/or a waterborne dispersion of Fischer Tropsch polyethylene wax, supplied at 40% solids, such as Michelman, Inc. ME98040.
- the exemplary crystalline component of binder material 20b may have a low melt viscosity and a melting temperature of 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C,110°C, 115°C, 120°C, 125 C, 130°C, 135°C, 140°C, or any range delimited by any pair of the foregoing values. More particularly, a carnauba wax may have a melting point of approximately 75-85°C and a low melt viscosity.
- a micro- crystalline wax may be have a melting temperature of approximately 60-90°C and a low melt viscosity.
- a Fischer-Tropsch wax may have a melting temperature of 95-100°C and a low melt viscosity.
- a paraffin wax may have a melting temperature of 50-70°C and a low melt viscosity.
- polyethylene waxes may have a melting temperature of 90-140°C and, depending on the structure of the polyethylene wax, may have low, moderate, or high viscosity. As such, the crystalline component has a sharp melting temperature range that may only span about 5-50°C which allows the crystalline component to melt and cool rapidly.
- the melting point and melt viscosity of the crystalline component may be different than the softening temperature and viscosity of the amorphous component.
- the crystalline component melts rapidly and begins to flow around the solid amorphous component which does not appreciably melt at temperatures within the melting point range of the crystalline component.
- the molten crystalline component is then able to fill any voids within the blended binder material 20b and also within composite 20.
- the crystalline component cools rapidly to again form a solid phase.
- the crystalline component flowed around the solid amorphous component when at its melting temperature, the crystalline component is embedded and mixed with the amorphous component once cooled.
- a cast film of binder material 20b maintains discreet regions of the crystalline polyurethane resin within the larger mass of the amorphous synthetic rubber.
- the amorphous regions of the synthetic rubber remain solid but the discreet crystalline regions of the polyurethane resin melt and flow into voids within fiber material 20a which improves the fluid resistance of composite 20 by reducing capillary forces and reducing the total effective surface area of composite 20.
- composite 20 remains flexible due to the amorphous synthetic rubber but has improved ballistic resistance due to the crystalline polyurethane resin.
- the softening temperature of the amorphous component may be less than the melting temperature of the crystalline component.
- the viscosity and/or surface energy of the amorphous component is greater than that of the crystalline component when at a temperature greater than the melting temperature of the crystalline component, the amorphous component will remain solid or highly viscous and, therefore, the crystalline component will flow around the amorphous component and the amorphous and crystalline components do not mix.
- the crystalline and amorphous components are selected such that the melting temperature of the crystalline component is less than the softening temperature of the amorphous component and/or the viscosity of the crystalline component is less than the viscosity of the amorphous component when at a temperature above the melting temperature of the crystalline component.
- the amorphous and crystalline components may be selected so that, at a temperature above the melting temperature of the crystalline component, the surface energy of the crystalline component is less than the surface energy of the amorphous component. Additional details of the crystalline component of binder material 20b may be disclosed in U.S. Patent No. 7,994,075, issued on August 9, 2011, and U.S. Patent No.
- bimodal binder material 20b To form bimodal binder material 20b, the crystalline and amorphous components are mixed together through various processes.
- the crystalline and amorphous components may be mixed by forming wet blend emulsions and/or wet blend solutions. More particularly, the wet blend emulsion and/or wet blend solution includes a solvent in which both the amorphous component and the crystalline component are soluble. This wet blend solution and/or wet blend emulsionthen may be cast into a dry film in which the crystalline component and the amorphous component are maintained in discreet regions in this dry film.
- Binder material 20b may also be mixed by coarsely dispersing a solid form of the crystalline component into either a waterborne emulsion of the amorphous component or into a solvent-based solution of the amorphous component (FIG. 3).
- binder material 20b is applied to fiber material 20a to form composite 20.
- Binder material 20b is applied to fiber material 20a through various processes, such as with a spray gun,fiber pultrusion,fiber impregnation, hot melt extrusion, gravure coating, and/or other roll coating methods.
- a fiber impregnation method may be used to apply binder material 20b to fiber material 20a.
- an excess of a waterborne emulsion or dispersion of binder material 20b is applied to fiber material 20a.
- a series of stationary bars and pressure rollers squeeze out the excess binder material 20b to form composite 20.
- Composite 20 may then be temporarily cast onto and transported by a silicone-coated release paper and, when the water is dried, composite 20 is wound onto a roll for further processing.
- a combination of the aforementioned methods may be used to apply binder material 20b to fiber material 20a.
- a single waterborne emulsion of the amorphous component may be applied to fiber material 20a through the fiber impregnation method.
- the crystalline component may be applied in a dry form to the surface of composite 20 by way of an electrostatic sprayer.
- the dry form of the crystalline component can be applied to fiber material 20a either before or after the water from the waterborne emulsion of the amorphous component has dried.
- the amorphous component may be applied to fiber material 20b as a solvent-cast film using the aforementioned fiber impregnation method.
- the crystalline component is then applied in a dry form to the surface of the solvent-cast film of the amorphous component.
- fiber material 20a may be scoured with de-ionized water and dried before binder material 20b is applied thereto. Fiber material 20a then may be plasma treated at an energy flux of 50-80 watts/ft 2 /min, preferably 67 watts/ft 2 /min. Binder material 20b is subsequently applied to fiber material 20a through one or more of the aforementioned processes for adhering the individual fibers of fiber material 20a together and for adhering the various plies of fiber material 20a to each other. More particularly, fiber material 20a is coated with binder material 20b at a resin content of 5-30%, and preferably at a resin content of 17%). Once binder material 20b is applied to fiber material 20a, fiber material 20a may be rolled onto spools and stored as rolls until further processing occurs.
- binder material 20b is applied to fiber material 20a
- binder material 20b is applied to at least another layer of fiber material 20a to define a second ply of fibers.
- the various layers of plies of fibers are then positioned in a stacked arrangement and each ply is oriented 90 degrees from adjacent plies. Any number of plies may be included in composite 20 to accommodate various applications for composite 20.
- Composite 20 then may be formed with a flat-bed laminator 30 which includes a first or upper belt 32rotatable about a plurality of rollers 33 and a second or lower belt 34 rotatable about a plurality of rollers 35.
- First and second belts 32, 34 may be coated with a non-stick coating, for example a fluoropolymer-based material such asTEFLON ® , commercially available from E. I. DuPont De Nemours and Company of Wilmington, Delaware.
- First and second belts 32, 34 are spaced apart from each other by a passageway 36 for composite 20 to pass through. As shown in FIG.
- first belt 32 rotates in a counter-clockwise direction and second belt 34 rotates in a clockwise direction which advances composite 20 through flat-bed laminator 30.
- first and second belts 32, 34 rotate at a speed of 1-15 meters/second, and preferably 3
- first and second belts 32, 34 have approximately the same length such that composite 20 is in contact with both first and second belt 32, 34 for approximately the same length of time.
- Flat-bed laminator 30 of FIG. 2further includes a heating portion or zone 38, a cooling portion or zone 40, and a plurality of nip or pressure rollers 42 positioned
- heating portion 38 may be configured for operation at temperatures of as little as 50°C, 60°C, 70°C, 80°C, or as great as 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or any range delimited by any pair of the foregoing values.
- the temperature of heating portion 38 is within the melting temperature range of the crystalline component such that the crystalline component of binder 20b melts in heating portion 38.
- composite 20 may be heated for as little as 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, 3.0 seconds, or as much as 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes, or any range delimited by any pair of the foregoing values.
- the heating time and temperature are based on the nature of the crystalline component and the specific melting temperature range thereof.
- Pressure rollers may be comprised of various materials, such as metals (e.g., steel), polymers (e.g., elastic rubber), and/or ceramics. Additionally, one of pressure rollers 42 may have a fixed position and the other of pressure rollers 42 may be movable when a force is applied thereto, such that when a force is applied to one of pressure rollers 42, a force also is applied to composite 20. More particularly, pressure rollers 42 may apply a pressure of less than one bar to composite 20.
- pressure rollers 42 may apply a nip pressure to composite 20 of 10 psi, 30 psi, 50 psi, 70 psi, 90 psi, 110 psi, 130 psi, 150 psi, 170 psi, 190 psi, 210 psi, 230 psi, 250 psi, 270 psi, 290 psi, 310 psi, or within any range delimited by any pair of the foregoing values.
- pressure rollers may apply a pressure of 14 psi to composite 20.
- the greatest pressure applied to composite 20 occurs at a tangent 50 of pressure rollers 42 which is parallel to first and second belts 32, 34.
- smaller amounts of pressure are applied to composite 20 as the surfaces of pressure rollers 42 adjacent tangent 50 are in contact with composite 20.
- an increasing amount of pressure is gradiently applied to composite 20 as composite 20 is initially positioned between pressure rollers 42.
- greater pressure is applied to composite 20, with the greatest pressure applied to composite 20 when directly between tangents 50 of pressure rollers 42.
- a decreasing amount of pressure is gradiently applied to composite 20 until composite 20 is no longer positioned between pressure rollers 42.
- Different designs of flat-bed laminator 30 may apply different pressures to composite 20.
- pressure rollers 42 have outer surfaces comprised of steel, the contact footprint of pressure rollers 42 on composite 20 is relatively small and the average point pressure applied to composite 20 is large.
- pressure rollers 42 have outer surfaces comprised of elastic rubber, the contact footprint of pressure rollers 32 on composite 20 is relatively large and the average point pressure applied to composite 20 is small.
- Pressure from pressure rollers 42 is applied to composite 20 for about 0.02 seconds to about 5 seconds. More particularly, pressure may be applied to composite 20 for a duration of time of as little as about 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, or as great as 3.0 second, 3.5 seconds, 4.0 seconds, 4.5 seconds, 5.0 seconds, or within any range delimited by any pair of the foregoing values. In one embodiment, pressure may be applied to composite 20 for a timeduration of 0.01-0.05 seconds. Additionally, because pressure rollers 42 have circular cross-sections, the aforementioned times signify the total time duration that composite 20 experiences pressure. For example, using an order of magnitude calculation, if the length of the footprint between pressure rollers 42 is one cm and the line speed of flat-bed laminator 30 is 5
- the residence time that composite 20 experiences pressure applied by pressure rollers 42 is 0.12 seconds.
- 0.12 seconds represents the total amount of time that composite 20 experiences pressure from pressure rollers 42, there is a gradient of rising pressure for the first 0.06 seconds and a gradient of decreasing pressure for the last 0.06 seconds.
- the pressure applied by pressure rollers 42 to composite 20 is not continuous because pressure is not applied to composite 20 when passing through heating portion 38 and cooling portion 40.
- flat-bed laminator 30 may be configured to apply pressure to composite 20 as composite 20 is still within heating portion 38 and the crystalline component has melted. However, pressure will not be applied to composite 20 when passing through cooling portion 40 in order to minimize stresses applied to composite 20 during cooling. As such, flat-bed laminator 30 is not configured to apply continuous pressure to composite 20.
- cooling portion 40 is configured for temperatures less than the melting temperature of the crystalline component of binder material 20b.
- cooling portion 40 may be configured for operation at temperatures of 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 80°C, 90°C or within any range delimited by any pair of the foregoing values, depending on the particular crystalline component included within binder material 20b.
- composite 20 may be cooled for approximately the same amount of time it is heated. More particularly, composite 20 may be cooled for as little as 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, 3.0 seconds, or as much as 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes, or any range delimited by any pair of the foregoing values. As composite 20 passes through cooling portion 40, it is necessary that composite 20 remain flat and is not bent so as to minimize stresses applied to composite 20 during cooling.
- cooling portion 40 may be eliminated from flat-bed laminator 30 if it is possible for composite 20 to radiate sufficient heat to its surroundings to decrease its temperature below the melting temperature of the crystalline component to allow the crystalline component to solidify.
- it may be desirableto minimize or eliminate stresses to composite 20 when cooling below the melting temperature of the crystalline component of binder material 20b. Because pressure is not applied to composite 20 when cooling, stresses are not introduced into the crystal structure of the crystalline component.
- the discreet portions of the crystalline component which flowed around the amorphous component and into any voids within fiber material 20a when the crystalline component melted are maintained without chemically or physically mixing with the amorphous component.
- the amorphous and crystalline components remain discreet within binder material 20b and are incompatible with each other.
- first and second belts 32, 34 may apply a low pressure to composite 20 which is less than the pressure applied by rollers 42. Because the pressure applied by first and second belts 32, 34 is low, additional stresses are not introduced into composite 20 when passing through cooling portion 40. Alternatively, belts 32, 34 may not apply any pressure to composite 20 when passing through cooling portion 40.
- first and second belts 32, 34 may apply a pressure to composite 20 of as little as 0.01 psi, 0.05 psi, 0.10 psi, 0.15 psi, 0.20 psi, or 0.25 psi, or as great as 1.0 psi, 2.0 psi, 3.0 psi, 4.0 psi, 5.0 psi, 6.0 psi, 7.0 psi, 8.0 psi, 9.0, psi or 10.0 psi, or within any range delimited by any pair of the foregoing values, as composite 20 passes through heating portion 38 and cooling portion 40.
- the pressure applied by first and second belts 32, 34 is less than 0.5 psi. More particularly, the pressure applied by first and second belts 32, 34 is applied for a time duration which is inversely proportional to the belt speed of flat-bed laminator 30. In one embodiment, the residence time that pressure is applied to composite 20 by first and second belts 32, 34 ranges from as little as 1 second, 3 seconds, 5 seconds, 7 seconds, 9 seconds, or 11 seconds, or as much as 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes, or any range delimited by any pair of the foregoing values. As such, composite 20 may experience two distinct pressures - a first low pressure applied by first and second belts 32, 34 when passing through heating and/or cooling portions 38, 40, and a second higher pressure applied by pressure rollers 42.
- composite 20 also may be formed with an alternative embodiment of flat-bed laminator 30 which is shown as flat-bed laminator 30'.
- Flat-bed laminator 30' includes first belt 32 which is rotatable in a counter-clockwise direction about rollers 33 and a second belt 34' which is rotatable in a clockwise direction about a plurality of rollers 35' .
- first and second belts 32, 34' rotate at a speed of 1-15 meters/second, and preferably at a speed of 3 meters/second.
- the length of second belt 34' is greater than the length of first belt 32 such that composite 20 is in contact with second belt 34' for a longer period of time than with first belt 32.
- flat-bed laminator 30' further includes heating portion 38, cooling portion 40, and pressure rollers 42 positioned therebetween. Based on the location of pressure rollers 42, composite 20 is not under pressure when moving through heating portion 38 and cooling portion 40 but does receive a nip pressure when passing between rollers 42 of 10 psi, 30 psi, 50 psi, 70 psi, 90 psi, 110 psi, 130 psi, 150 psi, 170 psi, 190 psi, 210 psi, 230 psi, 250 psi, 270 psi, 290 psi, 310 psi, or within any range delimited by any pair of the foregoing values.
- Flat-bed laminator 30' of FIG. 3 also includes at least one coating device 44.
- flat-bed laminator 30' includes a first coating device 44a and a second coating device 44b, which may be hot melt applicators or a dry coating applicator. More particularly, coating devices 44a, 44b are positioned upstream of heating and cooling portions 38, 40 and first coating device 44a is configured to apply binder material 20b contained therein on second belt 34' while second coating device 44b is configured to apply binder material 20b contained therein on top of fiber material 20a before fiber material 20a enters passageway 36.
- fiber material 20a moves along a plurality of rollers 46 toward first and second belts 32, 34'.
- First coating device 44a applies a predetermined amount of binder material 20b to second belt 34' .
- binder material 20b on second belt 34' is applied to the lower surface of fiber material 20a.
- binder material 20b from second coating device 44b is applied to the top surface of fiber material 20b before fiber material 20b contacts first belt 32. In this way, binder material 20b is applied to both the top and bottom surfaces of fiber material 20a to define composite 20 before composite 20 enters passageway 36, heating portion 38, cooling portion 40, and pressure rollers 42.
- pressure rollers 42 may apply a pressure for a duration of time of as little as about 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, or as great as 3.0 second, 3.5 seconds, 4.0 seconds, 4.5 seconds, 5.0 seconds, or within any range delimited by any pair of the foregoing values.
- composite 20 moves through cooling portion 40 and exits flat-bed laminator 30' .
- the pressure applied by pressure rollers 42 to composite 20 is not continuous because pressure is not applied to composite 20 as composite 20 passes through heating portion 38 and cooling portion 40.
- the crystalline component of binder material 20b has a lower melt viscosity and lower surface energy, and may have a lower melting temperature, than the amorphous component, there may be greater wetting, greater displacement of air, and greater compaction in the crystalline component when pressure rollers 42 apply pressure to composite 20. As such, the presence of voids, air pockets, interstices, or other internal openings within the amorphous component is decreased during formation of composite 20 in flat-bed laminator 30, 30' .
- composite 20 includes a smooth surface generally free of voids which reduces capillary forces and the total effective surface area of composite 20, thereby increasing the ballistic resistance of composite 20 because environmental conditions, such as sea water, gasoline, petroleum, solvents, and lubricants do not penetrate composite 20. Furthermore, besides decreasing voids at the surface of composite 20, internal voids, pockets, and channels within composite 20 are removed or displaced through the compaction of composite 20, thereby reducing the tendency for wicking of fluids or other infiltration. Composite 20 formed according to the aforementioned disclosure may be used for ballistic resistant articles and is resistant to environmental conditions which may degrade composite 20.
- the binder material was applied tofiber material comprised of Honeywell
- 1 150-denier SPECTRA® Merge 95121 UHMWPE fiber More particularly, using a fiber impregnation coater, the binder material was applied to a first unidirectional fiber web and the coated fiber web was dried. The dried fiber web was wound onto a roll. A second roll of a second unidirectional fiber web also was coated with the fiber impregnation coater, dried, and wound onto a roll. The first coated fiber web on the first roll was cut into squares. The second roll of wound fiber was installed at or near the entrance of flat-bed laminator 30, 30' and the second fiber web was unrolled and fed through flat-bed laminator 30, 30' .
- the temperature of heating portion 38 of flat-bed laminator 30, 30' was set to a temperature below the melting temperature of the crystalline component.
- the squares of the first coated fiber web were placed on top of the second coated fiber web prior to the second fiber web entering flat-bed laminator 30, 30' .
- the fiber direction of each square of the first fiber web was positioned in a
- each square of the first fiber web was positioned to rearwardlyabut the previous, adjacent square on the second fiber web to define a continuous, coated, two-ply fiber material.
- This continuous, two-ply fiber material entered flat-bed laminator 30, 30' and the pressure applied by rollers 42 adhered the squares of the first fiber web to the second fiber web.
- the pressure from rollers 42 and the heat of heating portion 38 did not melt the crystalline component of the binder material, if any crystalline component was present in the binder material.
- the two-ply fiber web formed of the cut squares of the first fiber web and the continuous roll of the second fiber web was then wound onto a roll after passing through flatbed laminator 30, 30' and adhered together.
- the temperature of heating portion 38 of flatbed laminator 30, 30' was then increased to a temperature within the melting point range of the crystalline component within the binder material, if any crystalline component was present.
- the roll of the two-ply fiber material was then unrolled and the two-ply fiber material passed through flat-bed laminator 30, 30' . Because the temperature of heating portion 38 was within the melting point range of the crystalline component with the binder material, compaction or densification was imparted to the two-ply fiber material when passing through rollers 42.
- the two-ply fiber material was cut into squares and ballistic samples were produced by stacking 52 layers of the two-ply fiber material. The total areal density of each sample, or the total weight per area of multiple layers of the fabric, was 0.89 pounds/ft 2 .
- Comparative Example 1, Example 1, and Example 2 were each soaked in salt water at a concentration of 3.5% sea salt in tap waterfor 24 hours. Comparative Example 1, Example 1 and Example 2 were hung to drip dry for 15 minutes. Next, Comparative Example 1, Example 1 and Example 2 were each placed onto a clay block or platform, as disclosed further in NIJ STD 0101.06 Level III, and 357 Magnum SJHP Remington shots were fired at Comparative Example 1, Example 1 and Example 2 at a velocity of 1430 +/- 30 ft/sec.
- Example 1 contains a fluorocarbon amorphous component and carnauba wax crystalline component.
- Example B Bimodal Binder Material with Varying Concentrations of Amorphous and Crystalline Components
- Binder ( oiiipoiienl ( on i pa i tij i
- Comparative Example 1 which was not a bimodal binder, had the lowest V50 velocity compared to Examples 1, 2, and 3. As such, the samples of Examples 1-3 were able to withstand bullets shot at higher velocities without the bullet fully penetrating the sample. Additionally, Example 1, which contained 15% of the crystalline component, and Example 3, which contained 40% of the crystalline component, each had similar V50 velocities.
- Example C Bimodal Binder Material with Varying Crystalline Components
- each sample of Comparative Example 1 and Examples 1-6 were each placed onto a clay block or platform, as disclosed further in NIJ STD 0101.06 Level III, and 9 mm shots were fired at each sample of Comparative Example 1 and Examples 1-6 at varying velocities shown in Table 6. More particularly, Table 6 provides a theoretical velocity, V50, at which 50% of the bullets stopped within Comparative Example 1 and Examples 1-6 and 50%) of the bullets completely penetratedComparative Example 1 and Examples 1-6. For example, to determine the V50 velocity, a plurality of shots were fired at each sample of Comparative Example 1 and Examples 1-6 at varying velocities to determine the velocity range at which a bullet completely penetrated the sample and a velocity range at which a bullet partially penetrated a sample. These shot groupings on each sample underwent statistical analysis to determine the V50 velocity for each sample of Comparative Example 1 and Examples 1-6 tested.
- Comparative Example 1 which was not a bimodal binder, had the lowest V50 velocity compared to Examples 1-6. As such, the samples of Examples 1-6 were able to withstand bullets shot at higher velocities without the bullet fully penetrating the sample. Additionally, Example 3, which contained microcrystalline wax, had the greatest V50.
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Laminated Bodies (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112017020608A BR112017020608A2 (pt) | 2015-03-26 | 2016-03-21 | compósito com resistência balística, e método para formar compósito com resistência balística |
CN201680030194.7A CN107635763A (zh) | 2015-03-26 | 2016-03-21 | 防弹复合材料 |
JP2017550155A JP2018513954A (ja) | 2015-03-26 | 2016-03-21 | 耐弾性複合材料 |
KR1020177031063A KR20180011457A (ko) | 2015-03-26 | 2016-03-21 | 탄도 저항성 복합체 재료 |
EP16769487.6A EP3274649A4 (fr) | 2015-03-26 | 2016-03-21 | Matériau composite à résistance balistique |
CA2980540A CA2980540A1 (fr) | 2015-03-26 | 2016-03-21 | Materiau composite a resistance balistique |
MX2017012079A MX2017012079A (es) | 2015-03-26 | 2016-03-21 | Material mixto resistente a balas. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562138548P | 2015-03-26 | 2015-03-26 | |
US62/138,548 | 2015-03-26 | ||
US15/060,862 | 2016-03-04 | ||
US15/060,862 US20160281272A1 (en) | 2015-03-26 | 2016-03-04 | Ballistic resistant composite material |
Publications (1)
Publication Number | Publication Date |
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WO2016154102A1 true WO2016154102A1 (fr) | 2016-09-29 |
Family
ID=56976559
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2016/023387 WO2016154102A1 (fr) | 2015-03-26 | 2016-03-21 | Matériau composite à résistance balistique |
Country Status (10)
Country | Link |
---|---|
US (1) | US20160281272A1 (fr) |
EP (1) | EP3274649A4 (fr) |
JP (1) | JP2018513954A (fr) |
KR (1) | KR20180011457A (fr) |
CN (1) | CN107635763A (fr) |
BR (1) | BR112017020608A2 (fr) |
CA (1) | CA2980540A1 (fr) |
MX (1) | MX2017012079A (fr) |
TW (1) | TW201710574A (fr) |
WO (1) | WO2016154102A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11530513B2 (en) * | 2018-07-20 | 2022-12-20 | Honeywell International Inc. | Ballistic translation efficiency of high performance fibers |
WO2020148639A1 (fr) * | 2019-01-14 | 2020-07-23 | Tata Advanced Materials Limited | Procédé de fabrication de couche de protection d'article vestimentaire |
IT202100005618A1 (it) * | 2021-03-10 | 2022-09-10 | Saati Spa | Materiale composito fibrorinforzato e metodo ed impianto per la sua produzione |
IT202100005624A1 (it) * | 2021-03-10 | 2022-09-10 | Saati Spa | Materiale in rotolo anticoltello, metodo ed impianto per la sua produzione |
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US20090068453A1 (en) * | 2006-10-11 | 2009-03-12 | Sengshiu Chung | Impact-resistant lightweight polymeric laminates |
US20100170637A1 (en) * | 2007-02-05 | 2010-07-08 | Alenia Aeronautica S.P.A. | Pre-impregnated material with semi-crystalline matrix and amorphous surface layer |
US7994075B1 (en) | 2008-02-26 | 2011-08-09 | Honeywell International, Inc. | Low weight and high durability soft body armor composite using topical wax coatings |
US8017530B1 (en) | 2007-03-28 | 2011-09-13 | Honeywell International Inc. | Environmentally resistant ballistic composite based on a fluorocarbon-modified matrix binder |
US20120141720A1 (en) * | 2010-06-11 | 2012-06-07 | E. I. Du Pont De Nemours And Company | Enhanced Flexible Lightweight Ballistic, Stab and Spike resistant Materials |
US20120167751A1 (en) * | 2007-08-01 | 2012-07-05 | Ardiff Henry G | Composite ballistic fabric structures for hard armor applications |
WO2012118518A1 (fr) | 2010-06-11 | 2012-09-07 | E. I. Du Pont De Nemours And Company | Mélanges polymères utiles dans des applications balistiques |
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US2958685A (en) * | 1957-08-09 | 1960-11-01 | Du Pont | Polymers of perfluoropropylene |
GB1577012A (en) * | 1973-12-17 | 1980-10-15 | Galt G S | Plastics armour |
CA1335913C (fr) * | 1987-12-15 | 1995-06-13 | Louis Henry Miner | Element composite rigide |
ITMI20030295A1 (it) * | 2003-02-19 | 2004-08-20 | Citterio Flli Spa | Materiale composito flessibile resistente alla penetrazione |
AU2005301309A1 (en) * | 2004-05-28 | 2006-05-11 | Addison Closson Adhesive Textiles, Inc. | Method of forming adhesives mixtures and ballistic composites utilizing the same |
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2016
- 2016-03-04 US US15/060,862 patent/US20160281272A1/en not_active Abandoned
- 2016-03-21 JP JP2017550155A patent/JP2018513954A/ja not_active Ceased
- 2016-03-21 KR KR1020177031063A patent/KR20180011457A/ko unknown
- 2016-03-21 MX MX2017012079A patent/MX2017012079A/es unknown
- 2016-03-21 WO PCT/US2016/023387 patent/WO2016154102A1/fr active Application Filing
- 2016-03-21 EP EP16769487.6A patent/EP3274649A4/fr not_active Withdrawn
- 2016-03-21 CN CN201680030194.7A patent/CN107635763A/zh active Pending
- 2016-03-21 BR BR112017020608A patent/BR112017020608A2/pt not_active Application Discontinuation
- 2016-03-21 CA CA2980540A patent/CA2980540A1/fr not_active Abandoned
- 2016-03-24 TW TW105109292A patent/TW201710574A/zh unknown
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US4544694A (en) | 1982-12-27 | 1985-10-01 | American Hoechst Corporation | Extrusion lubricant composition and process |
US20090068453A1 (en) * | 2006-10-11 | 2009-03-12 | Sengshiu Chung | Impact-resistant lightweight polymeric laminates |
US20100170637A1 (en) * | 2007-02-05 | 2010-07-08 | Alenia Aeronautica S.P.A. | Pre-impregnated material with semi-crystalline matrix and amorphous surface layer |
US8017530B1 (en) | 2007-03-28 | 2011-09-13 | Honeywell International Inc. | Environmentally resistant ballistic composite based on a fluorocarbon-modified matrix binder |
US20120167751A1 (en) * | 2007-08-01 | 2012-07-05 | Ardiff Henry G | Composite ballistic fabric structures for hard armor applications |
US7994075B1 (en) | 2008-02-26 | 2011-08-09 | Honeywell International, Inc. | Low weight and high durability soft body armor composite using topical wax coatings |
US20120141720A1 (en) * | 2010-06-11 | 2012-06-07 | E. I. Du Pont De Nemours And Company | Enhanced Flexible Lightweight Ballistic, Stab and Spike resistant Materials |
WO2012118518A1 (fr) | 2010-06-11 | 2012-09-07 | E. I. Du Pont De Nemours And Company | Mélanges polymères utiles dans des applications balistiques |
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Also Published As
Publication number | Publication date |
---|---|
MX2017012079A (es) | 2018-02-21 |
JP2018513954A (ja) | 2018-05-31 |
US20160281272A1 (en) | 2016-09-29 |
TW201710574A (zh) | 2017-03-16 |
BR112017020608A2 (pt) | 2018-06-26 |
EP3274649A4 (fr) | 2018-10-31 |
CA2980540A1 (fr) | 2016-09-29 |
CN107635763A (zh) | 2018-01-26 |
EP3274649A1 (fr) | 2018-01-31 |
KR20180011457A (ko) | 2018-02-01 |
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