WO2008140567A2 - Traitement par micro-ondes de matériaux composites pare-balles - Google Patents

Traitement par micro-ondes de matériaux composites pare-balles Download PDF

Info

Publication number
WO2008140567A2
WO2008140567A2 PCT/US2007/084531 US2007084531W WO2008140567A2 WO 2008140567 A2 WO2008140567 A2 WO 2008140567A2 US 2007084531 W US2007084531 W US 2007084531W WO 2008140567 A2 WO2008140567 A2 WO 2008140567A2
Authority
WO
WIPO (PCT)
Prior art keywords
fibers
microwave
fabric
temperature
fiber
Prior art date
Application number
PCT/US2007/084531
Other languages
English (en)
Other versions
WO2008140567A3 (fr
Inventor
Ashok Bhatnagar
Lori L. Wagner
Brian D. Arvidson
Henry G. Ardiff
Original Assignee
Honeywell International Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Honeywell International Inc. filed Critical Honeywell International Inc.
Priority to CA002669761A priority Critical patent/CA2669761A1/fr
Priority to EP07874269A priority patent/EP2089203A2/fr
Priority to MX2009005091A priority patent/MX2009005091A/es
Priority to JP2009537315A priority patent/JP2010525960A/ja
Publication of WO2008140567A2 publication Critical patent/WO2008140567A2/fr
Publication of WO2008140567A3 publication Critical patent/WO2008140567A3/fr
Priority to IL198620A priority patent/IL198620A0/en

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0485—Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
    • B29B13/023—Half-products, e.g. films, plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/08—Conditioning or physical treatment of the material to be shaped by using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0855—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0089—Impact strength or toughness

Definitions

  • the present invention relates to the production of moldable, ballistic resistant articles.
  • ballistic resistant fabrics are heated with microwave energy as an alternative to conventional preheating heating methods, reducing heating time and increasing production efficiency.
  • High strength fibers conventionally used include polyethylene fibers, para-aramid fibers such as poly(phenylenediamine terephthalamide), graphite fibers, nylon fibers, glass fibers and the like.
  • the fibers may be used in a woven or knitted fabric.
  • the fibers are encapsulated or embedded in a matrix material to form either rigid or flexible fabrics.
  • U.S. patents 4,623,574 and 4,748,064 disclose simple composite structures comprising high strength fibers embedded in an elastomeric matrix.
  • U.S. patent 4,650,710 discloses a flexible article of manufacture comprising a plurality of flexible layers comprised of high strength, extended chain polyolefin (ECP) fibers. The fibers of the network are coated with a low modulus elastomeric material.
  • U.S. patents 5,552,208 and 5,587,230 disclose an article and method for making an article comprising at least one network of high strength fibers and a matrix composition that includes a vinyl ester and diallyl phthalate.
  • patent 6,642,159 discloses an impact resistant rigid composite having a plurality of fibrous layers which comprise a network of filaments disposed in a matrix, with elastomeric layers there between. The composite is bonded to a hard plate to increase protection against armor piercing projectiles.
  • ballistic resistant articles are formed by molding a combination of fibers, any matrix composition and any additional polymeric layers in a desired configuration by subjecting the combination to heat and pressure for a particular mold cycle time.
  • the molding temperature is low enough to avoid damage to the component fibers of the ballistic resistant fabric.
  • the molding temperature is less than the melting point of the polymer from which the fibers are formed or the temperature at which fiber damage occurs.
  • molding temperatures of about 68 0 F (20 0 C) to about 293°F (145°C) are generally acceptable.
  • the fibers are affected after prolonged exposure to heat above 265°F (129°C), and SPECTRA® fibers melt at 300 0 F (149°C). Temperatures higher than 265°F may cause the filaments of the fibrous layers to deform, reducing their ballistic resistance properties.
  • Other fiber types may be able to tolerate higher molding temperatures.
  • the upper limitation of the temperature range is generally about 20 0 C to about 30 0 C higher than for extended chain polyethylene fibers.
  • common convection heating standard molding times range from about 20 to 60 minutes at a temperature range of about 176°F (8O 0 C) to about 293°F (145°C) and at a pressure of from about 10 psi (69 kPa) to about 10,000 psi (69,000 kPa).
  • common convection heating requires the molding machine to be pre-heated for at least 10 minutes prior to molding. Accordingly, there is a need in the art for a more efficient fabric molding process that can effectively form ballistic resistant articles at a relatively low temperature with a relatively short molding time.
  • the present invention provides a solution to this need in the art.
  • the invention presents a method of forming ballistic resistant articles with reduced heating time in preparation for molding of said articles.
  • Ballistic resistant fabrics such as Spectra Shield® fabrics manufactured by Honeywell International, Inc., are generally poor conductors of heat. Accordingly, a long pre-heating time is necessary before such fabrics are hot enough to be moldable into ballistic resistant articles. By reducing this pre-heating time, production efficiency can be significantly improved.
  • the invention provides a method of molding a ballistic resistant article comprising heating a ballistic resistant fabric with microwave energy followed by molding the heated fabric. By heating with microwave energy, the overall heating and molding time is significantly reduced.
  • the inventive process is more efficient than conventional heating techniques, and allows for considerably improved productivity.
  • Microwave processing avoids this problem by allowing short heating times and avoiding significant temperature gradients within the samples due to even distribution of microwave energy and heating uniformity.
  • the invention provides a method of forming an article comprising: a) providing a fabric comprising a plurality of fibers arranged in an array, said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; said fibers having an optional microwave-reactive composition thereon; and b) heating said fabric inside a microwave oven by subjecting the fabric to microwave energy sufficient to thereby heat the fibers or the optional microwave- reactive composition to at least about the softening temperature of the fibers or the softening temperature of the optional microwave-reactive composition; c) molding the heated fabric into an article while said fabric has a temperature of at least about the softening temperature of the fibers or the softening temperature of the optional microwave-reactive composition due to the application of microwave energy; and d) allowing the molded fabric to cool.
  • the invention also provides a method of forming a consolidated fiber network, said consolidated network of fibers comprising a plurality of fiber layers, each fiber layer comprising a plurality of fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; and said fibers having a polymeric matrix composition thereon; which consolidated fiber network is consolidated under heat and pressure, wherein the heat of consolidation is generated by the application of microwave energy sufficient to thereby heat the polymeric matrix composition to a temperature of at least about the softening temperature of polymeric matrix composition.
  • the invention further provides a ballistic resistant article comprising a ballistic resistant fabric, the ballistic resistant fabric comprising a plurality of fibers arranged in an array, said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; said fibers having a dry, microwave-reactive composition coated thereon, which microwave-reactive composition has been heated above its softening point temperature by the application of microwave energy.
  • Microwave ovens provide an effective way of uniformly heating many non- conductive materials, such as ballistic resistant fabrics.
  • Microwave processing of ballistic resistant fabrics provides desirable benefits, including economic benefits through the saving of energy and time, and increased process yield and throughput.
  • the materials produced herein ostensibly have uniquely uniform microstructures that are not achieved by other heating methods due to the even energy distribution and uniform heating from the microwave.
  • fabrics having superior ballistic penetration resistance describe those which exhibit excellent properties against high speed projectiles.
  • a "fiber" is an elongate body the length dimension of which is much greater than the transverse dimensions of width and thickness. The cross-sections of fibers for use in this invention may vary widely.
  • fibers may be circular, flat or oblong in cross-section. Accordingly, the term fiber includes filaments, ribbons, strips and the like having regular or irregular cross-section. They may also be of irregular or regular multi-lobal cross-section having one or more regular or irregular lobes projecting from the linear or longitudinal axis of the fibers. Most commonly, fibers are single lobed and have a substantially circular cross-section.
  • a “yarn” is a strand of interlocked fibers.
  • a "parallel array” describes an orderly parallel arrangement of fibers or yarns.
  • a fiber “layer” describes a planar arrangement of woven or non- woven fibers or yarns.
  • a fiber “network” denotes a plurality of interconnected fiber or yarn layers.
  • a fiber network can have various configurations.
  • the fibers or yarn may be formed as a felt or another woven, non- woven or knitted, or formed into a network by any other conventional technique.
  • a “fabric” may relate to either a woven or non-woven material, or a combination thereof.
  • the term “fabric” describes structures including multiple fibrous layers either before or after molding to form a composite.
  • a "high-strength, high tensile modulus fiber” is one which has a preferred tenacity of at least about 7 g/denier or more, a preferred tensile modulus of at least about 150 g/denier or more, both as measured by ASTM D2256 and preferably an energy-to-break of at least about 8 J/g or more.
  • the term "denier” refers to the unit of linear density, equal to the mass in grams per 9000 meters of fiber or yarn.
  • the term “tenacity” refers to the tensile stress expressed as force (grams) per unit linear density (denier) of an unstressed specimen.
  • the "initial modulus" of a fiber is the property of a material representative of its resistance to deformation.
  • tensile modulus refers to the ratio of the change in tenacity, expressed in grams-force per denier (g/d) to the change in strain, expressed as a fraction of the original fiber length (in/in).
  • high-strength, high tensile modulus fiber materials include extended chain polyolefin fibers, such as highly oriented, high molecular weight polyethylene fibers, particularly ultra-high molecular weight polyethylene fibers, and ultra-high molecular weight polypropylene fibers.
  • extended chain polyvinyl alcohol fibers extended chain polyacrylonitrile fibers
  • para- aramid fibers polybenzazole fibers, such as polybenzoxazole (PBO) and polybenzothiazole (PBT) fibers and liquid crystal copolyester fibers.
  • PBO polybenzoxazole
  • PBT polybenzothiazole
  • preferred fibers are extended chain polyethylenes having molecular weights of at least 500,000, preferably at least one million and more preferably between two million and five million.
  • extended chain polyethylene (ECPE) fibers may be grown in solution spinning processes such as described in U.S. patent 4,137,394 or 4,356,138, which are incorporated herein by reference, or may be spun from a solution to form a gel structure, such as described in U.S. patent 4,551,296 and 5,006,390, which are also incorporated herein by reference.
  • polyethylene fibers for use in the invention are polyethylene fibers sold under the trademark Spectra® from Honeywell International Inc. Spectra® fibers are well known in the art and are described, for example, in commonly owned U.S. patents 4,623,547 and 4,748,064 to Harpell, et al. Ounce for ounce, Spectra® high performance fiber is ten times stronger than steel, while also light enough to float on water. The fibers also possess other key properties, including resistance to impact, moisture, abrasion chemicals and puncture.
  • Suitable polypropylene fibers include highly oriented extended chain polypropylene (ECPP) fibers as described in U.S. patent 4,413,110, which is incorporated herein by reference.
  • ECPP extended chain polypropylene
  • PV-OH polyvinyl alcohol
  • PV-OH polyvinyl alcohol
  • PAN polyacrylonitrile
  • Suitable aramid (aromatic polyamide) or para-aramid fibers are commercially available and are described, for example, in U.S. patent 3,671,542.
  • useful poly(p-phenylene terephthalamide) filaments are produced commercially by Dupont corporation under the trade name of KEVLAR®.
  • poly(m-phenylene isophthalamide) fibers produced commercially by Dupont under the trade name NOMEX®.
  • Suitable polybenzazole fibers for the practice of this invention are commercially available and are disclosed for example in U.S. patents 5,286,833, 5,296,185, 5,356,584, 5,534,205 and 6,040,050, each of which are incorporated herein by reference.
  • Preferred polybenzazole fibers are ZYLON® brand fibers from Toyobo Co.
  • Suitable liquid crystal copolyester fibers for the practice of this invention are commercially available and are disclosed, for example, in U.S. patents 3,975,487; 4,118,372 and 4,161,470, each of which is incorporated herein by reference.
  • the other suitable fiber types for use in the present invention include glass fibers, fibers formed from carbon, fibers formed from basalt or other minerals, M5® fibers and combinations of all the above materials, all of which are commercially available.
  • M5® fibers are manufactured by Magellan Systems International of Richmond, Virginia and are described, for example, in U.S. patents 5,674,969, 5,939,553, 5,945,537, and 6,040,478, each of which is incorporated herein by reference.
  • a high-strength, high tensile modulus fiber is one which has a preferred tenacity of about 7 g/denier or more, a preferred tensile modulus of about 150 g/denier or more and a preferred energy-to-break of about 8 J/g or more, each as measured by ASTM D2256.
  • the tenacity of the fibers should be about 15 g/denier or more, preferably about 20 g/denier or more, more preferably about 25 g/denier or more and most preferably about 30 g/denier or more; the fibers preferably also have a tensile modulus of about 300 g/denier or more, more preferably about 400 g/denier or more, more preferably about 500 g/denier or more, more preferably about 1,000 g/denier or more and most preferably about 1,500 g/denier or more.
  • Fibers with increased ballistic protection properties also have a preferred energy- to-break of about 15 J/g or more, more preferably about 25 J/g or more, more preferably about 30 J/g or more and most preferably have an energy-to-break of about 40 J/g or more.
  • These combined high strength properties are obtainable by employing well known solution grown or gel fiber processes.
  • U.S. patents 4,413,110, 4,440,711, 4,535,027, 4,457,985, 4,623,547 4,650,710 and 4,748,064 generally discuss the preferred high strength, extended chain polyethylene fibers employed in the present invention, and their disclosures are incorporated herein by reference.
  • Ballistic resistant fabrics may comprise one or more woven or non-woven fibrous layers, or a combination thereof.
  • Woven and non-woven fibrous layers may be formed using techniques that are commonly known in the art. Suitable non-woven fibrous layers include those comprising randomly oriented fibers, as with a felt, and a plurality of fibers or yarns arranged in a substantially parallel array.
  • the non- woven fibrous layers of the invention comprise a single-layer, consolidated network of fibers in an elastomeric or rigid polymer composition, referred to in the art as a matrix composition.
  • a "polymeric matrix composition” is a binder material that binds the fibers together after a consolidation or lamination step.
  • a “consolidated network” describes a consolidated combination of multiple fiber layers with the matrix composition.
  • a “single layer” structure refers to structure composed of one or more individual fiber layers that have been consolidated into a single unitary structure, wherein consolidation can occur via drying, cooling, heating, pressure or a combination thereof.
  • the consolidated network may also comprise a plurality of yarns that are coated with such a matrix composition, formed into a plurality of layers and consolidated into a single fabric layer.
  • the individual fibers forming the fabric layer may or may not be coated on, impregnated with, embedded in, or otherwise applied with a matrix composition, using well known techniques in the art.
  • the matrix composition may be applied to the high strength fibers either before or after the layers are formed, then followed by consolidating the matrix material-fibers combination together to form a multilayer complex.
  • the non- woven fibrous layers of the invention comprise: i) a plurality of layers, each layer comprising a plurality of unidirectionally aligned, parallel fibers, wherein said layers are cross-plied at an angle relative to a longitudinal fiber direction of each adjacent fiber layer; and wherein said fibers optionally have a polymeric matrix composition thereon; or ii) one or more layers comprising a plurality of randomly aligned fibers; and wherein said fibers optionally have a polymeric matrix composition thereon.
  • non-woven fabrics achieve excellent ballistic resistance when the individual component fiber layers are cross-plied such that the fiber alignment direction of one layer is rotated at an angle with respect to the fiber alignment direction of another layer, such that they are non- parallel.
  • a preferred structure has two fiber layers of the invention positioned together such that the longitudinal fiber direction of one layer is perpendicular to the longitudinal fiber direction of the other layer.
  • a five layered structure is formed in which the second, third, fourth and fifth layers are rotated +45°, - 45°, 90° and 0°, with respect to the first layer, but not necessarily in that order.
  • adjacent layers may be aligned at virtually any angle between about 0° and about 90° with respect to the longitudinal fiber direction of another layer, but the about 0° and about 90° fiber orientations are preferred. While the examples above illustrate fabrics that include either two or five individual fiber layers, such is not intended to be limiting.
  • the non-woven fibrous layers can be constructed via a variety of well known methods, such as by the methods described in U.S. patent 6,642,159. It should be understood that the single-layer consolidated networks of the invention may generally include any number of cross-plied layers, such as about 20 to about 40 or more layers as may be desired for various applications.
  • Woven fibrous layers may be formed using techniques that are well known in the art using any fabric weave, such as plain weave, crowfoot weave, basket weave, satin weave, twill weave and the like. Plain weave is most common. Prior to weaving, the individual fibers of each woven fibrous material may or may not be coated with a polymeric matrix composition in a similar fashion as the non-woven fibrous layers using the same matrix compositions as the non-woven fibrous layers.
  • the fabrics may comprise a hybrid combination of alternating or non- alternating woven and non- woven fibrous layers, such as a non- woven/woven/non-woven or woven/non-woven/woven structure.
  • Ballistic resistant fabrics may include any number of combined woven and/or non- woven layers, and each non-woven layer may comprise single-layer consolidated networks which incorporate multiple component layers. Adjacent layers may optionally be attached with an intermediate adhesive layer. Each woven layer, in particular, is preferably attached to an adjacent layer via an adhesive layer.
  • Suitable adhesives non-exclusively include elastomeric materials such as polyethylene, cross-linked polyethylene, chlorosulfonated polyethylene, ethylene copolymers, polypropylene, propylene copolymers, polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, polysulfide polymers, polyurethane elastomers, polychloroprene, plasticized polyvinylchloride using one or more plasticizers that are well known in the art (such as dioctyl phthalate), butadiene acrylonitrile elastomers, poly (isobutylene-co-isoprene), polyacrylates, polyesters, unsaturated polyesters, polyethers, fiuoroelastomers, silicone elastomers, copolymers of ethylene, thermoplastic elastomers, phenolics, polybutyrals, epoxy polymers
  • Particularly preferred adhesive compositions include methacrylate adhesives, cyanoacrylate adhesives, UV cure adhesives, urethane adhesives, epoxy adhesives, ethylene vinyl acetate adhesives and blends of the above materials.
  • the adhesive comprises a thermoplastic polymer, particularly ethylene vinyl acetate.
  • Such adhesives may be applied, for example, in the form of a hot melt, film, paste or spray, or as a two-component liquid adhesive.
  • the woven or non- woven fibrous layers of the invention may be prepared using a variety of matrix materials, including both low modulus, elastomeric matrix materials and high modulus, rigid matrix materials.
  • Suitable matrix materials non-exclusively include low modulus, elastomeric materials having an initial tensile modulus less than about 6,000 psi (41.3 MPa), and high modulus, rigid materials having an initial tensile modulus at least about 300,000 psi (2068 MPa), each as measured at 37°C by ASTM D638.
  • tensile modulus means the modulus of elasticity as measured by ASTM 2256 for a fiber and by ASTM D638 for a matrix material.
  • An elastomeric matrix composition may comprise a variety of polymeric and non- polymeric materials.
  • a preferred elastomeric matrix composition comprises a low modulus elastomeric material.
  • a low modulus elastomeric material has a tensile modulus, measured at about 6,000 psi (41.4 MPa) or less according to ASTM D638 testing procedures.
  • the tensile modulus of the elastomer is about 4,000 psi (27.6 MPa) or less, more preferably about 2400 psi (16.5 MPa) or less, more preferably 1200 psi (8.23 MPa) or less, and most preferably is about 500 psi (3.45 MPa) or less.
  • the glass transition temperature (Tg) of the elastomer is preferably less than about 0 0 C, more preferably the less than about -40 0 C, and most preferably less than about - 50 0 C.
  • the elastomer also has an preferred elongation to break of at least about 50%, more preferably at least about 100% and most preferably has an elongation to break of at least about 300%.
  • a wide variety of matrix materials and formulations having a low modulus may be utilized as the matrix.
  • Representative examples include polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymers, ethylene-propylene- diene terpolymers, polysulf ⁇ de polymers, polyurethane elastomers, chlorosulfonated polyethylene, polychloroprene, plasticized polyvinylchloride, butadiene acrylonitrile elastomers, poly(isobutylene-co-isoprene), polyacrylates, polyesters, polyethers, fluoroelastomers, silicone elastomers, copolymers of ethylene, and combinations thereof, and other low modulus polymers and copolymers curable below the melting point of the polyolefin fiber.
  • blends of different elastomeric materials, or blends of elastomeric materials with one or more thermoplastics are also preferred.
  • Block copolymers of conjugated dienes and vinyl aromatic monomers are particularly useful.
  • Butadiene and isoprene are preferred conjugated diene elastomers.
  • Styrene, vinyl toluene and t-butyl styrene are preferred conjugated aromatic monomers.
  • Block copolymers incorporating polyisoprene may be hydrogenated to produce thermoplastic elastomers having saturated hydrocarbon elastomer segments.
  • A is a block from a polyvinyl aromatic monomer
  • B is a block from a conjugated diene elastomer.
  • Many of these polymers are produced commercially by Kraton Polymers of Houston, TX and described in the bulletin "Kraton Thermoplastic Rubber", SC-68-81.
  • the most preferred matrix polymer comprises styrenic block copolymers sold under the trademark KRATON® commercially produced by Kraton Polymers.
  • the most preferred low modulus matrix composition comprises a polystyrene- polyisoprene-pol
  • Preferred high modulus, rigid matrix materials useful herein include materials such as a vinyl ester polymer or a styrene-butadiene block copolymer, and also mixtures of polymers such as vinyl ester and diallyl phthalate or phenol formaldehyde and polyvinyl butyral.
  • a particularly preferred rigid matrix material for use in this invention is a thermosetting polymer, preferably soluble in carbon- carbon saturated solvents such as methyl ethyl ketone, and possessing a high tensile modulus when cured of at least about 1x10 psi (6895 MPa) as measured by ASTM D638.
  • Particularly preferred rigid matrix materials are those described in U.S. patent 6,642,159, which is incorporated herein by reference.
  • the rigidity, impact and ballistic properties of the articles formed from the fabric composites of the invention are affected by the tensile modulus of the matrix polymer.
  • U.S. patent 4,623,574 discloses that fiber reinforced composites constructed with elastomeric matrices having tensile moduli less than about 6000 psi (41,300 kPa) have superior ballistic properties compared both to composites constructed with higher modulus polymers, and also compared to the same fiber structure without a matrix.
  • low tensile modulus matrix polymers also yield lower rigidity composites.
  • a suitable matrix composition may combine both low modulus and high modulus materials to form a single matrix composition.
  • Ballistic resistant fabrics may be used for various applications.
  • one or more fabrics of the invention may be arranged together to form flexible articles, including garments such as vests, pants, hats, or other articles of clothing, as is well known in the art.
  • the fabrics of the invention may also be formed into other personal protective articles such as helmets, or may be formed into protective shields, covers or blankets as desired.
  • Other common structures include flat, planar panels or customized shaped panels.
  • Molded fabrics may be used, for example, to fortify armored civilian vehicles for NIJ Level I, IIA, II, IIIA and III protection; as armored doors and roofs for police cars and other vehicles; as trauma pads or breast plate inserts for ballistic resistant vests for NIJ Level I, IIA, II, IIIA and III protection; for hand-held riot shields at NIJ Level I, IIA, II, IIIA and III protection, or for explosion management devices.
  • Multiple fabrics may be stacked or arranged in a bonded or non-bonded array. Bonding may be done using any conventional means in the art, such as stitching or bonding together with adhesive materials, other thermoplastic materials, or non- thermoplastic fibers or materials.
  • a fabric which may comprise any number of woven and/or non- woven layers (also referred to as "plies"), is heated or pre-heated to a desired molding temperature which allows it to be formed into a shaped article or panel.
  • the heated fabric is either shaped or compressed in a suitable molding apparatus, typically under pressure.
  • Typical molding pressures range from about 50 psi to about 5000 psi, more commonly from about 200 psi to about 1500 psi.
  • the molding step may take from about 4 seconds to about 45 minutes.
  • the fabric is heated in a microwave oven instead of by any other traditional heating method.
  • Microwave heating is a more efficient alternative to conventional heating because of its efficient volumetric heat production. Volumetric heating is defined as heating of the bulk, as opposed to transferring heat inward from the surface. Microwaves cause heating within a material by generating waves that excite molecules, causing them to rotate. Any molecule which is "polar" and has positive and negative ends will be rotated back and forth to align with the changing electric field of the waves in the oven. This rotation produces energy in the form of heat. Unlike conventional heating, this effect occurs simultaneously throughout the whole material being microwaved. Microwaves are electromagnetic waves in the frequency band from 300 MHz (3 x 108 cycles/second) to 300 GHz (3 ⁇ 1011 cycles/second).
  • All domestic microwave ovens and laboratory microwave processors operate at 2.45 GHz, corresponding to a wavelength of about 12.2 cm.
  • Industrial microwaves may operate at a 2.45 GHz frequency, and may also operate at lower frequencies, such as 900MHz or at greater frequencies, such as 10 GHz, and are generally available at 1000 watts to 3000 watts power.
  • the present invention is not restricted to any particular microwave frequency.
  • microwave processing systems consist of a microwave source, an applicator to deliver the power to the sample, and systems to control the heating.
  • Microwave generators are generally vacuum tubes or solid state devices. In microwave ovens, the tubes are generally rated at 1.5 kW. The tubes need a magnetic field in order to operate, and the field is supplied by either a permanent magnet or an electromagnet. The magnetron is the most common microwave source in materials processing applications.
  • microwave energy is applied to materials through multi-mode or single-mode microwave applicators, and temperature control is typically accomplished by varying input power or through pulsed sources.
  • the invention encompasses the use of any specialized microwave, including microwave ovens sufficient for use at home, industrial microwave ovens, and other unique microwave ovens, which may or may not use unique wavelengths for unique applications.
  • microwaves One significant factor limiting the potential use of microwaves for materials processing is the ability of materials to absorb microwave radiation (essentially high frequency radio waves). In contrast to conventional heating, microwaves penetrate the material with penetrating radiation. Whether or not heat is generated is determined by the specific dielectric properties of the material itself, such as the dielectric constant and dielectric loss tangent of the material.
  • microwave-power absorption is proportional to the water content of the material.
  • materials processing unlike microwaving of food, coupling of microwave energy is to atoms or atomic groups other than water.
  • many polymeric materials are not capable of absorbing microwave radiation.
  • many types of high strength fibers suitable for forming fabrics having superior ballistic penetration resistance may be capable of absorbing microwave radiation, others are not.
  • blending microwave absorbent additives with a polymeric matrix composition, or otherwise applying a microwave-reactive composition onto a material fabrics that are otherwise not capable of absorbing microwave radiation may be suitably processed with microwave radiation.
  • a microwave-reactive composition is a composition that absorbs sufficient microwave radiation to heat a fiber or a polymeric matrix composition to at least the softening temperature of the fiber or polymeric matrix composition, respectively.
  • polymeric materials are not capable of absorbing microwave radiation.
  • aramid fibers are sufficiently absorbent to microwave radiation, but polyethylene fibers are not, to heat a fabric to at least the softening temperature of the fibers, or more particularly, to at least about 60°C.
  • Spectra® polyethylene fibers have been found to be substantially transparent to microwave radiation.
  • Nylon, polyester and polyethylene naphthalate fibers are also at least partially microwave absorbing.
  • a fabric is formed from fibers that are transparent to microwave radiation, the fibers must be at least partially coated or contacted with a material that is sufficiently microwave absorbent to reach the softening temperature of the fibers or of the polymeric matrix composition.
  • a microwave absorbent material such as a microwave absorbent polymeric matrix composition
  • a polymeric matrix composition may be microwave absorbent by itself, or by being blended with a microwave-reactive additive.
  • a microwave-reactive additive will absorb the microwave energy and transfer it to the fibers.
  • Polar materials in particular, including polar polymeric fibers, polar polymeric matrix compositions and polar additives, are microwave reactive.
  • Conductive materials such as conductive fibers (e.g.
  • microwave-reactive additives non-exclusively include metal particles, including but not limited to magnetic particles, and metal powders, dielectric particles and dielectric powders, insoluble microwave-absorbing polymeric particles and non-dispersible microwave-absorbing polymeric particles. While solid metals are known to reflect microwave radiation, powder metals do absorb microwave radiation and can be heated.
  • Useful dielectric and polymeric powders include those that allow a polymeric matrix material to be heated to at least the softening point of the polymeric matrix material in a conventional microwave oven.
  • suitable materials are described in the book Microwave Processing of Materials III, edited by Ronald L. Beatty, Willard H. Sutton and Magdy F. Iskander, published by Materials Research Society, vol. 269 (October 1992), which is incorporated herein by reference.
  • materials described in U.S. patents 5,349,168 and 6,066,375 the disclosures of which are incorporated herein by reference.
  • metal powders such as powdered nickel, antimony, copper, molybdenum, bronze, iron, steel, chromium, tin, zinc, silver, gold, cobalt, tungsten, titanium, aluminum, including leafing aluminum powder, and alloys thereof.
  • Other useful additives are conductive materials such as carbon black, carbon fibers, metal fibers, and metal flakes, spheres or needles with sizes typically ranging from about 0.1 to 100 ⁇ m. These microwave-reactive additives are particularly useful when blended with a polymeric matrix composition.
  • conductive materials such as graphite and semi-conductive materials such as silicon carbides and magnetic material such as metal oxides (if available in particulate form) may also be utilized.
  • These materials are non-exclusive and generally any other additive material may be used that allows a polymeric matrix material or polymeric fiber to be heated to at least the softening temperature of the matrix or fiber in a conventional microwave oven at 2.45 GHz.
  • Such materials employed are in particulate form, and may be flakes or powders. The size of such particles will vary in accordance with a number of factors, including the particular material selected, the amount of heat to be generated, the manner in which the coating composition is to be applied, and the like.
  • microwave-reactive additives include oils, such as watch oil, as well as glycerol, silicon carbide, calcium nitride and calcium aluminates.
  • suitable additives include additives such as organic salts and inorganic salts having a high freedom of rotational, vibrational or translational movement, as well as non-conductive additives including metal oxides and metal dioxides, such as titanium dioxide, cobalt oxide, iron oxide, nickel oxide and manganese dioxide.
  • Suitable organic salts include monosodium glutamate (MSG), potassium citrate, calcium carbonate, potassium tartrate, ammonium formate, sodium bicarbonate, maganese carbonate, and combinations thereof, as well as many others.
  • Suitable inorganic salts include magnesium sulfate, calcium chloride, trisodium phosphate, ferrous sulphate, maganese sulphate, zinc sulphate, sodium metabisulphite, and combinations thereof, as well as many others. Also suitable are the materials disclosed in U.S. patent 4,219,361, the disclosure of which is incorporated by reference herein. These microwave-reactive additives are excited by microwaves of 2.45 GHz frequency and convert the microwave energy into thermal energy due to molecular friction.
  • the amount of additive may vary depending on the type of polymeric matrix and type of additive.
  • the microwave-reactive additive should comprise from about 0.01% to about 10.0% by weight of the polymeric matrix composition, more typically 0.01% to about 3.0% and most typically 0.01% to about 1.0% by weight of the polymeric matrix composition. Greater quantities may be used if determined to be necessary by one skilled in the art. However, in larger quantities, the additive will not stay in the matrix resin mix and will precipitate in the mixing tank when the additive is blended with the matrix resin. Depending on the temperature sensitivity of the composite's raw materials and the temperature required to achieve consolidation or reaction, both the ultimate temperature and the rate at which the composite reaches that temperature may need to be manipulated. Each specific combination would have its own preferred concentration of additive, and that concentration may vary greatly. In general, metals are more efficient than polymers, salts and other materials at reacting with and absorbing microwave radiation. Accordingly, smaller quantities of metallic based additives are typically needed.
  • Non-symmetrical polar molecules are easily rotated by microwave energy and heat up quickly.
  • the principal mechanism of coupling of microwave radiation to polymers is through dipolar reorientation by an electric field.
  • materials having a high concentration of a strong dipole are considered to be active absorbers of microwave energy and are particularly effective.
  • a dipole is a chemical arrangement where a positive charge and a negative charge are held at a fixed distance from each other. As a reaction of a material with microwave radiation proceeds, the type and concentration of dipole moments change, and a phase change occurs, changing the mobility of the dipoles.
  • a dipole moment is formed by adjacent groups having different electron withdrawing/donating properties resulting in a net charge or partial charge localization on one atom or group and can be viewed as a small, weak bar magnet.
  • Typical groups which form these dipoles include hydroxyl, amino, cyanate, etc.
  • the efficiency of this coupling is dependent on a number of factors, including dipole strength, the mobility of the dipole and the mass of the dipole. Small strong dipoles appear to couple to microwave radiation most efficiently and liquids couple the strongest, followed by rubbers, glassy polymers and crystalline materials.
  • Water-based resins, as well as solvent-based and 100% solids materials, which contain dipoles will absorb microwave radiation to some extent.
  • the strength of those dipoles, coupled with the concentration of those dipoles and the freedom of movement of the polymer, which allows the dipole to try to align itself with the oscillating magnetic field, causing friction and heat, will determine how much energy will be converted to heat.
  • a urethane linkage (-NH-COO-) is a strong dipole and polyurethane resins have a high concentration of these groups. Accordingly, polyurethane-containing matrix polymers are very effective.
  • Polymers containing carboxylic acid groups, also a dipole are also preferred.
  • Other preferred polymers include poly-electrolytes, ionomers, polyvinyl alcohol, polyvinyl butyral, silicones and polyamides.
  • polymers that have weaker dipoles or lower concentrations of dipoles non-exclusively include acrylics, ethylene vinyl acetate and ethylene acrylic acid. These materials are active to some extent with the magnitude of the warming related to the strength and concentration of the dipoles. Also suitable are blends of matrix polymers, such as a two-phase matrix of an active resin dispersed in a non-active resin, allowing the non-active resin to be processed with microwave energy.
  • the selection of the most effective microwave-reactive additive is generally dependent upon the frequency, power and duration of the microwave energy to be absorbed. It is known that heating is accelerated by ionic effects and the specific heat of a composite material. For example, oils are useful materials because of their low specific heat. Many factors also contribute to the minimum amount of microwave-reactive additive required. Highly active materials will generally require a lower weight or volume percentage. Synergistic compositions (some absorbed free water, induced dipoles in other constituents of the composite, etc.) will reduce the required level of active component. Lower targeted process temperatures would also require lower levels of highly active component, or higher levels of a lower absorbing material.
  • the minimum amount of microwave-reactive additive required will be less than about 10% by weight of the fabric, more preferably, less than 10% by weight of the polymeric matrix composition. More preferably, the quantity of microwave-reactive additive will be from about 1% to about 6% by weight, more preferably from about 3% to about 6% by weight of the polymeric matrix composition, or by weight of the fabric if no matrix is present. If the microwave-reactive additive is dispersed as a mixture in a solvent, mixture will typically include about 70% to about 80% by weight of the solvent.
  • a fabric is heated inside a microwave oven by subjecting the fabric to microwave energy sufficient to thereby heat the fibers or the optional microwave-reactive composition to at least about the softening temperature of the fibers or of the optional microwave-reactive composition.
  • microwave energy sufficient to thereby heat the fibers or the optional microwave-reactive composition to at least about the softening temperature of the fibers or of the optional microwave-reactive composition.
  • the ballistic resistant fabric and optional microwave-reactive composition be completely dry and free of volatile substances.
  • the material should be heated to a temperature less than a temperature at which the material is degraded or burned.
  • the fabric is molded or consolidated into an article while said fabric has a temperature of at least about the softening temperature of the fibers or the softening temperature of the optional microwave-reactive composition, if present.
  • the term "immediately thereafter" means that the fabric is molded or consolidated while still at or above the softening temperature due to microwave generated heat. Thereafter, the heated fabric is molded into an article while said fabric has a temperature of at least about the softening temperature of the fibers or the softening temperature of the optional microwave-reactive composition, if present. Alternately, the fabric may be heated and molded consecutively in a single multifunctional apparatus having both heating and molding capabilities.
  • the process is conducted such that molding is commenced while the fabric retains sufficient microwave generated heat to allow the fabric to be molded into any desired shape or form, and allowing the fabric to retain said shape if so intended. Finally, the molded fabric is allowed to cool.
  • a fabric of the invention must be heated until it reaches a temperature suitable for molding.
  • the minimum molding temperature of a fabric is typically determined by the softening temperature point of either the polymeric matrix composition or the softening temperature point of the fibers if no matrix composition is present.
  • the softening point of plastics may be measured by the ASTM Dl 525 Vicat Softening Temperature testing method, which covers determination of the temperature at which a specified needle penetration occurs when specimens are subjected to specified controlled test conditions. More particularly, in this testing method, a flat-ended needle loaded with a specified mass is placed in direct contact with a test specimen. The specimen and needle are heated at a permissible rate, and the temperature at which the needle has penetrated to a depth of 1 ⁇ 0.01 mm is recorded as Vicat softening temperature.
  • Suitable minimum molding temperatures typically range from about 60 0 C to about 180 0 C, but vary depending on the particular fiber type, and may be beyond this range.
  • Spectra® polyethylene fibers are affected after prolonged exposure to heat above 265°F (129.4°C) and melt at 300 0 F (148.9°C). Accordingly, Spectra® polyethylene fibers are preferably heated to greater than about 200 0 F (93.3°C) but less than about 257°F (125°C).
  • the heating step commonly adds an additional 10 to 30 minutes to the fabric processing time and requires pre-heating of the convection oven. This heating time is substantially reduced by microwaving the fabric.
  • the exposure time to microwave energy should be enough to sufficiently heat the fabric to the desired temperature, while brief enough to avoid degradation of the fibers.
  • the fabric is capable of being heated in a microwave oven to 200 0 F or greater within three minutes.
  • the complete molded fabrics of the invention comprise a combination of fibers, an optional matrix composition, optional intermediate adhesive layers and an optional microwave sensitive material.
  • the proportion of fibers preferably comprises from about 45% by weight to about 95% by weight of the fabric, more preferably from about 60% to about 90% by weight of the fabric, and most preferably from about 65 to about 85% by weight of the composite.
  • the matrix composition and/or optional adhesive may also include other additives such as fillers, such as carbon black or silica, may be extended with oils, or may be vulcanized by sulfur, peroxide, metal oxide or radiation cure systems as is well known in the art.
  • various parameters such as the number and type of fabric layers and the type of matrix may be controlled.
  • 2 fabric layers i.e. two woven fibrous layers, or two single layer, consolidated networks of non- woven, unidirectional fibers, each formed from two fiber layer plies cross-plied at 0°/90°, having a rubber layer on either outer surface of the combined fabric.
  • fabrics including 14 fabric layers and 10 fabric layers, respectively are preferred.
  • the fabrics of the invention are capable of being heated to a temperature of at least about 60 0 C by microwave radiation in a microwave oven.
  • the microwave oven may operate at any frequency and at any microwave power setting.
  • fabrics of the invention are capable of being heated in a microwave oven to 200°F (93.3 0 C) or greater within three minutes.
  • Spectra Shield® (“SS”) non-woven fabric samples formed with Spectra® fibers (1300-denier, type 1000), and KRATON® styrene-isoprene-styrene (SIS) polymeric matrix resin (KRATON® D-1161 : 40 wt. % supplied solids, diluted to 16 wt. % solids content applied onto fabric) or SANCURE® 12929 polyurethane matrix resin (commercially available from Noveon, Inc. of Cleveland, Ohio, a subsidiary of the Lubrizol Corporation).
  • the samples were made with 20 ⁇ 2 wt. % resin content, and had a non-woven, cross-plied Spectra Shield® material (0°, 90° construction).
  • the KRATON® polymeric matrix material failed to reach a temperature of about 113 0 F when subjected to microwave radiation at the specified conditions, much lower than the softening point of the KRATON® polymer. Accordingly, KRATON® polymer alone is insufficiently microwave absorbent to generate the minimum amount of heat required for molding of Spectra Shield® material.
  • the tested polymeric matrix polymers were:
  • Example 17 Airflex® 4500, an amide-modified ethylene-vinyl chloride copolymer available from Air Products and Chemicals, Inc.
  • Example 18 PermaxTM 230, a polyurethane resin available from Noveon, Inc.
  • Example 19 Hycar® 26523, an acrylic available from Noveon, Inc.
  • Example 20 Hycar® 26-1475, an acrylic available from Noveon, Inc.
  • Example 21 Hycar® 26-1199, an acrylic available from Noveon, Inc.
  • Example 22 Sancure® 20023, a polyurethane resin available from Noveon, Inc.
  • Example 23 Good-Rite® SB-1168, a carboxyl -modified styrene-butadiene- styrene copolymer available from Noveon, Inc.
  • Example 24 Daran® SLl 12, a PVdC polymer available from W. R. Grace & Co.
  • Example 25 PermaxTM 803, an acrylic-PVdC copolymer available from Noveon, Inc.
  • Example 26 Sancure® 777, a polyurethane resin available from Noveon, Inc.
  • Example 27 Sancure® 843, a polyurethane resin available from Noveon, Inc.
  • Example 28 Dispercoll® U53, a polyurethane resin available from Bayer AG.
  • Example 29 Vycar® 460X251 , a PVC copolymer available from Noveon, Inc.
  • Example 30 Sancure® 20025, a polyurethane resin available from Noveon, Inc.
  • Example 31 Butvar® RS-261 , a polyvinylbutyral available from Solutia, Inc.
  • Example 32 Sancure® 2026, a polyurethane resin available from Noveon, Inc.
  • the samples Prior to subjecting samples to microwave radiation, the samples were heated in an oven to remove any water or other volatile components in the resin dispersion. The samples were initially dried in an oven at 150 0 F (65.56°C) for five days. Once microwave testing commenced, some samples popped indicating the presence of residual water or other volatiles. These samples were then placed back into the oven for another five days at 200 0 F (93.33 0 C) to complete the removal of any water and/or volatiles.
  • a circular 1" (2.54 cm) thick section of ST YROFO AMTM was placed onto the carousel of a 1500 watt residential-use microwave oven. This STYROFOAMTM was used to isolate any heat generated by the sample under evaluation from any heat generated by the ceramic carousel plate.
  • Tempilstik® temperature indicators manufactured by Illinois Tool Works Inc. of Illinois, were used to evaluate temperature thresholds.
  • the desired temperature ranges were tested using two Tempilstik crayons with temperature ratings below the targeted temperature and two crayons with activation ranges above the targeted temperature.
  • each of the four samples of consolidated fabric were marked with one of the four temperatures. Shavings were scraped from one of the crayons onto the fabric sample that has the appropriate temperature writing on its surface. This was also done with the other three crayons and the other three samples.
  • the microwave oven was closed, set to the desired power level, a duration time was set and the microwave heating was initiated.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)

Abstract

L'invention concerne la production d'articles pare-balles. Avant le moulage, on chauffe le tissu pare-balles par énergie micro-ondes au lieu d'utiliser des procédés de chauffage à préchauffage classiques, réduisant de la sorte le temps de chauffage et augmentant l'efficacité de production.
PCT/US2007/084531 2006-11-15 2007-11-13 Traitement par micro-ondes de matériaux composites pare-balles WO2008140567A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002669761A CA2669761A1 (fr) 2006-11-15 2007-11-13 Traitement par micro-ondes de materiaux composites pare-balles
EP07874269A EP2089203A2 (fr) 2006-11-15 2007-11-13 Traitement par micro-ondes de matériaux composites pare-balles
MX2009005091A MX2009005091A (es) 2006-11-15 2007-11-13 Procesamiento con microondas de compuestos balisticos.
JP2009537315A JP2010525960A (ja) 2006-11-15 2007-11-13 弾道複合体のマイクロ波加工
IL198620A IL198620A0 (en) 2006-11-15 2009-05-07 Microwave processing of ballistic composites

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59982606A 2006-11-15 2006-11-15
US11/599,826 2006-11-15

Publications (2)

Publication Number Publication Date
WO2008140567A2 true WO2008140567A2 (fr) 2008-11-20
WO2008140567A3 WO2008140567A3 (fr) 2009-03-12

Family

ID=40002801

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2007/084531 WO2008140567A2 (fr) 2006-11-15 2007-11-13 Traitement par micro-ondes de matériaux composites pare-balles

Country Status (8)

Country Link
EP (1) EP2089203A2 (fr)
JP (1) JP2010525960A (fr)
CN (1) CN101594973A (fr)
CA (1) CA2669761A1 (fr)
IL (1) IL198620A0 (fr)
MX (1) MX2009005091A (fr)
TW (1) TW200844291A (fr)
WO (1) WO2008140567A2 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011156577A1 (fr) * 2010-06-11 2011-12-15 E. I. Du Pont De Nemours And Company Matériaux de flexibilité et de légèreté supérieure résistants aux impacts balistiques, aux armes tranchantes et aux perforations
WO2012098154A1 (fr) * 2011-01-18 2012-07-26 Teijin Aramid B.V. Article pare-balles comprenant une résine de styrène butadiène et procédé de fabrication dudit article
WO2014124876A1 (fr) 2013-02-14 2014-08-21 Teijin Aramid Gmbh Article balistique lourd et procédé pour fabriquer ledit article
WO2017212394A1 (fr) * 2016-06-07 2017-12-14 Aseo S.R.L. Procédé de fabrication de skis, au moyen de matériaux thermoformables ayant une structure porteuse à base de fibres de carbone, moules de thermoformage pour un tel produit, skis obtenus par ce procédé
US11040466B2 (en) 2017-06-27 2021-06-22 Koninklijke Philips N.V. Inductively heated mold for personal use
US11355733B2 (en) 2017-10-23 2022-06-07 Lg Chem, Ltd. Optical film having antistatic layers, optical film manufacturing method, and organic light-emitting electronic device manufacturing method
US11502272B2 (en) 2017-10-23 2022-11-15 Lg Chem, Ltd. Optical film having antistatic layers, optical film preparation method and organic light-emitting electronic device preparation method

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8256019B2 (en) * 2007-08-01 2012-09-04 Honeywell International Inc. Composite ballistic fabric structures for hard armor applications
US20150011666A1 (en) * 2012-01-13 2015-01-08 Johnson Controls Technology Company Systems and methods for manufacturing foam parts
KR102012753B1 (ko) 2017-03-29 2019-08-21 주식회사 엘지화학 탄소섬유 제조용 전구체 섬유, 이의 제조방법 및 이를 이용한 탄소섬유의 제조방법
KR102192357B1 (ko) 2017-10-23 2020-12-17 주식회사 엘지화학 광학 필름, 및 광학 필름을 이용한 유기발광전자장치의 제조 방법
KR102192363B1 (ko) 2017-10-23 2020-12-17 주식회사 엘지화학 광학 필름, 및 광학 필름을 이용한 유기발광전자장치의 제조 방법
KR102147418B1 (ko) 2018-04-27 2020-08-24 주식회사 엘지화학 탄소섬유 제조용 전구체 섬유의 안정화 방법 및 이를 이용한 탄소섬유의 제조방법
KR102115655B1 (ko) * 2018-05-25 2020-06-05 (재)한국건설생활환경시험연구원 3d 프린터용 다층구조 빌드시트 및 그 제조방법
US11207863B2 (en) 2018-12-12 2021-12-28 Owens Corning Intellectual Capital, Llc Acoustic insulator
US11666199B2 (en) 2018-12-12 2023-06-06 Owens Corning Intellectual Capital, Llc Appliance with cellulose-based insulator
KR102618963B1 (ko) 2019-06-07 2023-12-29 주식회사 엘지화학 탄소섬유 제조 장치
CN113400501A (zh) * 2021-06-23 2021-09-17 周新宇 一种高分子厨卫板材及其制备方法
CN113619003A (zh) * 2021-08-17 2021-11-09 成都正西液压设备制造有限公司 一种用于smc材料模压成型前工序的带预热自动上料机

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5173138A (en) * 1990-08-08 1992-12-22 Blauch Denise A Method and apparatus for the continuous production of cross-plied material
EP0620410A1 (fr) * 1993-04-02 1994-10-19 AlliedSignal Inc. Blindage composite souple
US6004123A (en) * 1989-12-06 1999-12-21 C.A. Lawton Company Apparatus for making preforms
WO2006005983A2 (fr) * 2003-11-26 2006-01-19 Hardin Montgomery G B Materiau fournissant une protection contre les chocs
WO2006049651A2 (fr) * 2004-05-28 2006-05-11 Addison Closson Adhesive Textiles, Inc. Procede d'elaboration de melanges adhesifs et composites balistiques les utilisant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6004123A (en) * 1989-12-06 1999-12-21 C.A. Lawton Company Apparatus for making preforms
US5173138A (en) * 1990-08-08 1992-12-22 Blauch Denise A Method and apparatus for the continuous production of cross-plied material
EP0620410A1 (fr) * 1993-04-02 1994-10-19 AlliedSignal Inc. Blindage composite souple
WO2006005983A2 (fr) * 2003-11-26 2006-01-19 Hardin Montgomery G B Materiau fournissant une protection contre les chocs
WO2006049651A2 (fr) * 2004-05-28 2006-05-11 Addison Closson Adhesive Textiles, Inc. Procede d'elaboration de melanges adhesifs et composites balistiques les utilisant

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011156577A1 (fr) * 2010-06-11 2011-12-15 E. I. Du Pont De Nemours And Company Matériaux de flexibilité et de légèreté supérieure résistants aux impacts balistiques, aux armes tranchantes et aux perforations
CN103370596B (zh) * 2011-01-18 2016-07-06 帝人芳纶有限公司 包含苯乙烯丁二烯树脂的耐冲击制品和生产所述制品的方法
WO2012098154A1 (fr) * 2011-01-18 2012-07-26 Teijin Aramid B.V. Article pare-balles comprenant une résine de styrène butadiène et procédé de fabrication dudit article
CN103370596A (zh) * 2011-01-18 2013-10-23 帝人芳纶有限公司 包含苯乙烯丁二烯树脂的耐冲击制品和生产所述制品的方法
KR20140014136A (ko) * 2011-01-18 2014-02-05 데이진 아라미드 비.브이. 스티렌 부타디엔 수지를 포함하는 방탄 제품 및 상기 제품을 제조하는 방법
US9134096B2 (en) 2011-01-18 2015-09-15 Teijin Aramid B.V. Ballistic resistant article comprising a styrene butadiene resin and process to manufacture said article
KR101879566B1 (ko) * 2011-01-18 2018-07-19 데이진 아라미드 비.브이. 스티렌 부타디엔 수지를 포함하는 방탄 제품 및 상기 제품을 제조하는 방법
RU2578255C2 (ru) * 2011-01-18 2016-03-27 Тейджин Арамид Б.В. Пуленепробиваемое изделие, включающее сополимер стирола и бутадиена, и способ изготовления указанного изделия
WO2014124876A1 (fr) 2013-02-14 2014-08-21 Teijin Aramid Gmbh Article balistique lourd et procédé pour fabriquer ledit article
AU2014218035B2 (en) * 2013-02-14 2017-03-23 Teijin Aramid Gmbh Hard-ballistic article and process to manufacture said article
KR20150124444A (ko) * 2013-02-14 2015-11-05 데이진 아라미드 게엠베하 고방탄 제품 및 상기 제품의 제조 방법
KR102083780B1 (ko) 2013-02-14 2020-04-16 데이진 아라미드 게엠베하 고방탄 제품 및 상기 제품의 제조 방법
WO2017212394A1 (fr) * 2016-06-07 2017-12-14 Aseo S.R.L. Procédé de fabrication de skis, au moyen de matériaux thermoformables ayant une structure porteuse à base de fibres de carbone, moules de thermoformage pour un tel produit, skis obtenus par ce procédé
US11040466B2 (en) 2017-06-27 2021-06-22 Koninklijke Philips N.V. Inductively heated mold for personal use
US11355733B2 (en) 2017-10-23 2022-06-07 Lg Chem, Ltd. Optical film having antistatic layers, optical film manufacturing method, and organic light-emitting electronic device manufacturing method
US11502272B2 (en) 2017-10-23 2022-11-15 Lg Chem, Ltd. Optical film having antistatic layers, optical film preparation method and organic light-emitting electronic device preparation method

Also Published As

Publication number Publication date
JP2010525960A (ja) 2010-07-29
TW200844291A (en) 2008-11-16
CA2669761A1 (fr) 2008-11-20
WO2008140567A3 (fr) 2009-03-12
CN101594973A (zh) 2009-12-02
MX2009005091A (es) 2009-06-03
EP2089203A2 (fr) 2009-08-19
IL198620A0 (en) 2010-02-17

Similar Documents

Publication Publication Date Title
WO2008140567A2 (fr) Traitement par micro-ondes de matériaux composites pare-balles
CA2631019C (fr) Protection contre la fragmentation
EP2561132B1 (fr) Performance balistique améliorée de fibres polymères
EP0197279B1 (fr) Matériau composite complexe à résistance pare-balles
EP1501673B1 (fr) Tissus balistiques lamines
KR101569803B1 (ko) 니트릴 고무 바인더에 기초한 내환경성 탄도 복합체
US4613535A (en) Complex composite article having improved impact resistance
CA2847370C (fr) Composite ud a haute resistance au cisaillement interlaminaire et faible signature de face arriere et processus pour sa fabrication
WO2008105754A2 (fr) Plastions retenus, plaques de blindage de véhicule et casques
WO2007067405A1 (fr) Blindage ignifuge
WO2008060650A2 (fr) Meilleure efficacité balistique en immersion liquide, par le biais de l'hybridation
US8759236B2 (en) Polyolefin fiber reinforced rubber
CA2497473C (fr) Materiau resistant a la penetration et articles fabriques avec celui-ci
JPH05501683A (ja) 高強力繊維で強化されたセラミック防護外装及び該防護外装製急断抵抗性物品
MX2008006667A (en) Frag shield

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780049946.5

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07874269

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2007874269

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 198620

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: 3060/DELNP/2009

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: MX/A/2009/005091

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2009537315

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2669761

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE