Claims
- 1. An article of manufacture, comprising:
- (a) at least one network comprising fibers selected from the group of extended chain polyolefin fibers, extended chain polyvinyl alcohol fibers and extended chain poly acrylonitrile fibers; and
- (b) a low modulus elastomeric material which substantially coats said fibers and has a tensile modulus (measured at 23.degree. C.) of less than about 6,000 psi (41,300 kPa).
- 2. An article as recited in claim 1, wherein said fibers have a tensile modulus of at least about 500 g/denier and an energy-to-break of at least about 22 J/g.
- 3. An article as recited in claim 1, wherein said fibers have a tensile modulus of at least about 1000 g/denier and an energy-to-break of at least 50 J/g.
- 4. An article as recited in claim 1 wherein said fibers have a tensile modulus of at least about 1300 g/denier and an energy-to-break of at least about 55 J/g.
- 5. An article as recited in claim 1, wherein said network is a non-woven network.
- 6. An article as recited in claim 1, wherein said network is a woven network.
- 7. An article as recited in claim 1, wherein said elastomeric material comprises an elastomer having a glass transition temperature of less than about 0.degree. C.
- 8. An article as recited in claim 7, wherein said elastomer has a glass transition temperature of less than about -40.degree. C.
- 9. An article as recited in claim 7, wherein said elastomer has a glass transition temperature of less than about -50.degree. C.
- 10. An article as recited in claim 1, wherein said elastomeric material has tensile modulus of less than about 5,000 psi.
- 11. An article as recited in claim 1, wherein said elastomeric material has a tensile modulus of less than about 1,000 psi.
- 12. An article as recited in claim 1, wherein said elastomeric material has a tensile modulus of less than about 500 psi.
- 13. An article as recited in claim 1, wherein said fibers are ECPE fibers having a weight average molecular weight of at least about 500,000 and a tenacity of at least about 15 g/denier.
- 14. An article as recited in claim 1, wherein said article is comprises a plurality of networks each defining a layer.
- 15. An article as recited in claim 14, wherein said layers have an arrangement in which the fiber alignment directions in selected layers are rotated with respect to the fiber alignment direction of another layer.
- 16. An article as recited in claim 1, wherein a plurality of said fibers are grouped together to form a yarn and a plurality of the yarns are arranged to form the network.
- 17. An article as recited in claim 1, wherein said network is a plain weave network.
- 18. An article as recited in claim 1, wherein said low modulus elastomeric material comprises less than about 10 vol % of each coated fiber network.
- 19. An article as recited in claim 1, wherein said elastomeric material consists essentially of a polystyrene-polyisoprene-polystyrene, tri-block copolymer extended chain polyethylene strips.
- 20. An article as recited in claim 1, wherein said elastomeric material consists essentially of a polystyrene-polyisoprene-polystyrene, tri-block copolymer.
- 21. An article as recited in claim 1, wherein said network of fibers is comprised of high molecular weight, extended chain polyethylene strips.
- 22. An article as recited in claim 21, wherein said strips are woven to form the network.
- 23. An article as recited in claim 1 wherein the coating comprises between about 0.1 and about 30% (by weight of fibers) of the coated fiber network.
- 24. An article as recited in claim 1 wherein the aspect ratio of the fiber is at least about 5:1.
- 25. An article as recited in claim 1 wherein the aspect ratio of the fiber is at least about 50:1.
- 26. An article as recited in claim 1 wherein the fiber comprises at least about 70% by volume of the coated fiber network.
- 27. A fiber comprising a polymer having a weight average molecular weight of at least about 500,000, a modulus of at least about 200 g/denier and a tenacity of at least about 10 g/denier and coated with an elastomeric material having a tensile modulus (measured at about 25.degree. C.) not greater than about 6000 psi.
- 28. The fiber of claim 27 wherein the coating is between about 0.1 and about 60% by weight of the fiber.
- 29. The fiber of claim 27 wherein the fiber has an aspect ratio of at least about 5:1.
- 30. The fiber of claim 27 wherein said polymer is selected from the group of polyolefin fiber, polyacrylonitrile fiber and polyvinyl alcohol fiber.
- 31. The fiber of claim 30 wherein the elastomeric material consists essentially of an elastomer.
REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of copending application Ser. No. 704,848 filed Feb. 25, 1985, now abandoned.
Ballistic resistant articles such as bulletproof vests, curtains, mats, raincoats and umbrellas containing high strength fibers are known. Fibers conventionally used include aramid fibers such as poly(phenylenediamine terephthalamide), nylon fibers, glass fibers and the like. For many applications, such as vests or parts of vests, the fibers are used in a woven or knitted fabric.
In "The Application of High Modulus Fibers to Ballistic Protection" R. C. Laible et al., J. Macromol. Sci.-Chem. A7(1), pp. 295-322 1973, it is indicated on p. 298 that a fourth requirement is that the textile material have a high degree of heat resistance; for example, a polyamide material with a melting point of 255.degree. C. appears to possess better impact properties ballistically than does a polyolefin fiber with equivalent tensile properties but a lower melting point.
J. W. S. Hearle, et al.; "Ballistic Impact Resistance of Multi-Layer Textile Fabrics," NTIS Acquisition No. AD A127641, (1981); disclose that coatings did not improve the ballistic performance of Kevlar 29 fabric. C. E. Morris, et al.; Contract No. A 93 B/189 (1980); disclose that the addition of a rubber matrix to a Kevlar fabric seriously reduced its ballistic performance. W. Stein; "Construction and Action of Bullet Resistant Vests," Melli and Textilberichte, 6/1981; discloses that coatings produced no improvement in ballistic resistance. R. C. Laible; "Fibrous Armor", Ballistic Materials and Penetration Mechanics, Elsevier Scientific Publishing Co. (1980); discloses on page 81 that attempts to raise the ballistic resistance of polypropylene yarns to the level predicted from the yarn stress-strain properties by the application of selected coatings were unsuccessful.
The present invention provides an improved, flexible fabric which is particularly useful as, ballistic-resistant "soft" armor. The fabric is comprised of at least one a network layer of high strength, extended chain polyolefin (ECP) fibers selected from the group consisting of extended chain polyethylene (ECPE) and extended chain polypropylene (ECPP) fibers, extended chain polyvinyl alcohol (PVA) fiber, and extended chain polyacrylonitrile (PAN) fiber. The fiber of the network is coated with a low modulus elastomeric material which has a tensile modulus of less than about 6,000 psi (41,300 kPa). Preferably, the fibers have a tensile modulus of at least about 500 grams/denier and an energy-to-break of at least about 22 Joules/ gram.
Compared to conventional ballistic-resistant fabric structures, the fabric of the present invention can advantageously provide a selected level of ballistic protection while employing a reduced weight of protective material. Alternatively, the fabric of the present invention can provide increased ballistic protection when the article has a weight equal to the weight of a conventionally constructed piece of flexible, fabric-type armor.
For the purposes of the present invention, a fiber is an elongate body the length dimension of which is much greater than the transverse dimensions of width and thickness. Accordingly, the term fiber includes single filament, ribbon, strip, and the like having regular or irregular cross-section.
A fabric of the present invention includes at least one network comprised of a high strength, extended chain polyolefin (ECP) fibers selected from the group consisting of extended chain polyethylene and extended chain polypropylene fibers, extended chain PVA fiber and extended chain PAN fiber. The fibers of the network are coated with a low modulus elastomeric material which has a tensile modulus of less than about 6,000 psi (41,300 kPa), measured at room temperature.
U.S. Pat. Nos. 4,413,110, 4,440,711, 4,535,027 and 4,457,985 generally discuss the high strength, extended chain fiber, employed in the present invention, and the disclosures of these patents are hereby incorporated by reference to the extent not inconsistent herewith.
Suitable polyethylene fibers are those having a molecular weight of at least 500,000, preferably at least one million and more preferably between two million and five million. Such extended chain polyethylene (ECPE) fibers may be grown in solution such as described in U.S. Pat. No. 4,137,394 to Meihuzen et al., or U.S. Pat. No. 4,356,138 of Kavesh et al., issued Oct. 26, 1982, or a fiber spun from a solution to form a gel structure, as described in German Off. No. 3,004,699 and GB No. 2051667, and especially as described in Application Ser. No. 572,607 of Kavesh et al. filed Jan. 20, 1984 (see EPA 64,167, published Nov. 10, 1982). Depending upon the formation technique, the draw ratio and temperatures, and other conditions, a variety of properties can be imparted to these fibers. The tenacity of the fibers should be at least 15 grams/denier, preferably at least 20 grams/denier, more preferably at least 25 grams/denier and most preferably at least 30 grams/denier. Similarly, the tensile modulus of the fibers, as measured by an Instron tensile testing machine, is at least 300 grams/denier, preferably at least 500 grams/denier and more preferably at least 1,000 grams/denier and most preferably at least 1,500 grams/denier. These highest values for tensile modulus and tenacity are generally obtainable only by employing solution grown or gel fiber processes. Many of the fibers have melting points higher than the melting point of the polymer from which they were formed. Thus, for example, ultra-high molecular weight polyethylenes of 500,000, one million and two million generally have melting points in the bulk of 138.degree. C. The highly oriented polyethylene fibers made of these materials have melting points 7.degree.-13.degree. C. higher. Thus, a slight increase in melting point reflects the crystalline perfection of the fibers. Nevertheless, the melting points of these fibers remain substantially below nylon; and the efficacy of these fibers for ballistic resistant articles is contrary to the various teachings cited above which indicate temperature resistance as a critical factor in selecting ballistic materials.
Similarly, highly oriented extended chain polypropylene (ECPP) fibers of molecular weight at least 750,000, preferably at least one million and more preferably at least two million may be used. Such ultra-high molecular weight polypropylene may be formed into reasonably well oriented fibers by the techniques prescribed in the various references referred to above, and especially be the technique of U.S. Ser. No. 259,266, filed Apr. 30, 1981, and the continuations-in-part thereof, both of Kavesh et al. and commonly assigned. Since polypropylene is a much less crystalline material than polyethylene and contains pendant methyl groups, tenacity values achievable with polypropylene are generally substantially lower than the corresponding values for polyethylene. Accordingly, a suitable tenacity is at least 8 grams/denier, with a preferred tenacity being at least 11 grams/denier. The tensile modulus for the polypropylene is at least 160 grams/denier, preferably at least 200 grams/denier. The melting point of the polypropylene is generally raised several degrees by the orientation process, such that the polypropylene fiber preferably has a main melting point of at least 168.degree. C., more preferably at least 170.degree. C. The particularly preferred ranges for the above-described parameters can advantageously provide improved performance in the final article.
For improved ballistic resistance of the fabric article, the ECP fiber preferably has a tensile modulus which preferably is at least about 500 g/den, more preferably is at least about 1000 g/den and most preferable is at least about 1300 g/den. Additionally, the ECP fiber has an energy-to-break which preferably is at least about 22 J/g, more preferably is at least about 50 J/g and most preferably is at least 55 J/g.
As used herein, the terms polyethylene and polypropylene mean predominantly linear polyethylene and polypropylene materials that may contain minor amounts of chain branching or comonomers not exceeding 5 modifying units per 100 main chain carbon atoms, and that may also contain admixed therewith not more than about 25 wt % of one or more polymeric additives such as alkene-1-polymers; in particular, low density polyethylene, polypropylene or polybutylene, copolymers containing mono-olefins as primary monomers, oxidized polyolefins, graft polyolefin copolymers and polyoxymethylenes, or low molecular weight additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated therewith.
In the case of polyvinyl alcohol (PV-OH), PV-OH fiber of molecular weight of at least about 500,000, preferably at least about 750,000, more preferably between about 1,000,000 and about 4,000,000, and most preferably between about 1,500,000 and about 2,500,000 may be employed in the present invention. Particularly useful PV-OH fiber should have a modulus of at least about 300 g/denier, a tenacity of at least about 7 g/denier (preferably at least about 10 g/denier, more preferably at about 14 g/denier, and most preferably at least about 17 g/denier), and an energy to break of at least about 22 joules/g. PV-OH fibers having a weight average molecular weight of at least about 500,000, a tenacity of at least about 300 g/denier, a modulus of at least about 10 g/denier, and an energy to break of about 22 joules/g are more useful in producing a ballistic resistant article. PV-OH fiber having such properties can be produced, for example, by the process disclosed in U.S. patent application Ser. No. 569,818, filed Jan. 11, 1984, to Kwon et al., and commonly assigned.
In the case of polyacrylonitrile (PAN), PAN fiber of molecular weight of at least about 400,000, and preferably at least 1,000,000 may be employed. Particularly useful PAN fiber should have a tenacity of at least about 10 g/denier and an energy to break of at least about 22 joule/g. PAN fiber having a molecular weight of at least about 400,000, a tenacity of at least about 15-20 g/denier and an energy to break of at least about 22 joule/g is most useful in producing ballistic resistant articles; and such fibers are disclosed, for example, in U.S. Pat. No. 4,535,027.
In the fabrics of the invention, the fiber network can have various configurations. For example, a plurality of fibers can be grouped together to form a twisted or untwisted yarn. The fibers or yarn may be formed as a felt, knitted or woven (plain, basket, satin and crow feet weaves, etc.) into a network, or formed into a network by any of a variety of conventional techniques. For example, the fibers may be formed into woven or nonwoven cloth by conventional techniques.
A preferred embodiment of the present invention includes multiple layers of coated fiber networks. The layers individually retain the high flexibility characteristic of textile fabrics and remain separate from each other. The multilayer article exhibits the flexibility of plied fabrics, and is readily distinguished from composite structures described in co-pending U.S. patent application Ser. No. 691,048 of Harpell, et al. and entitled "Ballistic Resistant Composite Article". Vests and other articles of clothing comprised of multiple layers of fabric constructed in accordance with the present invention have good flexibility and comfort coupled with excellent ballistic protection.
The flexibility of the ballistic resistant fabric structures of the present invention is demonstrated by the following test: A 30 cm square fabric sample comprised of multiple fabric layers having a total areal density of 2 kg/m.sup.2 when clamped horizontally along one side edge, will drape so that the opposite side edge is at least 21 cm below the level of the clamped side.
The multiple layers of fabric may be stitched together to provide a desired level of ballistic protection; for example, as against multiple ballistic impacts. However, stitching can reduce the flexibility of the fabric.
The fibers or yarns are coated with a low modulus, elastomeric material comprising an elastomer coating with this material substantially increases the ballistic resistance of the network. The elastomeric material has a tensile modulus, measured at about 23.degree. C., of less than about 6,000 psi (41,300 kPa). Preferably, the tensile modulus of the elastomeric material is less than about 5,000 psi (34,500 kPa), more preferably, is less than 1,000 psi (6,900 kPa) and most preferably is less than about 500 psi (3,450 kPa) to provide even more improved performance. The glass transition temperature (Tg) of the elastomer of the elastomeric material (as evidenced by a sudden drop in the ductility and elasticity of the material) is less than about 0.degree. C. Preferably, the Tg of the elastomer is less than about -40.degree. C., and more preferably is less than about -50.degree. C. The elastomer also has an elongation to break (measured at about 23.degree. C.) of at least about 50%. Preferably, the elongation to break is at least about 100%, and more preferably, it is about 300% for improved performance.
Coated fibers may be arranged (in the same fashion as uncoated fibers) into woven, non-woven or knitted fabrics. The fabric layers may be arranged in parallel arrays and/or incorporated into multilayer fabric articles. Furthermore, the fibers, used either alone or with coatings, may be wound or connected in a conventional fashion.
The proportion of coating on the coated fiber may vary from relatively small amounts (e.g. 0.1% by weight of fibers) to relatively large amounts (e.g. 60% by weight of fibers), depending upon whether the coating material has any ballistic-resistant properties of its own (which is generally not the case) and upon the rigidity, shape, heat resistance, wear resistance, flammability resistance and other properties desired for the fabric. In general, ballistic resistant fabrics of the present invention containing coated fibers should have a relatively minor proportion of coating (e.g. 0.1-30%, by weight of fibers), since the ballistic-resistant properties are almost entirely attributable to the fiber. Nevertheless, coated fabrics with higher coating contents may be employed.
The coating may be applied to the fiber in a variety of ways. One method is to apply the neat resin of the coating material to the fibers either as a liquid, a sticky solid or particles in suspension or as a fluidized bed. Alternatively, the coating may be applied as a solution or emulsion in a suitable solvent which does not adversely affect the properties of the fiber at the temperature of application. While any liquid capable of dissolving or dispersing the coating polymer may be used, preferred groups of solvents include water, paraffin oils, aromatic solvents or hydrocarbon solvents, with illustrative specific solvents including paraffin oil, xylene, toluene and octane. The techniques used to dissolve or disperse the coating polymers in the solvents will be those conventionally used for the coating of similar elastomeric materials on a variety of substrates.
Other techniques for applying the coating to the fibers may be used, including coating of the high modulus precursor (gel fiber) before the high temperature stretching operation, either before or after removal of the solvent from the fiber. The fiber may then be stretched at elevated temperatures to produce the coated fibers. The gel fiber may be passed through a solution of the appropriate coating polymer (solvent may be paraffin oil, aromatic or aliphatic solvent) under conditions to attain the desired coating. Crystallization of the high molecular weight polyethylene in the gel fiber may or may not have taken place before the fiber passes into the cooling solution. Alternatively, the fiber may be extruded into a fluidized bed of the appropriate polymeric powder.
If the fiber achieves its final properties only after a stretching operation or other manipulative process, e.g. solvent exchanging, drying or the like, it is contemplated that the coating may be applied to the precursor material. In this embodiment, the desired and preferred tenacity, modulus and other properties of the fiber should be judged by continuing the manipulative process on the fiber precursor in a manner corresponding to that employed on the coated fiber precursor. Thus, for example, if the coating is applied to the xerogel fiber described in U.S. application Ser. No. 572,607 of Kavesh et al., and the coated xerogel fiber is then stretched under defined temperature and stretch ratio conditions, the applicable fiber tenacity and fiber modulus values would be the measured values of an uncoated xerogel fiber which is similarly stretched.
A preferred coating technique is to form network layer and then dip the layer into a bath of a solution containing the low modulus elastomeric coating material. Evaporation of the solvent produces an elastomeric material coated fiber network. The dipping procedure may be repeated several times as required to place a desired amount of elastomeric material coating on the network fibers.
A wide variety of elastomeric materials and formulations may be utilized in this invention. The essential requirement is that the elastomeric material have the appropriately low modulus. Representative examples of suitable elastomers of the elastomeric material have their structures, properties, formulations together with crosslinking procedures summarized in the Encyclopedia of Polymer Science, Volume 5 in the section "Elastomers-Synthetic" (John Wiley & Sons Inc., 1964). For example, any of the following elastomers may be employed: polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, polysulfide polymers, polyurethane elastomers, chlorosulfonated polyethylene, polychloroprene, plasticized polyvinylchloride using dioctyl phthate or other plasticers well known in the art, butadiene acrylonitrile elastomers, poly(isobutylene-co-isoprene), polyacrylates, polyesters, polyethers, fluoroelastomers, silicone elastomers, thermoplastic elastomers, copolymers of ethylene.
Particularly useful elastomers are block copolymers of conjugated dienes and vinyl aromatic monomers. 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. The polymers may be simple tri-block copolymers of the type A-B-A, multi-block copolymers of the type (AB),(n=2-10) or radial configuration copolymers of the type R-(BA),(x=3150); wherein A is a block from a polyvinyl aromatic monomer and B is a block from a conjugated diene elastomer. Many of these polymers are produced commercially by the Shell Chemical Co. and described in the bulletin "Kraton Thermoplastic Rubber", SC-68-81.
Most preferably, the low modulus elastomeric material consists essentially of at least one of the above-mentioned elastomers. The low modulus elastomeric materials may also include fillers such as carbon black, silica, etc. and may be extended with oils and vulcanized by sulfur, peroxide, metal oxide, or radiation cure systems using methods well known to rubber technologists. Blends of different elastomeric materials may be used together or one or more elastomer materials may be blended with one or more thermoplastics. High density, low density, and linear low density polyethylene may be cross-linked to obtain a coating matrix material of appropriate properties, either alone or as blends. In every instance, the modulus of the coating should not exceed about 6000 psi (41,300 kPa), preferably is less than about 5000 psi (34,500 kPa), more preferably is less than 1000 psi (6900 kPa), and most preferably is less than 500 psi (3450 kPa).
A coated yarn can be produced by pulling a group of fibers through the solution of low modulus elastomeric material to substantially coat each of the individual fibers, and then evaporating the solvent to form a coated yarn. The yarn can then be employed to form coated fabrics which in turn, can be used to form desired multilayer fabric structures.
Multilayer fabric articles may be constructed and arranged in a variety of forms. It is convenient to characterize the geometries of such multilayer fabric structures by the geometries of the fibers and then to indicate that substantially no matrix material, elastomeric or otherwise, occupies the region between fabric layers. One such suitable arrangement is a plurality of layers in which each layer is comprised of coated fibers arranged in a sheet-like array and successive layers of such fabrics are rotated with respect to the previous layer. An example of such multilayer fabric structures is a fine layered structure in which the second, third, fourth and fifth layers are rotated +45.degree., -45.degree., 90.degree. and 0.degree., with respect to the first layer, but not necessarily in that order. Other examples include multilayer fabrics with alternating fabric layers rotated 90.degree. with respect to each other.
In various forms of the fabric of the invention, the fiber network occupies different proportions of the total volume of the fabric layer. Preferably, however, the fiber network comprises at least about 50 volume percent of the fabric layer, more preferably between about 70 volume percent, and most preferably at least about 90 volume percent. Similarly, the volume percent of low modulus elastomer in a fabric layer is preferably less than about 15 Vol %, more preferably is less than about 10 Vol %, and most preferably is less than about 5 Vol %.
It has been discovered that coated fabric comprised of strip or ribbon (fiber with an aspect ratio, ratio of fiber width to thickness, of at least about 5) can be even more effective than other forms of fiber or yarn when producing ballistic resistant articles. In particular embodiments of the invention, the aspect ratio of the strip is at least 50, preferably is at least 100 and more preferably is at least 150 for improved performance. Surprisingly, even though an ECPE strip material had significantly lower tensile properties than the ECPE yarn material of the same denier but a generally circular cross-section, the ballistic resistance of the coated fabric constructed from ECPE strip was significantly higher than the ballistic resistance of the coated fabric constructed from the ECPE yarn.
Most screening studies of ballistic composites employ a 0.22 caliber, non-deforming steel fragment of specified weight (19 grains), hardness and dimensions (Mil-Spec. MIL-P-46593A(ORD)). Limited studies were made employing 0.22 caliber lead bullets weighing 40 grains. The protective power of a structure is normally expressed by citing the impacting velocity at which 50% of the projectiles are stopped, and is designated the V.sub.50 value.
Usually, a flexible fabric, "soft" armor is a multiple layer structure. The specific weight of the multilayer fabric article can be expressed in terms of the areal density (AD). This areal density corresponds to the weight per unit area of the multiple layer structure.
To compare structures having different V.sub.50 values and different areal densities, the following examples state the ratios of (a) the kinetic energy (Joules) of the projectile at the V.sub.50 velocity, to (b) the areal density of the fabric (kg/m.sup.2). This ratio is designated as the Specific Energy Absorption (SEA).
US Referenced Citations (4)
| Number |
Name |
Date |
Kind |
|
4403012 |
Harpell et al. |
Sep 1983 |
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4428998 |
Hawkinson |
Jan 1984 |
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4457985 |
Harpell et al. |
Jul 1984 |
|
|
4501856 |
Harpell et al. |
Feb 1985 |
|
Non-Patent Literature Citations (4)
| Entry |
| "The Application of High Modulus Fibers to Ballistic Protection", R. C. Laible et al, J. Macromel Sci. Chem. A7(1), pp. 295-322, (1973). |
| J. W. S. Hearle et al., "Ballistic Impact Resistance of Multi-Layer Textile Fabrics", NTIS Acquisition No. AD A127641, (1981). |
| W. Stein, "Construction and Action of Bullet Resistant Vests", Melli and Textilberichte, 6/1981. |
| R. C. Laible, "Fibrous Armor", Ballistic Materials and Penetration Mechanics, Elsevier Scientific Publishing Co., (1980), p. 81. |
Continuation in Parts (1)
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Number |
Date |
Country |
| Parent |
704848 |
Feb 1985 |
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Patent Grant
4650710
