ENHANCED PHYSICAL AND ADHESION PROPERTIES AND THE PROCESS OF MAKING CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of co-pending United States Provisional Application Serial No. 61/531,302, filed on September 6, 2011, the disclosure of which is incorporated by reference herein in its entirety. This application also claims the benefit of co-pending United States Provisional Application Serial No. 61/566,320, filed on December 2, 2011, the disclosure of which is incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The invention pertains to methods for modifying high tenacity fibers without reducing the physical strength properties of the fibers. More particularly, the invention pertains to methods for modifying fibers with a plasma treatment or a corona treatment without reducing the physical strength properties of the fibers.

DESCRIPTION OF THE RELATED ART

Many different techniques are known for the fabrication of high tenacity fibers and filaments, including high molecular weight polyethylene fibers and filaments. In addition, ballistic resistant articles fabricated from composites comprising high tenacity synthetic fibers are well known. Articles such as bullet resistant vests, helmets, vehicle panels and structural members of military equipment are typically made from fabrics comprising high tenacity fibers such as SPECTRA® polyethylene fibers or KEVLAR® aramid fibers. For many applications, high tenacity fibers may be used in a woven or knitted fabric. For other applications, the fibers may be encapsulated or embedded in a polymeric matrix material and formed into non-woven fabrics. For example, U.S. patents 4,403,012, 4,457,985, 4,613,535, 4,623,574, 4,650,710,

4,737,402, 4,748,064, 5,552,208, 5,587,230, 6,642, 159, 6,841,492, 6,846,758, all of which are incorporated herein by reference, describe ballistic resistant composites which formed from high tenacity fibers, such as extended chain ultra-high molecular weight polyethylene ("UHMW PE") fibers. Each type of high tenacity fiber has its own unique characteristics and properties, and ballistic resistant composites fabricated from high tenacity fibers exhibit varying degrees of projectile penetration resistance and backface signature ("BFS"). Backface signature, also known in the art as backface deformation or trauma signature, is the measure of the depth of deflection of body armor resulting from a projectile impact.

One defining characteristic of a fiber is the ability of the fiber to bond with or adhere with surface coatings, including as resin coatings. Strong adhesion of polymeric binder materials is important in the manufacture of ballistic resistant fabrics. Poor adhesion of polymeric binder materials on the fiber surfaces may reduce fiber-fiber bond strength and fiber-binder bond strength and thereby cause united fibers to disengage from each other and/or cause the binder to delaminate from the fiber surfaces. This reduces the ballistic resistance properties, also known as anti-ballistic performance, of such composites and can result in catastrophic product failure. For example, as described in co-pending application Serial Nos. 61/531,233; 61/531,255;

61/531,268; 61/531,302; and 61/531,323, there is a direct correlation between backface signature and the tendency of the component fibers of a ballistic resistant composite to delaminate from each other and/or delaminate from fiber surface coatings as a result of a projectile impact. By improving the bond between a fiber surface and a fiber surface coating, the fiber- fiber disengagement and/or fiber-coating delamination effect are reduced, thereby increasing friction on the fibers and increasing projectile engagement with the fibers. This improvement in bond strength results in the improvement of composite structural properties, allowing the energy of a projectile impact to be dissipated in a manner that reduces the backface deformation of the composite.

As is known in the art, the ability of a fiber to bond with or adhere with surface coatings may be improved by corona treating or plasma treating the fibers. Corona treatment is a process in which a fiber is passed through a corona discharge station, thereby passing the fiber web through a series of high voltage electric discharges, which tend to act on the surface of the fiber web in a variety of ways, including pitting, roughing and introducing polar functional groups by way of partially oxidizing the surface of the fiber. A plasma treatment is similar to a corona treatment but differs from a corona treatment mainly in that a plasma treatment is conducted in a controlled, reactive atmosphere of gases, whereas in corona treatment the reactive atmosphere is air. These treatments modify the fibers, such as by ablating the fiber surface, pitting or roughening of the fiber surface, removing

contaminants from the fiber surface, oxidizing the fiber surface, polarizing the fiber surface, causing chain scission and molecular weight reduction of the polymer molecules at the fiber surface, and/or by crosslinking polymer chains near the fiber surface through free radical bonding. As a result of these modifications, the ability of subsequently applied materials to adsorb to, adhere to or bond to the fiber surface is enhanced, thereby reducing the tendency of fiber surface coatings to delaminate, and thereby reducing composite backface deformation upon projectile impact. However, it has now been recognized that the harsh conditions of plasma treating and corona treating are destructive of fiber tenacity. Data has shown that fiber tenacity pre-treatment is significantly greater than fiber tenacity post-treatment. This is undesirable because fiber penetration resistance is directly proportional to the physical strength of the fibers forming the composite, so a reduction in physical strength correlates with a decrease in V50 velocity, and achieving the desired improvements in BFS comes with a sacrifice of penetration resistance. Accordingly, there is an ongoing need in the art for a method to produce ballistic resistant composites having reduced backface signature without sacrificing superior V50 ballistic performance properties. The invention provides a solution to this need.

SUMMARY OF THE INVENTION The invention provides a process for producing a modified, high tenacity fiber which has been modified by a plasma treatment or modified by a corona treatment, said modified, high tenacity fiber having a tenacity of at least about 33 g/denier at ambient room temperature, said process comprising the steps of: a) providing a high tenacity fiber having a tenacity of at least about 33 g/denier at ambient room temperature, wherein said fiber has fiber surfaces and wherein said surfaces are at least partially covered by a fiber surface finish or wherein said fiber is substantially free of a fiber surface finish; b) where said fiber surfaces are at least partially covered by a fiber surface finish, removing at least a portion of the fiber surface finish from the fiber surfaces; and c) subjecting the high tenacity fiber to a plasma treatment or to a corona treatment within a chamber maintained at a non- vacuum pressure under conditions effective to modify the high tenacity fiber; thereby producing a modified, high tenacity fiber which has been modified by a plasma treatment or modified by a corona treatment, which modified high tenacity fiber has a tenacity of at least about 33 g/denier at ambient room temperature. The invention also provides a process for producing a modified polymeric fiber which has been modified by a plasma treatment or modified by a corona treatment, said process comprising the steps of: a) providing a polymeric fiber wherein said fiber has fiber surfaces and wherein said surfaces are at least partially covered by a fiber surface finish or wherein said fiber is substantially free of a fiber surface finish; b) where said fiber surfaces are at least partially covered by a fiber surface finish, removing at least a portion of the fiber surface finish from the fiber surfaces; and c) subjecting the polymeric fiber to a plasma treatment or to a corona treatment within a chamber maintained at a non- vacuum pressure under conditions effective to modify the polymeric fiber; thereby producing a modified fiber which has been modified by a plasma treatment or modified by a corona treatment. The invention further provides a process for producing a modified polymeric fiber which has been modified by a plasma treatment or modified by a corona treatment, said process comprising the steps of: a) providing a polymeric fiber having surfaces that are at least partially free of a fiber surface finish such that at least part of fiber surface is exposed and not covered by a fiber surface finish; and c) subjecting the polymeric fiber to a plasma treatment or to a corona treatment within a chamber maintained at a non- vacuum pressure under conditions effective to modify the polymeric fiber; thereby producing a modified fiber which has been modified by a plasma treatment or modified by a corona treatment.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of the invention, articles that have superior ballistic penetration resistance describe those which exhibit excellent properties against deformable projectiles, such as bullets, and against penetration of fragments, such as shrapnel.

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. The cross-sections of fibers for use in this invention may vary widely, and they may be circular, flat or oblong in cross-section. Thus the term "fiber" includes filaments, ribbons, strips and the like having regular or irregular cross-section, but it is preferred that the fibers have a substantially circular cross-section. As used herein, the term "yarn" is defined as a single strand consisting of multiple fibers. A single fiber may be formed from just one filament or from multiple filaments. A fiber formed from just one filament is referred to herein as either a "single-filament" fiber or a

"monofilament" fiber, and a fiber formed from a plurality of filaments is referred to herein as a "multifilament" fiber.

A "fiber layer" as used herein may comprise a single-ply of unidirectionally oriented fibers, a plurality of non-consolidated plies of unidirectionally oriented fibers, a plurality of consolidated plies of unidirectionally oriented fibers, a woven fabric, a plurality of consolidated woven fabrics, or any other fabric structure that has been formed from a plurality of fibers, including felts, mats and other structures, such as those comprising randomly oriented fibers. A "layer" describes a generally planar arrangement. Each fiber layer will have both an outer top surface and an outer bottom surface. A "single-ply" of unidirectionally oriented fibers comprises an arrangement of non-overlapping fibers that are aligned in a unidirectional, substantially parallel array. This type of fiber arrangement is also known in the art as a "unitape",

"unidirectional tape", "UD" or "UDT." As used herein, an "array" describes an orderly arrangement of fibers or yarns, which is exclusive of woven fabrics, and a "parallel array" describes an orderly parallel arrangement of fibers or yarns. The term "oriented" as used in the context of "oriented fibers" refers to the alignment of the fibers as opposed to stretching of the fibers. The term "fabric" describes structures that may include one or more fiber plies, with or without molding or consolidation of the plies. For example, a woven fabric or felt may comprise a single fiber ply. A non-woven fabric formed from unidirectional fibers typically comprises a plurality of fiber plies stacked on each other and consolidated. When used herein, a "single-layer" structure refers to any monolithic fibrous structure composed of one or more individual plies or individual layers that have been merged, i.e. consolidated by low pressure lamination or by high pressure molding, into a single unitary structure together with a polymeric binder material. By "consolidating" it is meant that the polymeric binder material together with each fiber ply is combined into a single unitary layer. Consolidation can occur via drying, cooling, heating, pressure or a combination thereof. Heat and/or pressure may not be necessary, as the fibers or fabric layers may just be glued together, as is the case in a wet lamination process. The term "composite" refers to combinations of fibers with at least one polymeric binder material. A "complex composite" as used herein refers to a consolidated combination of a plurality of fiber layers. As described herein, "non-woven" fabrics include all fabric structures that are not formed by weaving. For example, non-woven fabrics may comprise a plurality of unitapes that are at least partially coated with a polymeric binder material, stacked/overlapped and consolidated into a single-layer, monolithic element, as well as a felt or mat comprising non-parallel, randomly oriented fibers that are preferably coated with a polymeric binder composition. A fiber surface finish is typically applied to all fibers to facilitate their processability. To permit direct plasma or corona treatment of the fiber surfaces, it is necessary that existing fiber surface finishes be at least partially removed from the fiber surfaces, and preferably substantially completely removed from all or some of the fiber surfaces of some or all of the component fibers forming a fibrous composite. This removal of the fiber finish will also serve to enhance fiber- fiber friction and to permit direct bonding of resins or polymeric binder materials to the fiber surfaces, thereby increasing the fiber-coating bond strength. The at least partial removal of the fiber surface finish will preferably begin once all fiber drawing/stretching steps have been completed. The step of washing the fibers or otherwise removing the fiber finish will remove enough of the fiber finish so that at least some of the underlying fiber surface is exposed, although different removal conditions should be expected to remove different amounts of the finish. For example, factors such as the composition of the washing agent (e.g. water), mechanical attributes of the washing technique (e.g. the force of the water contacting the fiber; agitation of a washing bath, etc.), will affect the amount of finish that is removed. For the purposes herein, minimal processing to achieve minimal removal of the fiber finish will generally expose at least 10% of the fiber surface area. Preferably, the fiber surface finish is removed such that the fibers are predominantly free of a fiber surface finish. As used herein, fibers that are "predominantly free" of a fiber surface finish are fibers which have had at least 50% by weight of their finish removed, more preferably at least about 75% by weight of their finish removed. It is even more preferred that the fibers are substantially free of a fiber surface finish. Fibers that are "substantially free" of a fiber finish are fibers which have had at least about

90% by weight of their finish removed, and most preferably at least about 95% by weight of their finish removed, thereby exposing at least about 90% or at least about 95% of the fiber surface area that was previously covered by the fiber surface finish. Most preferably, any residual finish will be present in an amount of less than or equal to about 0.5% by weight based on the weight of the fiber plus the weight of the finish, preferably less than or equal to about 0.4% by weight, more preferably less than or equal to about 0.3% by weight, more preferably less than or equal to about 0.2% by weight and most preferably less than or equal to about 0.1% by weight based on the weight of the fiber plus the weight of the finish.

Depending on the surface tension of the fiber finish composition, a finish may exhibit a tendency to distribute itself over the fiber surface, even if a substantial amount of the finish is removed. Thus, a fiber that is

predominantly free of a fiber surface finish may still have a portion of its surface area covered by a very thin coating of the fiber finish. However, this remaining fiber finish will typically exist as residual patches of finish rather than a continuous coating. Accordingly, a fiber having surfaces that are predominantly free of a fiber surface finish preferably has its surface at least partially exposed and not covered by a fiber finish, where preferably less than 50% of the fiber surface area is covered by a fiber surface finish. The fibrous composites of the invention comprising fiber surfaces that are predominantly free of a fiber finish are then coated with a polymeric binder material. Where removal of the fiber finish has resulted in less than 50% of the fiber surface area being covered by a fiber surface finish, the polymeric binder material will thereby be in direct contact with greater than 50% of the fiber surface area.

Most preferably, the fiber surface finish is substantially completely removed from the fibers and the fiber surfaces are substantially completely exposed. In this regard, a substantially complete removal of the fiber surface finish is the removal of at least about 95%, more preferably at least about 97.5% and most preferably at least about 99.0% removal of the fiber surface finish, and whereby the fiber surface is at least about 95% exposed, more preferably at least about 97.5% exposed and most preferably at least about 99.0% exposed. Ideally, 100% of the fiber surface finish is removed, thereby exposing 100% of the fiber surface area. Following removal of the fiber surface finish, it is also preferred that the fibers are cleared of any removed finish particles prior to application of a polymeric binder material, resin or other adsorbate onto the exposed fiber surfaces. As processing of the fibers to achieve minimal removal of the fiber finish will generally expose at least about 10% of the fiber surface area, a comparable composite which has not been similarly washed or treated to remove at least a portion of the fiber finish will have less than 10% of the fiber surface area exposed, with zero percent surface exposure or substantially no fiber surface exposure.

Increasing fiber-coating bond strength also reduces the amount of binder needed to adequately bind the fibers together. This reduction in binder quantity allows a greater number of fibers to be included in a fabric, which allows for potentially producing lighter ballistic materials having improved strength. This also leads to improved stab resistance of the resulting fabric composites.

Any conventionally known method for removing fiber surface finishes is useful within the context of the present invention, including both mechanical and chemical techniques means. The necessary method is generally dependent on the composition of the finish. For example, in the preferred embodiment of the invention, the fibers are coated with a finish that is capable of being washed off with only water. Typically, a fiber finish will comprise a combination of one or more lubricants, one or more non-ionic emulsifiers

(surfactants), one or more anti-static agents, one or more wetting and cohesive agents, and one or more antimicrobial compounds. The finish formulations preferred herein can be washed off with only water. Mechanical means may also be employed together with a chemical agent to improve the efficiency of the chemical removal. For example, the efficiency of finish removal using de- ionized water may be enhanced by manipulating the force, direction velocity, etc. of the water application process.

Most preferably, the fibers are washed and/or rinsed with water as a fiber web, preferably using de-ionized water, with optional drying of the fibers after washing, without using any other chemicals. In other embodiments where the finish is not water soluble, the finish may be removed or washed off with, for example, an abrasive cleaner, chemical cleaner or enzyme cleaner. For example, U.S. patents 5,573,850 and 5,601,775, which are incorporated herein by reference, teach passing yarns through a bath containing a non-ionic surfactant (HOSTAPUR® CX, commercially available from Clariant

Corporation of Charlotte, N.C.), trisodium phosphate and sodium hydroxide, followed by rinsing the fibers. Other useful chemical agents non-exclusively include alcohols, such as methanol, ethanol and 2-propanol; aliphatic and aromatic hydrocarbons such as cyclohexane and toluene; chlorinated solvents such as di-chloromethane and tri-chloromethane. Washing the fibers will also remove any other surface contaminants, allowing for more intimate contact between the fiber and resin or other coating material. The preferred means used to clean the fibers with water is not intended to be limiting except for the ability to substantially remove the fiber surface finish from the fibers. In a preferred method, removal of the finish is accomplished by a process that comprises passing a fiber web through pressurized water nozzles to wash (or rinse) and/or physically remove the finish from the fibers. The fibers may optionally be pre-soaked in a water bath before passing the fibers through said pressurized water nozzles, and/or soaked after passing the fibers through the pressurized water nozzles, and may also optionally be rinsed after any of said optional soaking steps by passing the fibers through additional pressurized water nozzles. The washed/soaked/rinsed fibers are preferably also dried after washing/soaking/rinsing is completed. The equipment and means used for washing the fibers is not intended to be limiting, except that it must be capable of washing individual multifilament fibers/multifilament yarns rather than fabrics, i.e. before they are woven or formed into non-woven fiber layers or plies.

The removal of the fiber surface finish prior to fabric formation is especially intended herein for the production of non-woven fabrics that are formed by consolidating a plurality of fiber plies that comprise a plurality of

unidirectionally aligned fibers. In a typical process for forming non-woven unidirectionally aligned fiber plies, fiber bundles are supplied from a creel and led through guides and one or more spreader bars into a collimating comb, followed by coating the fibers with a polymeric binder material. Alternately the fibers can be coated before encountering the spreader bars, or they may be coated between two sets of spreader bars, one before and one after the coating section. A typical fiber bundle (e.g. a yarn) will have from about 30 to about 2000 individual filaments, each fiber typically including, but not limited to, from about 120 to about 240 individual filaments. The spreader bars and collimating comb disperse and spread out the bundled fibers, reorganizing them side-by-side in a coplanar fashion. Ideal fiber spreading results in the individual fibers, or even individual filaments, being positioned next to one another in a single fiber plane, forming a substantially unidirectional, parallel array of fibers with a minimal amount of fibers overlapping each other.

Removing the fiber surface finish before or during this spreading step may enhance and accelerate the spreading of the fibers into such a parallel array due to the physical interaction of the cleaning agent (e.g. water) with which the fibers/filaments interact. Following fiber spreading and collimating, the fibers of such a parallel array will typically contain from about 3 to 16 fiber ends per inch (1.2 to 6.3 ends per cm), depending on the fiber thickness. Accordingly, removal of the fiber surface finish achieves a dual benefit of enhancing fiber spreading and improves the bond strength of subsequently applied materials/adsorbates on the fiber surfaces.

After the fiber surface finish is removed to the desired degree, the fibers are subjected to either a plasma treatment or a corona treatment. Both the plasma treatment and the corona treatment will modify the fibers at the fiber surfaces, thereby further enhancing the adsorbability/bonding of a subsequently applied adsorbate (e.g. polymer/resin) on the fiber surfaces. Removal of the fiber finish allows these additional processes to act directly on the surface of the fiber and not on the fiber surface finish or on surface contaminants. Plasma treatment and corona treatment are each desirable for optimizing the interaction between the bulk fiber and fiber surface coatings to improve the anchorage of the coatings to fiber surfaces. This modified interaction can easily be seen in improvements in BFS. Corona treatment is a process in which a fiber is passed through a corona discharge station, thereby passing the fiber web through a series of high voltage electric discharges, which tend to act on the surface of the fiber web in a variety of ways, including pitting, roughing and introducing polar functional groups by way of partially oxidizing the surface of the fiber. Corona treatment typically oxidizes the fiber surface and/or adds polarity to the fiber surface. Corona treatment also acts by burning small pits or holes into the surface of the fiber. When the fibers are oxidizable, the extent of oxidation is dependent on factors such as power, voltage and frequency of the corona treatment. Residence time within the corona discharge field is also a factor, and this can be manipulated by corona treater design or by the line speed of the process. Suitable corona treatment units are available, for example, from Enercon Industries Corp., Menomonee Falls, Wis., from Sherman Treaters Ltd, Thame, Oxon., UK, or from Softal Corona & Plasma GmbH & Co of Hamburg, Germany.

In a preferred embodiment, the fibers are subjected to a corona treatment of from about 2 Watts/ft ² /min to about 100 Watts/ft ² /min, more preferably from about 5 Watts/ft ² /min to about 50 Watts/ft ² /min, and most preferably from about 20 Watts/ft ² /min to about 50 Watts/ft ² /min. Lower energy corona treatments from about 1 Watts/ft ² /min to about 5 Watts/ft ² /min are also useful but may be less effective. In addition to applying a charge to the fiber surface, a corona treatment may roughen the surface by pitting the surface of the fiber. In a plasma treatment, the fibers, typically as a fiber web, are passed through an ionized atmosphere in a chamber that is filled with an inert or non-inert gas, such as oxygen, argon, helium, ammonia, or another appropriate inert or non- inert gas, including combinations of the above gases, to thereby contact the fibers with a combination of neutral molecules, ions, free radicals, as well as ultraviolet light. At the fiber surfaces, collisions of the surfaces with charged particles (ions) result in both the transfer of kinetic energy and the exchange of electrons, etc. In addition, collisions between the surfaces and free radicals will result in similar chemical rearrangements. Chemical changes to the fiber substrate are also caused by bombardment of the fiber surface by ultraviolet light, which is emitted by excited atoms, and by molecules relaxing to lower states. As a result of these interactions, the plasma treatment may modify both the chemical structure of the fiber as well as the topography of the fiber surfaces. For example, like corona treatment, a plasma treatment may also add polarity to the fiber surface and/or oxidize fiber surface moieties. Plasma treatment may also serve to increase the surface energy of the fiber, reduce the contact angle, modify the crosslink density of the fiber surface thereby increasing hardness, melting point and the mass anchorage of subsequent coatings, and may add a chemical functionality to the fiber surface and potentially ablate the fiber surface. These effects are likewise dependent on the fiber chemistry, and are also dependent on the type of plasma employed.

The selection of gas is important for the desired surface treatment because the chemical structure of the surface is modified differently using different plasma gases. Such would be determined by one skilled in the art. It is known, for example, that amine functionalities may be introduced to a fiber surface using ammonia plasma, while carboxyl and hydroxyl groups may be introduced by using oxygen plasma. Accordingly, the reactive atmosphere may comprise one or more of argon, helium, oxygen, nitrogen, ammonia, and/or other gas known to be suitable for plasma treating of fabrics. The reactive atmosphere may comprise one or more of these gases in atomic, ionic, molecular or free radical form. For example, in a preferred continuous process of the invention, an array of fibers is passed through a controlled reactive atmosphere that preferably comprises argon atoms, oxygen molecules, argon ions, oxygen ions, oxygen free radicals, as well as other trace species. In a preferred embodiment, the reactive atmosphere comprises both argon and oxygen at concentrations of from about 90% to about 95% argon and from about 5% to about 10% oxygen, with 90/10 or 95/5 concentrations of argon/oxygen being preferred. In another preferred embodiment, the reactive atmosphere comprises both helium and oxygen at concentrations of from about 90% to about 95% helium and from about 5% to about 10% oxygen, with 90/10 or 95/5 concentrations of helium/oxygen being preferred. Another useful reactive atmosphere is a zero gas atmosphere, i.e. room air comprising about 79% nitrogen, about 20% oxygen and small amounts of other gases, which is also useful for corona treatment to some extent.

A plasma treatment differs from a corona treatment mainly in that a plasma treatment is conducted in a controlled, reactive atmosphere of gases, whereas in corona treatment the reactive atmosphere is air. The atmosphere in the plasma treater can be easily controlled and maintained, allowing surface polarity to be achieved in a more controllable and flexible manner than corona treating. The electric discharge is by radio frequency (RF) energy which dissociates the gas into electrons, ions, free radicals and metastable products. Electrons and free radicals created in the plasma collide with the fiber surface, rupturing covalent bonds and creating free radicals on the fiber surface. In a batch process, after a predetermined reaction time or temperature, the process gas and RF energy are turned off and the leftover gases and other byproducts are removed. In a continuous process, which is preferred herein, an array of fibers is passed through a controlled reactive atmosphere comprising atoms, molecules, ions and/or free radicals of the selected reactive gases, as well as other trace species. The reactive atmosphere is constantly generated and replenished, likely reaching a steady state composition, and is not turned off or quenched until the coating machine is stopped.

Plasma treatment may be carried out using any useful commercially available plasma treating machine, such as plasma treating machines available from Softal Corona & Plasma GmbH & Co of Hamburg, Germany; 4 State, Inc of Belmont California; Plasmatreat US LP of Elgin Illinois; Enercon Surface Treating Systems of Milwaukee, Wisconsin. Plasma treating may be conducted in a chamber maintained under a vacuum or in a chamber maintained at atmospheric conditions. When atmospheric systems are used, a fully closed chamber is not mandatory. Plasma treating or corona treating the fibers in a non-vacuum environment, i.e. in a chamber that is not maintained at either a full or partial vacuum, may increase the potential for fiber

degradation. This is because the concentration of the reactive species is proportional to the treatment pressure. This increased potential for fiber degradation may be countered by reducing the residence time in the treatment chamber. Treating fibers under a vacuum, coupled with the need to treat fibers through their fiber surface finish, results in the need for long treatment residence times. This undesirably causes a typical loss of fiber strength properties, such as fiber tenacity, of approximately 15% to 20%. The aggressiveness of the treatments may be reduced by reducing energy flux of the treatment, but this sacrifices the effectiveness of the treatments in enhancing bonding of adsorbates on the fibers, which limits improvements in BFS. However, it has also been unexpectedly found that when conducting the fiber treatments after at least partially removing the fiber finish, fiber tenacity loss is less than 5%, typically less than 2% or less than 1%, often no loss at all, and in some instances fiber strength properties actually increase, which is due to increased crosslink density of the polymeric fiber due to the direct treatment of the fiber surfaces. When conducting the fiber treatments after at least partially removing the fiber finish, the treatments are much more effective and may be conducted in less aggressive, non- vacuum environments at various levels of energy flux without sacrificing coating bond enhancement and BFS. In the most preferred embodiments of the invention, the high tenacity fibers are subjected to a plasma treatment or to a corona treatment in a chamber maintained at about atmospheric pressure or above atmospheric pressure. As a secondary benefit, plasma treatment under atmospheric pressure allows the treatment of more than one fiber at a time, whereas treatment under a vacuum is limited to the treatment of one fiber at a time. A preferred plasma treating process is conducted at about atmospheric pressure, i.e. 1 atm (760 mm Hg (760 torr)), with a chamber temperature of about room temperature (70°F-72°F). The temperature inside the plasma chamber may potentially change due to the treating process, but the temperature is generally not independently cooled or heated during treatments, and it is not believed to affect the treatment of the fibers as they rapidly pass through the plasma treater. The temperature between the plasma electrodes and the fiber web is typically approximately 100°C. The plasma treating process is preferably conducted under RF power at about 0.5 kW to about 3.5 kW, more preferably from about 1.0 kW to about 3.05 kW, and most preferably plasma treating is conducted using an atmospheric plasma treater set at 2.0 kW. This power is distributed over the width of the plasma treating zone (or the length of the electrodes) and this power is also distributed over the length of the substrate or fiber web at a rate that is inversely proportional to the line speed at which the fiber web passes through the reactive atmosphere of the plasma treater. This energy per unit area per unit time

(watts per square foot per minute or W/ft ² /min) or energy flux, is a useful way to compare treatment levels. Effective values for energy flux are preferably from about 0.5 to about 200 W/ft ² /min, more preferably from about 1 to about 100 W/ft ² /min, even more preferably from about 1 to about 80 W/ft ² /min, even more preferably from about 2 to about 40 W/fP/min, and most preferably from about 2 to about 20 W/ft ² /min. The total gas flow rate is approximately 16 liters/min, but this is not intended to be strictly limiting.

As the total gas flow rate is distributed over the width of the plasma treating zone, additional gas flow may be necessary with increases to the length/width of the plasma treating zone of the plasma treater. For example, a plasma treater having a treating zone width of 2x may need twice as much gas flow compared to a plasma treater having a treating zone width of lx. The plasma treatment time (or residence time) of the fiber is also is relative to the dimensions of the plasma treater employed and is not intended to be strictly limiting. In a preferred atmospheric system, the fibers are exposed to the plasma treatment with a residence time of from about ½ second to about three seconds, with an average residence time of approximately 2 seconds. A more appropriate measure is the amount of plasma treatment in terms of RF power applied to the fiber per unit area over time.

Additionally, composites and fabrics of the invention may comprise some fibers that are treated and some fibers that are not treated. For example, composites herein may be fabricated from some fibers that are corona treated and some fibers that are plasma treated. Each of these exemplary processes, through their action on the surface of the fiber, can be employed to modify, improve or reduce the interaction between the bulk fiber and subsequent coating materials, depending on fiber chemistry. The various treatment steps of the invention may be utilized as a recipe for manipulating the fibers in order to place the composite within the desired range for backface signature or other properties. If BFS testing determines that a particular composite has a worse BFS than desired, that is indicative that further fiber washing and/or further surface treatment should be conducted to further increase said properties to fall within the desired range.

The plasma and corona treatments will be conducted after the at least partial removal of the fiber surface finish but prior to the application of any binder/matrix resins or other surface adsorbates/coatings. Treating the exposed fiber surfaces immediately before coating the aligned fiber web with a polymeric binder material or resin is most preferred because it will cause the least disruption to the fiber manufacturing process and will leave the fiber in a modified and unprotected state for the shortest period of time. It is ideal to remove the fiber surface finish and treat the exposed fiber surfaces immediately after unwinding fibers from a fiber spool (wound fiber package) and aligning the fibers into a fiber web, followed by immediately coating or impregnating the fibers with a polymer/resin coating. This will also leave the fibers in a treated and uncoated state for the shortest length of time should there be considerations about the shelf-life or decay rate of the surface modification of the fiber. However, this is ideal primarily for causing the least disruption to the overall fabrication process, and not necessarily for achieving an improvement in BFS performance of the composite.

Fibrous composites produced according to the methods described herein have been found to exhibit excellent backface signature properties. Backface signature is a measure of the depth of deflection of either soft or hard armor into a backing material or into a user body due to a projectile impact. More specifically, BFS, also known in the art as "backface deformation", "trauma signature" or "blunt force trauma", is a measure of how much impact a projectile leaves under the armor once the armor stops the projectile from penetrating, indicating the potential blunt trauma experienced by the body underneath the armor. The reduction in backface deformation results from modifying the component fibers of the fibrous composites to enhance fiber- fiber engagement and/or reduce fiber-coating delamination tendency. The reduction in fiber- fiber disengagement and/or fiber-coating delamination upon projectile impact is optimized by plasma treating or corona treating the fibers after at least partially removing a pre-existing fiber surface finish from the fibers prior to processing the fibers into a fabric, wherein forming a fabric includes interconnecting the fibers to thereby form woven fabric layers, non- woven fabric layers or a non-woven fiber plies. The removal of fiber surface finishes prior to the formation of non-woven fabric layers or non-woven fiber plies, or prior to the weaving of woven fabrics, has not hereinbefore been known because the fiber surface finish is generally known as a necessary processing aid as described above. In the fabrication of non- woven fabrics, a fiber surface finish is generally required to reduce static build-up, prevent fiber tangling, lubricate the fiber to allow it to slide over loom components, and improve fiber cohesion during processing, including during fiber drawing steps. Plasma treating or corona treating the fibers after removing at least a portion of a pre-existing fiber surface finish from the fibers allows the exposed fiber surfaces to be treated directly, thereby modifying the fiber surfaces rather than conducting the treatments on the fiber finish. The reduction in fiber- fiber disengagement and/or fiber-coating delamination yields composites having correspondingly superior backface signature performance against high velocity projectiles. The improvement in backface signature is particularly evident when the component fibers are polyethylene fibers, which are naturally superior to other fibers in their ballistic resistance abilities but not necessarily in their structural properties. Treating the surfaces of polyethylene fibers as described above prior to the fabrication of polyethylene-based fabrics formed therefrom achieves a combination of structural properties, ballistic penetration resistance and backface signature resistance properties that are comparatively superior to any other fiber type, including aramid fibers.

In this regard, the fibrous composites of the invention have a preferred backface signature of less than about 6 mm as measured for a composite having an areal density of 2.0 psf when impacted with a 124-grain, 9 mm FMJ R projectile fired at a velocity of from about 427 m/s to about 445 m/s (1430 feet/second (fps) ± 30 fps), measured at room temperature. This is not to say that all fibrous composites or articles of the invention will have an areal density of 2.0 psf, nor that all fibrous composites or articles of the invention will have a BFS of 6 mm against such an FMJ RN projectile at said velocity. Such only identifies that composites fabricated according to the processes of the invention are characterized in that when fabricated into a 2.0 psf panel, that 2.0 psf panel will have a BFS of less than about 6 mm against such an FMJ RN projectile at said velocity when measured at approximately room temperature (appx. 70°F-72°F).

It should also be understood that the terms BFS, backface deformation, trauma signature and blunt force trauma are not measures of the depth of depression of the composite due to projectile impact, but rather are measures of the depth of depression in a backing material or into a user body due to projectile impact. This is particularly relevant for the study of hard armor, particularly helmet armor. Helmet BFS is typically tested by placing a prototype helmet on a metallic head form, where the helmet is held on the head form by a suspension system that separates the helmet from the head form by ½ inch (1.27 cm). Sections of the head form are filled with clay, and the depth of depression in those clay areas is measured as the BFS without including the ½ inch spacing depth in the measurement. This is done for the purpose of correlating the laboratory BFS testing with actual BFS experienced by a soldier in field use, where a typical helmet incorporates a typical 1/2 inch offset from the head, due to helmet interior padding or a suspension system/retention harness. The BFS of soft armor, on the other hand, is conventionally tested by placing the armor directly on the clay surface with no spacing, which is consistent with its position in actual field use. Accordingly, BFS depth measurements are relative to the test method used, and when comparing BFS depth measurements, it is necessary to identify whether or not the test method used required positioning the test sample directly on a backing material or spaced from the backing material. In this regard, all backface signature data in this application was measured using an apparatus described in co-pending patent application serial no. 61/531,233 with a 1/2 inch space between the 2.0 psf sample and a clay backing material. In the preferred embodiments of the invention, the fibrous composites of the invention have a more preferred backface signature of less than about 5 mm when impacted with a 124-grain, 9 mm FMJ projectile fired at a velocity of from about 427 m/s to about 445 m/s under the projectile firing conditions of NIJ Standard 0101.04, more preferably less than about 4 mm, more preferably less than about 3 mm, more preferably less than about 2 mm, and most preferably have a backface signature of less than about 1 mm when impacted with a 124-grain, 9 mm FMJ RN projectile (a bullet comprising approximately 90% copper and 10% zinc excluding the base) fired at a velocity of from about 427 m/s to about 445 m/s, when measured approximately at room temperature. Testing BFS against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s is common in the art. Said fibrous composites achieving these BFS values each comprise a plurality of adjoined fiber layers, each fiber layer comprising fibers having surfaces that are at least partially covered with a polymeric material, wherein said fibers are predominantly free of a fiber surface finish such that said polymeric material is predominantly in direct contact with the fiber surfaces. Said fibrous composites achieving these BFS values also preferably exhibit a V50 against a 16-grain Right Circular Cylinder (RCC) projectile of at least about 3200 feet/sec (fps) (975.36 m/s), more preferably at least about 3300 fps (1005.84 m/s), even more preferably at least about 3400 fps (1036.32 m/s), still more preferably at least about 3500 fps (1066.8 m/s) and most preferably at least about 3600 fps (1097.28 m/s). All of the above V50 values are for armor panels having a composite areal density of approximately 2.0 lbs/ft ² (psf)(9.76 kg/m ² (ksm)). As with BFS, this is not to say that all fibrous composites or articles of the invention will have a particular areal density, nor that all fibrous composites or articles of the invention will have a V50 against a 16-grain RCC projectile of at least about 3300 feet/sec. Such only identifies that composites fabricated according to the processes of the invention are characterized in that when fabricated into a 2.0 psf panel, that 2.0 psf panel will have a V50 against a 16-grain RCC projectile of at least about 3200 feet/sec. In a preferred embodiment of the invention, the fibrous composites of the invention have a V50 against a 16-grain RCC projectile of at least about 3200 fps or at least about 3300 fps in addition to a BFS of about 5 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, more preferably a V50 against a 16-grain RCC projectile of at least about 3200 fps or at least about 3300 fps in addition to a BFS of about 4 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, and still more preferably a V50 against a 16-grain RCC projectile of at least about 3200 fps or at least about 3300 fps in addition to a BFS of about 3 mm or less, about 2 mm or less, or about 1 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, when measured

approximately at room temperature. In a more preferred embodiment of the invention, the fibrous composites of the invention have a V50 against a 16- grain RCC projectile of at least about 3400 fps or at least about 3500 fps in addition to a BFS of about 5 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, more preferably a V50 against a 16-grain RCC projectile of at least about 3400 fps or at least about 3500 fps in addition to a BFS of about 4 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, and most preferably a V50 against a 16-grain RCC projectile of at least about 3300 fps in addition to a BFS of about 3 mm or less, about 2 mm or less, or about 1 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, when measured approximately at room temperature. In a most preferred

embodiment of the invention, the fibrous composites of the invention have a V50 against a 16-grain RCC projectile of at least about 3600 fps in addition to a BFS of about 5 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, more preferably a V50 against a 16-grain RCC projectile of at least about 3600 fps in addition to a BFS of about 4 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, and most preferably a V50 against a 16-grain RCC projectile of at least about 3600 fps in addition to a BFS of about 3 mm or less, about 2 mm or less, or about 1 mm or less against a 124-grain, 9 mm FMJ RN projectile fired at a velocity of from about 427 m/s to about 445 m/s, when measured approximately at room temperature. As previously, this BFS data was measured using an apparatus described in co-pending patent application serial no. 61/531,233 with a 1/2 inch space between the 2.0 psf sample and a clay backing material, measured at room temperature.

The high-strength, high tensile modulus polymeric fibers forming the fiber layers and composites of the invention may be of any fiber tenacity provided that the fiber tenacity after plasma/corona treating is from about 95% to 100% of the original fiber tenacity prior to plasma/corona treating (i.e. fiber tenacity loss due to treatment is less than 5%), more preferably is from about 98% to 100% of the original fiber tenacity (i.e. fiber tenacity loss due to treatment is less than 2%), still more preferably is from about 99% to 100% of the original fiber tenacity (i.e. fiber tenacity loss due to treatment is less than 1%), still more preferably wherein the fiber tenacity after plasma/corona treating is equal to the original fiber tenacity before plasma/corona treating (i.e. no fiber tenacity loss due to treatment), and most preferably wherein the fiber tenacity after plasma/corona treating is greater than the original fiber tenacity prior to plasma/corona treating (i.e. fiber tenacity increase due to treatment). Accordingly, the fiber layers and composites formed herein are preferably ballistic resistant composites formed from high-strength, high tensile modulus polymeric fibers having a tenacity prior to plasma/corona treating of at least about 20 g/denier as well as a tenacity after plasma/corona treating of at least about 20 g/denier. More preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 25 g/denier as well as a tenacity after plasma/corona treating of at least about 25 g/denier. More preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 30 g/denier as well as a tenacity after plasma/corona treating of at least about 30 g/denier. More preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 33 g/denier as well as a tenacity after plasma/corona treating of at least about 33 g/denier. More preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 35 g/denier as well as a tenacity after plasma/corona treating of at least about 35 g/denier. Still more preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 37 g/denier as well as a tenacity after plasma/corona treating of at least about 37 g/denier. More preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 39 g/denier as well as a tenacity after plasma/corona treating of at least about 39 g/denier. More preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 45 g/denier as well as a tenacity after plasma/corona treating of at least about 45 g/denier. More preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 50 g/denier as well as a tenacity after plasma/corona treating of at least about 50 g/denier. More preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 55 g/denier as well as a tenacity after plasma/corona treating of at least about 55 g/denier. Still more preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 60 g/denier as well as a tenacity after plasma/corona treating of at least about 60 g/denier. Most preferably, the fibers have a tenacity prior to plasma/corona treating of at least about 65 g/denier as well as a tenacity after plasma/corona treating of at least about 65 g/denier. All tenacity

measurements identified herein are measured at ambient room temperature. As used herein, the term "denier" refers to the unit of linear density, equal to the mass in grams per 9000 meters of fiber or yarn. As used herein, the term "tenacity" refers to the tensile stress expressed as force (grams) per unit linear density (denier) of an unstressed specimen and is measured by ASTM D2256. The "initial modulus" of a fiber is the property of a material representative of its resistance to deformation. The term "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). The tensile modulus of fibers is also affected by the plasma and corona treatments like the fiber tenacity. However, plasma or corona treating the fibers under atmospheric pressure after removing the fiber surface finish has actually been found to raise the modulus due to an increase in crosslink density due to the direct treatment of the fiber surfaces.

The polymers forming the fibers are preferably high-strength, high tensile modulus fibers suitable for the manufacture of ballistic resistant

composites/fabrics. Particularly suitable high-strength, high tensile modulus fiber materials that are particularly suitable for the formation of ballistic resistant composites and articles include polyolefin fibers, including high density and low density polyethylene. Particularly preferred are extended chain polyolefin fibers, such as highly oriented, high molecular weight polyethylene fibers, particularly ultra-high molecular weight polyethylene fibers, and polypropylene fibers, particularly ultra-high molecular weight polypropylene fibers. Also suitable are aramid fibers, particularly para-aramid fibers, polyamide fibers, polyethylene terephthalate fibers, polyethylene naphthalate fibers, extended chain polyvinyl alcohol fibers, extended chain polyacrylonitrile fibers, polybenzazole fibers, such as polybenzoxazole (PBO) and polybenzothiazole (PBT) fibers, liquid crystal copolyester fibers and other rigid rod fibers such as M5® fibers. Each of these fiber types is

conventionally known in the art. Also suitable for producing polymeric fibers are copolymers, block polymers and blends of the above materials. The most preferred fiber types for ballistic resistant fabrics include polyethylene, particularly extended chain polyethylene fibers, aramid fibers, polybenzazole fibers, liquid crystal copolyester fibers, polypropylene fibers, particularly highly oriented extended chain polypropylene fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers and other rigid rod fibers, particularly M5® fibers. Specifically most preferred fibers are aramid fibers.

In the case of polyethylene, 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. Such 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. A particularly preferred fiber type 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 U.S. patents 4,623,547 and 4,748,064. In addition to polyethylene, another useful polyolefin fiber type is polypropylene (fibers or tapes), such as TEGRIS® fibers commercially available from Milliken & Company of Spartanburg, South Carolina.

Also particularly preferred are aramid (aromatic polyamide) or para-aramid fibers. Such are commercially available and are described, for example, in U.S. patent 3,671,542. For example, useful poly(p-phenylene

terephthalamide) filaments are produced commercially by DuPont under the trademark of KEVLAR®. Also useful in the practice of this invention are poly(m-phenylene isophthalamide) fibers produced commercially by DuPont under the trademark NOMEX® and fibers produced commercially by Teijin under the trademark TWARON®; aramid fibers produced commercially by Kolon Industries, Inc. of Korea under the trademark HERACRON®; p-aramid fibers SVM™ and RUSAR™ which are produced commercially by Kamensk Volokno JSC of Russia and ARMOS™p-aramid fibers produced

commercially by JSC Chim Volokno of Russia. 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 is incorporated herein by reference. 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. 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. Suitable polyvinyl alcohol (PV-OH) fibers are described, for example, in U.S. patents 4,440,711 and 4,599,267 which are incorporated herein by reference. Suitable polyacrylonitrile (PAN) fibers are disclosed, for example, in U.S. patent 4,535,027, which is incorporated herein by reference. Each of these fiber types is conventionally known and is widely commercially available. M5® fibers are formed from pyridobisimidazole-2,6-diyl (2,5-dihydroxy-p- phenylene) and 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. Also suitable are combinations of all the above materials, all of which are commercially available. For example, the fibrous layers may be formed from a combination of one or more of aramid fibers, UHMWPE fibers (e.g. SPECTRA® fibers), carbon fibers, etc., as well as fiberglass and other lower-performing materials. However, BFS and V50 values may vary by fiber type.

The fibers may be of any suitable denier useful to achieve fibers having tenacities as defined above. The selection is governed by considerations of ballistic effectiveness and cost. Finer fibers are more costly to manufacture and to weave, but can produce greater ballistic effectiveness per unit weight. Ultra high molecular weight polyethylene fibers having a tenacity of at least about 37 g/denier are obtainable, for example, by employing the process of copending application Serial No. 13/173,919, filed June 30, 2011.

Other known processes for the manufacture of high strength fibers are disclosed in, for example, U.S. patents 4,413,110, 4,440,711, 4,535,027,

4,457,985, 4,623,547 4,650,710 and 4,748,06, which are incorporated herein by reference to the extent consistent herewith. Such methods, including solution grown or gel fiber processes, are well known in the art. Methods of forming each of the other preferred fiber types, including para-aramid fibers, are also conventionally known in the art, and the fibers are commercially available.

After removing at least a portion of the fiber surface finish from the fiber surfaces as desired, and after the fiber surfaces are optionally treated under conditions effective to enhance the adsorbability of a subsequently applied adsorbate on the fiber surfaces, an adsorbate is then optionally applied onto at least a portion of at least some of the fibers. To this end, an "adsorbate" may be any solid, liquid or gas, including polymeric binder materials and resins, and adsorption includes any form of bonding of the materials to the fiber surfaces. The definition of "adsorbate" expressly includes all polymers useful as polymer binder materials, resins or polymeric matrix materials, but the class of useful adsorbates expressly excludes materials that do not have binding properties, including fiber surface finish substances such as a spin finish materials, which are not binder materials having binding properties. To the contrary, fiber surface finish materials are specifically removed from fiber surfaces according to the invention. The term "adsorbate" also expressly includes inorganic materials, such as silicon oxide, titanium oxide, aluminum oxide, tantalum oxide, hafnium oxide, zirconium oxide, titanium aluminate, titanium silicate, hafnium aluminate, hafnium silicate, zirconium aluminate, zirconium silicate, boron nitride or a combination thereof, as are disclosed in commonly-owned U.S. patent application publication no. 2008/01 19098, the disclosure of which is incorporated herein by reference.

The term "adsorption" (or "adsorbability" or "adsorb") is broadly intended to encompass both physisorption and chemisorption of any material (solid, liquid, gas or plasma) on the fiber surface, where "physisorption" is defined herein as physical bonding of a material on a fiber surface and

"chemisorption" is defined herein as chemical bonding of a material on a fiber surface, where a chemical reaction occurs at the exposed fiber (i.e. the adsorbant) surface. The term "adsorption" as used herein is intended to include any possible means of attaching, adhering or bonding a material to a substrate surface, physically or chemically, without limitation, including means for increasing fiber wetting/adhesion of fibers in polymer matrices. This expressly includes the adhesion or coating of any solid, liquid or gas material on the fiber surfaces, including any monomer, oligomer, polymer or resin, and including the application of any organic material or inorganic material onto the fiber surfaces.

It is most preferred herein that the fibers forming the woven or non-woven materials of the invention are coated with or impregnated with a polymeric binder material. The polymeric binder material adsorbate, such as a resin, either partially or substantially coats the individual fibers of the fiber layers, preferably substantially coating each of the individual fibers of each fiber layer. The polymeric binder material is also commonly known in the art as a "polymeric matrix" material, and these terms are used interchangeably herein. These terms are conventionally known in the art and describe a material that binds fibers together either by way of its inherent adhesive characteristics or after being subjected to well known heat and/or pressure conditions. Such a "polymeric matrix" or "polymeric binder" material may also provide a fabric with other desirable properties, such as abrasion resistance and resistance to deleterious environmental conditions, so it may be desirable to coat the fibers with such a binder material even when its binding properties are not important, such as with woven fabrics. Suitable polymeric binder materials include both low modulus, elastomeric materials and high modulus, rigid materials. As used herein throughout, the term tensile modulus means the modulus of elasticity as measured by ASTM 2256 for a fiber and by ASTM D638 for a polymeric binder material. A low or high modulus binder may comprise a variety of polymeric and non- polymeric materials. A preferred polymeric binder comprises a low modulus elastomeric material. For the purposes of this invention, 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. A low modulus polymer preferably has, 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°C, more preferably the less than about -40°C, and most preferably less than about -50°C. The elastomer also has a 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 materials and formulations having a low modulus may be utilized as the polymeric binder. Representative examples include polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, polysulfide polymers, polyurethane elastomers, chlorosulfonated polyethylene, polychloroprene, plasticized polyvinylchloride, butadiene acrylonitrile elastomers, poly(isobutylene-co- isoprene), polyacrylates, polyesters, polyethers, fluoroelastomers, silicone elastomers, copolymers of ethylene, polyamides (useful with some fiber types), acrylonitrile butadiene styrene, polycarbonates, and combinations thereof, as well as other low modulus polymers and copolymers curable below the melting point of the fiber. Also preferred are blends of different elastomeric materials, or blends of elastomeric materials with one or more thermoplastics.

Particularly useful 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 (n= 2-10) or radial configuration copolymers of the type R-(BA) _X (x=3-150); 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 Kraton Polymers of Houston, TX and described in the bulletin "Kraton Thermoplastic Rubber", SC-68-81. Also useful are resin dispersions of styrene-isoprene-styrene (SIS) block copolymer sold under the trademark PRINLIN® and commercially available from Henkel Technologies, based in Dusseldorf, Germany. Particularly preferred low modulus polymeric binder polymers comprise styrenic block copolymers sold under the trademark KRATON® commercially produced by Kraton Polymers. A particularly preferred polymeric binder material comprises a polystyrene-polyisoprene- polystyrene-block copolymer sold under the trademark KRATON®.

While low modulus polymeric matrix binder materials are most useful for the formation of flexible armor, such as ballistic resistant vests, high modulus, rigid materials useful for forming hard armor articles, such as helmets, are particularly preferred herein. Preferred high modulus, rigid materials generally have a higher initial tensile modulus than 6,000 psi. Preferred high modulus, rigid polymeric binder materials useful herein include polyurethanes (both ether and ester based), epoxies, polyacrylates, phenolic/polyvinyl butyral (PVB) polymers, vinyl ester polymers, styrene-butadiene block copolymers, as well as mixtures of polymers such as vinyl ester and diallyl phthalate or phenol formaldehyde and polyvinyl butyral. A particularly preferred rigid polymeric binder 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 ^s psi (6895 MPa) as measured by ASTM D638. Particularly preferred rigid polymeric binder materials are those described in U.S. patent 6,642,159, the disclosure of which is incorporated herein by reference. The polymeric binder, whether a low modulus material or a high modulus material, may also include 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.

Most specifically preferred are polar resins or polar polymers, particularly polyurethanes within the range of both soft and rigid materials at a tensile modulus ranging from about 2,000 psi (13.79 MPa) to about 8,000 psi (55.16 MPa). Preferred polyurethanes are applied as aqueous polyurethane dispersions that are most preferably, but not necessarily, cosolvent free. Such includes aqueous anionic polyurethane dispersions, aqueous cationic polyurethane dispersions and aqueous nonionic polyurethane dispersions. Particularly preferred are aqueous anionic polyurethane dispersions; aqueous aliphatic polyurethane dispersions, and most preferred are aqueous anionic, aliphatic polyurethane dispersions, all of which are preferably cosolvent free dispersions. Such includes aqueous anionic polyester-based polyurethane dispersions; aqueous aliphatic polyester-based polyurethane dispersions; and aqueous anionic, aliphatic polyester-based polyurethane dispersions, all of which are preferably cosolvent free dispersions. Such also includes aqueous anionic polyether polyurethane dispersions; aqueous aliphatic polyether-based polyurethane dispersions; and aqueous anionic, aliphatic polyether-based polyurethane dispersions, all of which are preferably cosolvent free dispersions. Similarly preferred are all corresponding variations (polyester- based; aliphatic polyester-based; polyether-based; aliphatic polyether-based, etc.) of aqueous cationic and aqueous nonionic dispersions. Most preferred is an aliphatic polyurethane dispersion having a modulus at 100% elongation of about 700 psi or more, with a particularly preferred range of 700 psi to about 3000 psi. More preferred are aliphatic polyurethane dispersions having a modulus at 100% elongation of about 1000 psi or more, and still more preferably about 1100 psi or more. Most preferred is an aliphatic, polyether- based anionic polyurethane dispersion having a modulus of 1000 psi or more, preferably 1100 psi or more.

The rigidity, impact and ballistic properties of the articles formed from the composites of the invention are affected by the tensile modulus of the polymeric binder polymer coating the fibers. For example, U.S. patent 4,623,574 discloses that fiber reinforced composites constructed with elastomeric matrices having tensile moduli less than about 6,000 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 polymeric binder material. However, low tensile modulus polymeric binder material polymers also yield lower rigidity composites. Further, in certain applications, particularly those where a composite must function in both anti-ballistic and structural modes, there is needed a superior combination of ballistic resistance and rigidity.

Accordingly, the most appropriate type of polymeric binder polymer to be used will vary depending on the type of article to be formed from the composites of the invention. In order to achieve a compromise in both properties, a suitable polymeric binder may combine both low modulus and high modulus materials to form a single polymeric binder. The polymeric binder material may be applied either simultaneously or sequentially to a plurality of fibers arranged as a fiber web (e.g. a parallel array or a felt) to form a coated web, applied to a woven fabric to form a coated woven fabric, or as another arrangement, to thereby impregnate the fiber layers with the binder. As used herein, the term "impregnated with" is synonymous with "embedded in" as well as "coated with" or otherwise applied with the coating where the binder material diffuses into the fiber layer and is not simply on a surface of the fiber layers. The polymeric material may also be applied onto at least one array of fibers that is not part of a fiber web, followed by weaving the fibers into a woven fabric or followed by formulating a non-woven fabric following the methods described previously herein.

Techniques of forming woven and non-woven fiber plies, layers and fabrics are well known in the art.

Although not required, fibers forming woven fiber layers are at least partially coated with a polymeric binder, followed by a consolidation step similar to that conducted with non-woven fiber layers. Such a consolidation step may be conducted to merge multiple woven fiber layers with each other, or to further merge the binder with the fibers of said woven fabric. For example, a plurality of woven fiber layers do not necessarily have to be consolidated, and may be attached by other means, such as with a conventional adhesive, or by stitching.

Generally, a polymeric binder coating is necessary to efficiently merge, i.e. consolidate, a plurality of non- woven fiber plies. The polymeric binder material may be applied onto the entire surface area of the individual fibers or only onto a partial surface area of the fibers. Most preferably, the coating of the polymeric binder material is applied onto substantially all the surface area of each individual fiber forming a fiber layer of the invention. Where a fiber layer comprises a plurality of yarns, each fiber forming a single strand of yarn is preferably coated with the polymeric binder material.

Any appropriate application method may be utilized to apply the polymeric binder material and the term "coated" is not intended to limit the method by which it is applied onto the filaments/fibers. The polymeric binder material is applied directly onto the fiber surfaces using any appropriate method that would be readily determined by one skilled in the art, and the binder then typically diffuses into the fiber layer as discussed herein. Most preferably, a method is used which at least partially coats each individual fiber with the polymeric material, preferably substantially coating or encapsulating each of the individual fibers and covering all or substantially all of the filament/fiber surface area with the polymeric binder material.

While it is necessary that the fibers be coated with a polymeric binder after the at least partial removal of the fiber surface finish, and preferably after a surface treatment that enhances the adsorbability of a subsequently applied adsorbate on the fiber surfaces, the fibers may be coated with the polymeric binder either before or after the fibers are arranged into one or more plies/layers, or before or after the fibers are woven into a woven fabric.

Woven fabrics 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, where fibers are woven together in an orthogonal 0 90° orientation. Either prior to or after weaving, the individual fibers of each woven fabric material may or may not be coated with the polymeric binder material. Typically, weaving of fabrics is performed prior to coating fibers with the polymeric binder, where the woven fabrics are thereby impregnated with the binder. However, the invention is not intended to be limited by the stage at which the polymeric binder is applied to the fibers, nor by the means used to apply the polymeric binder. Methods for the production of non-woven fabrics are well known in the art. In the preferred embodiments herein, a plurality of fibers are arranged into at least one array, typically being arranged as a fiber web comprising a plurality of fibers aligned in a substantially parallel, unidirectional array. As previously stated, in a typical process for forming non-woven unidirectionally aligned fiber plies, fiber bundles are supplied from a creel and led through guides and one or more spreader bars into a collimating comb, followed by coating the fibers with a polymeric binder material. A typical fiber bundle will have from about 30 to about 2000 individual fibers. The spreader bars and collimating comb disperse and spread out the bundled fibers, reorganizing them side-by- side in a coplanar fashion. Ideal fiber spreading results in the individual filaments or individual fibers being positioned next to one another in a single fiber plane, forming a substantially unidirectional, parallel array of fibers without fibers overlapping each other. At this point, removing the fiber surface finish before or during this spreading step may enhance and accelerate the spreading of the fibers into such a parallel array. After the fibers are coated with the binder material, the coated fibers are formed into non-woven fiber layers that comprise a plurality of overlapping, non-woven fiber plies that are consolidated into a single-layer, monolithic element. In a preferred non-woven fabric structure of the invention, a plurality of stacked, overlapping unitapes are formed wherein the parallel fibers of each single ply (unitape) are positioned orthogonally to the parallel fibers of each adjacent single ply relative to the longitudinal fiber direction of each single ply. The stack of overlapping non- woven fiber plies is consolidated under heat and pressure, or by adhering the coatings of individual fiber plies, to form a single-layer, monolithic element which has also been referred to in the art as a single-layer, consolidated network where a "consolidated network" describes a consolidated (merged) combination of fiber plies with the polymeric matrix/binder. Articles of the invention may also comprise hybrid

consolidated combinations of adjoined woven fabrics and non- woven fabrics, as well as combinations of non- woven fabrics formed from unidirectional fiber plies and non-woven felt fabrics.

Most typically, non-woven fiber layers or fabrics include from 1 to about 6 adjoined fiber plies, but may include as many as about 10 to about 20 plies as may be desired for various applications. The greater the number of plies translates into greater ballistic resistance, but also greater weight.

Accordingly, the number of fiber plies forming a fiber layer composite and/or fabric composite or an article of the invention varies depending upon the ultimate use of the fabric or article. For example, in body armor vests for military applications, in order to form an article composite that achieves a desired 1.0 pound per square foot or less areal density (4.9 kg/m ² ), a total of about 100 plies (or layers) to about 50 individual plies (or layers) may be required, wherein the plies/layers may be woven, knitted, felted or non- woven fabrics (with parallel oriented fibers or other arrangements) formed from the high-strength fibers described herein. In another embodiment, body armor vests for law enforcement use may have a number of plies/layers based on the NIJ threat level. For example, for an NIJ threat level IIIA vest, there may be a total of 40 plies. For a lower NIJ threat level, fewer plies/layers may be employed. The invention allows for the incorporation of a greater number of fiber plies to achieve the desired level of ballistic protection without increasing the fabric weight as compared to other known ballistic resistant structures. As is conventionally known in the art, excellent ballistic resistance is achieved when individual fiber plies are cross-plied such that the fiber alignment direction of one ply is rotated at an angle with respect to the fiber alignment direction of another ply. Most preferably, the fiber plies are cross-plied orthogonally at 0° and 90° angles, but adjacent plies can be aligned at virtually any angle between about 0° and about 90° with respect to the longitudinal fiber direction of another ply. For example, a five ply non-woven structure may have plies oriented at a 0°/45 ^ο /90 ^ο /45 ^ο /0° or at other angles. Such rotated unidirectional alignments are described, for example, in U.S. patents

4,457,985; 4,748,064; 4,916,000; 4,403,012; 4,623,574; and 4,737,402, all of which are incorporated herein by reference to the extent not incompatible herewith.

Methods of consolidating fiber plies to form fiber layers and composites are well known, such as by the methods described in U.S. patent 6,642,159. Consolidation can occur via drying, cooling, heating, pressure or a combination thereof. Heat and/or pressure may not be necessary, as the fibers or fabric layers may just be glued together, as is the case in a wet lamination process. Typically, consolidation is done by positioning the individual fiber plies on one another under conditions of sufficient heat and pressure to cause the plies to combine into a unitary fabric. Consolidation may be done at temperatures ranging from about 50°C to about 175°C, preferably from about 105°C to about 175°C, and at pressures ranging from about 5 psig (0.034 MPa) to about 2500 psig (17 MPa), for from about 0.01 seconds to about 24 hours, preferably from about .02 seconds to about 2 hours. When heating, it is possible that the polymeric binder coating can be caused to stick or flow without completely melting However, generally, if the polymeric binder material (if it is one that is capable of melting) is caused to melt, relatively little pressure is required to form the composite, while if the binder material is only heated to a sticking point, more pressure is typically required. As is conventionally known in the art, consolidation may be conducted in a calender set, a flat-bed laminator, a press or in an autoclave. Most commonly, a plurality of orthogonal fiber webs are "glued" together with the binder polymer and run through a flat bed laminator to improve the uniformity and strength of the bond. Further, the consolidation and polymer

application/bonding steps may comprise two separate steps or a single consolidation/lamination step.

Alternately, consolidation may be achieved by molding under heat and pressure in a suitable molding apparatus. Generally, molding is conducted at a pressure of from about 50 psi (344.7 kPa) to about 5,000 psi (34,470 kPa), more preferably about 100 psi (689.5 kPa) to about 3,000 psi (20,680 kPa), most preferably from about 150 psi (1,034 kPa) to about 1,500 psi (10,340 kPa). Molding may alternately be conducted at higher pressures of from about 5,000 psi (34,470 kPa) to about 15,000 psi (103,410 kPa), more preferably from about 750 psi (5,171 kPa) to about 5,000 psi, and more preferably from about 1,000 psi to about 5,000 psi. The molding step may take from about 4 seconds to about 45 minutes. Preferred molding temperatures range from about 200°F (~93°C) to about 350°F (~177°C), more preferably at a temperature from about 200°F to about 300°F and most preferably at a temperature from about 200°F to about 280°F. The pressure under which the fiber layers and fabric composites of the invention are molded typically has a direct effect on the stiffness or flexibility of the resulting molded product. Molding at a higher pressure generally produces stiffer materials, up to a certain limit. In addition to the molding pressure, the quantity, thickness and composition of the fiber plies and polymeric binder coating type also directly affects the stiffness of the articles formed from the composites.

While each of the molding and consolidation techniques described herein are similar, each process is different. Particularly, molding is a batch process and consolidation is a generally continuous process. Further, molding typically involves the use of a mold, such as a shaped mold or a match-die mold when forming a flat panel, and does not necessarily result in a planar product.

Normally consolidation is done in a flat-bed laminator, a calendar nip set or as a wet lamination to produce soft (flexible) body armor fabrics. Molding is typically reserved for the manufacture of hard armor, e.g. rigid plates. In either process, suitable temperatures, pressures and times are generally dependent on the type of polymeric binder coating materials, polymeric binder content, process used and fiber type. To produce a fabric article having sufficient ballistic resistance properties, the total weight of the binder/matrix coating preferably comprises from about 2% to about 50% by weight, more preferably from about 5% to about 30%, more preferably from about 7% to about 20%, and most preferably from about 1 1% to about 16% by weight of the fibers plus the weight of the coating, wherein 16% is most preferred for non- woven fabrics. A lower binder/matrix content is appropriate for woven fabrics, wherein a polymeric binder content of greater than zero but less than 10% by weight of the fibers plus the weight of the coating is typically most preferred. This is not intended as limiting. For example, phenolic/PVB impregnated woven aramid fabrics are sometimes fabricated with a higher resin content of from about 20% to about 30%, although around 12% content is typically preferred.

Following weaving or consolidation of the fiber layers, an optional thermoplastic polymer layer may be attached to one or both of the outer surfaces of the fibrous composite via conventional methods. Suitable polymers for the thermoplastic polymer layer non-exclusively include thermoplastic polymers non-exclusively may be selected from the group consisting of polyolefms, polyamides, polyesters (particularly polyethylene terephthalate (PET) and PET copolymers), polyurethanes, vinyl polymers, ethylene vinyl alcohol copolymers, ethylene octane copolymers, acrylonitrile copolymers, acrylic polymers, vinyl polymers, polycarbonates, polystyrenes, fluoropolymers and the like, as well as co-polymers and mixtures thereof, including ethylene vinyl acetate (EVA) and ethylene acrylic acid. Also useful are natural and synthetic rubber polymers. Of these, polyolefin and polyamide layers are preferred. The preferred polyolefm is a polyethylene. Non-limiting examples of useful polyethylenes are low density polyethylene (LDPE), linear low density polyethylene (LLDPE), Medium Density Polyethylene (MDPE), linear medium density polyethylene (LMDPE), linear very-low density polyethylene (VLDPE), linear ultra-low density polyethylene (ULDPE), high density polyethylene (HDPE) and co-polymers and mixtures thereof. Also useful are SPUNFAB® polyamide webs commercially available from

Spunfab, Ltd, of Cuyahoga Falls, Ohio (trademark registered to Keuchel Associates, Inc.), as well as THERMOPLAST™ and HELIOPLAST™ webs, nets and films, commercially available from Protechnic S.A. of Cernay, France. The thermoplastic polymer layer may be bonded to the composite surfaces using well known techniques, such as thermal lamination. Typically, laminating is done by positioning the individual layers on one another under conditions of sufficient heat and pressure to cause the layers to combine into a unitary film. The individual layers are positioned on one another, and the combination is then typically passed through the nip of a pair of heated laminating rollers by techniques well known in the art. Lamination heating may be conducted at temperatures ranging from about 95°C to about 175°C, preferably from about 105°C to about 175°C, at pressures ranging from about 5 psig (0.034 MPa) to about 100 psig (0.69 MPa), for from about 5 seconds to about 36 hours, preferably from about 30 seconds to about 24 hours.

The thickness of the individual fabrics/composites/fiber layers will correspond to the thickness of the individual fibers and the number of fiber layers incorporated into a fabric. A preferred woven fabric will have a preferred thickness of from about 25 μιη to about 600 μιη per layer, more preferably from about 50 μιη to about 385 μιη and most preferably from about 75 μιη to about 255 μιη per layer. A preferred non- woven fabric, i.e. a non- woven, single-layer, consolidated network, will have a preferred thickness of from about 12 μιη to about 600 μιη, more preferably from about 50 μιη to about 385 μιη and most preferably from about 75 μιη to about 255 μιη, wherein a single- layer, consolidated network typically includes two consolidated plies (i.e. two unitapes). Any thermoplastic polymer layers are preferably very thin, having preferred layer thicknesses of from about 1 μιη to about 250 μιη, more preferably from about 5 μιη to about 25 μιη and most preferably from about 5 μιη to about 9 μιη. Discontinuous webs such as SPU FAB® non-woven webs are preferably applied with a basis weight of 6 grams per square meter (gsm). While such thicknesses are preferred, it is to be understood that other thicknesses may be produced to satisfy a particular need and yet fall within the scope of the present invention.

The fabrics/composites of the invention will have a preferred areal density prior to consolidation/molding of from about 20 grams/m ² (0.004 lb/ft ² (psf)) to about 1000 gsm (0.2 psf). More preferable areal densities for the fabrics/composites of this invention prior to consolidation/molding will range from about 30 gsm (0.006 psf) to about 500 gsm (0.1 psf). The most preferred areal density for fabrics/composites of this invention will range from about 50 gsm (0.01 psf) to about 250 gsm (0.05 psf) prior to consolidation/molding. Articles of the invention comprising multiple fiber layers stacked one upon another and consolidated will have a preferred composite areal density of from about 1000 gsm (-0.2 psf) to about 40,000 gsm (8.2 psf), more preferably from about 2000 gsm (-0.41 psf) to about 30,000 gsm (6.1 psf), more preferably from about 3000 gsm (-0.61 psf) to about 20,000 gsm (4.1 psf), and most preferably from about 3750 gsm (0.77 psf) to about 15,000 gsm (3.1 psf). A typical range for composite articles shaped into helmets is from about 7,500 gsm (1.54 psf) to about 12,500 gsm (2.56 psf).

The fabrics of the invention may be used in various applications to form a variety of different ballistic resistant articles using well known techniques, including flexible, soft armor articles as well as rigid, hard armor articles. For example, suitable techniques for forming ballistic resistant articles are described in, for example, U.S. patents 4,623,574, 4,650,710, 4,748,064, 5,552,208, 5,587,230, 6,642,159, 6,841,492 and 6,846,758, all of which are incorporated herein by reference to the extent not incompatible herewith. The composites are particularly useful for the formation of hard armor and shaped or unshaped sub-assembly intermediates formed in the process of fabricating hard armor articles. By "hard" armor is meant an article, such as helmets, panels for military vehicles, or protective shields, which have sufficient mechanical strength so that it maintains structural rigidity when subjected to a significant amount of stress and is capable of being freestanding without collapsing. Such hard articles are preferably, but not exclusively, formed using a high tensile modulus binder material.

The structures can be cut into a plurality of discrete sheets and stacked for formation into an article or they can be formed into a precursor which is subsequently used to form an article. Such techniques are well known in the art. In a most preferred embodiment of the invention, a plurality of fiber layers are provided, each comprising a consolidated plurality of fiber plies, wherein a thermoplastic polymer is bonded to at least one outer surface of each fiber layer either before, during or after a consolidation step which consolidates the plurality of fiber plies, wherein the plurality of fiber layers are subsequently merged by another consolidation step which consolidates the plurality of fiber layers into an armor article or sub-assembly of an armor article.

The ballistic resistance properties of the fibrous composites of the invention, including both ballistic penetration resistance and backface signature, may be measured according to well known techniques in the art. The following examples serve to illustrate the invention.

EXAMPLES 1-10

In Examples 1-10, the physical properties of ultra high molecular weight polyethylene fibers were measured without being washed to remove their fiber finish and without being plasma treated. The fiber samples for all of

Examples 1-30 were selected from the same spool of ultra high molecular weight polyethylene fibers. The fiber denier, fiber load at maximum strain (pounds force, lbf), percent strain at maximum load, fiber tenacity (g/denier) and fiber initial tensile modulus (g/denier) were measured for ten control fiber samples. The results are outlined in Table 1 wherein the fibers are identified as Control fibers 1-10. TABLE 1

EXAMPLES 11-20

In Examples 11-20, the physical properties of ultra high molecular weight polyethylene fibers were measured after being washed to substantially remove their fiber finish but without being plasma treated. The fiber samples for all of Examples 1-30 were selected from the same spool of ultra high molecular weight polyethylene fibers.

To remove the finish, the fibers were directed through a pre-soak water bath containing de-ionized water, with an approximate residence time of about 18 seconds. After exiting the pre-soak water bath, the fibers were rinsed by a bank of 30 water nozzles. Water pressure of each water nozzle was approximately 42 psi with a water flow rate of approximately 0.5 gallons per minute per nozzle. The water exiting the nozzles was formed as a relatively flat stream and the angle of water contact on the fibers was either 0° or 30° relative to the angle of incidence of the stream emitting from adjacent nozzles. Water temperature was measured as 28.9°C. The line speed through the bank of water nozzles was approximately 12 ft/min. The water in the soak bath and water delivered to the nozzles was deionized by first passing through a separate de-ionizing system. The washed fibers were then dried and analyzed.

The fiber denier, fiber load at maximum strain, percent strain at maximum load, fiber tenacity and fiber initial tensile modulus were measured for ten washed fiber samples. The results are outlined in Table 2 wherein the fibers are identified as Washed fibers 1-10.

TABLE 2

EXAMPLES 21-30

In Examples 21-30, the physical properties of ultra high molecular weight polyethylene fibers were measured after being washed to substantially remove their fiber finish and then also subsequently plasma treated. The fiber samples for all of Examples 1-30 were selected from the same spool of ultra high molecular weight polyethylene fibers.

The fiber finish was substantially removed according to the process described for Examples 11-20. Plasma treatment was conducted by continuously passing the washed fibers through an atmospheric plasma treater (model: Enercon Plasma3 Station Model APT12DF-150/2, from Enercon Industries Corp., having 29-inch wide electrodes) at a line speed of approximately 12 ft/min, with a residence time of the fibers within the plasma treater of approximately 2.5 seconds and with the plasma treater set to a power of 1.5 kW. Treatment was conducted under standard atmospheric pressure (760 torr) in an atmosphere of 90% argon gas and 10% oxygen.

The fiber denier, fiber load at maximum strain, percent strain at maximum load, fiber tenacity and fiber initial tensile modulus were measured for ten washed fiber samples. The results are outlined in Table 3 wherein the fibers are identified as W&P fibers (washed and plasma treated fibers) 1-10.

TABLE 3

Conclusions:

Collectively, Examples 1-30 illustrate that fibers that were plasma treated after washing the fibers to substantially remove the fiber finish have approximately the same physical properties both before and after the treatments. Particularly, the combined treatments resulted in approximately no loss in fiber tenacity and, in many instances, resulted in an increase in initial tensile modulus. Based on the fiber property averages, the examples show a tenacity gain of approximately 1% and an initial tensile modulus increase of approximately 2.7% when washing the fibers before plasma treating. The increases in tenacity and initial tensile modulus may result, for example, from crosslinking polymer chains at the fiber surfaces due to plasma treatment directly on the fiber surfaces rather than through a fiber surface finish.

COMPARATIVE EXAMPLES 1-6

In Comparative Examples 1-6, the physical properties of ultra high molecular weight polyethylene fibers were measured after plasma treating but without being washed to remove their fiber finish before the plasma treatment. The fiber samples for all of Comparative Examples 1-6 were selected from the same spool of ultra high molecular weight polyethylene fibers. The fiber denier, fiber load at maximum strain, percent strain at maximum load, fiber tenacity and fiber initial tensile modulus were measured for three control fiber samples and three plasma treated samples. Plasma treatment was conducted by continuously passing the washed fibers through a low pressure plasma treater (Plasma Science Model PS 1010, commercially available from Plasmatreat US LP of Elgin, IL; modified to allow a single fiber to make multiple passes through the plasma atmosphere before exiting the chamber) at a line speed of approximately 10 m/min, with a residence time of the fibers within the plasma treater of approximately 1.4 minutes and with the plasma treater set to a power of 250 W. Treatment was conducted at a pressure of 400 milliTorr in an atmosphere of 90% argon gas and 10% oxygen. The results are outlined in Table 4 and Table 5. TABLE 4

TABLE 5

Conclusions:

Collectively, Comparative Examples 1 -6 illustrate that fibers that were plasma treated without first washing the fibers to substantially remove the fiber finish experience a significant loss in fiber tenacity due to the plasma treatment, a tenacity loss of approximately 17% based on the fiber averages. This is particularly revealing in view of the substantially less aggressive plasma treatment level in Comparative Examples 1-6 (i.e. 250 W) at low pressure relative to the plasma treatment level in Examples 1-30 (i.e. 1.5 kW) at atmospheric pressure. EXAMPLE 31

A four-ply non-woven composite was fabricated incorporating four plies of unidirectionally oriented, substantially parallel ultra high molecular weight polyethylene fibers having a fiber tenacity of approximately 45 g/d. Prior to forming the plies, the fibers were washed to substantially remove their fiber finish and subsequently plasma treated and dried. To remove the finish, a plurality of multi-filament fibers were unwound from a plurality of fiber spools (one spool per multi-filament fiber) and then passed through a fixed collimating comb to organize the fibers into an evenly spaced fiber web. The fiber web was then directed through a pre-soak water bath containing de- ionized water, with an approximate residence time of about 18 seconds. After exiting the pre-soak water bath, the fibers were rinsed by a bank of 30 water nozzles. Water pressure of each water nozzle was approximately 42 psi with a water flow rate of approximately 0.5 gallons per minute per nozzle. The water exiting the nozzles was formed as a relatively flat stream and the angle of water contact on the fibers was either 0° or 30° relative to the angle of incidence of the stream emitting from adjacent nozzles. Water temperature was measured as 28.9°C. Line speeds through the pre-soak water bath and through the bank of water nozzles ranged from about 4 m/min to about 20 m/min. The water in the soak bath and water delivered to the nozzles was deionized by first passing through a separate de-ionizing system. The washed fibers were then dried and transferred for further processing.

Plasma treatment was conducted by continuously passing a 29-inch wide web of washed fibers through an atmospheric plasma treater (model: Enercon Plasma3 Station Model APT12DF-150/2, from Enercon Industries Corp., having 29-inch wide electrodes) at a rate of approximately 12 ft/min, with the plasma treater set to a power of 1.5 kW. This resulted in a power distribution over the area of the fibers, measured in watt density, of 2000W/(29 in. x 12- FPM) or 67 Watts/ft ² /min applied to the fibers. The residence time of the fibers within the plasma treater was approximately 2.5 seconds. Treatment was conducted under standard atmospheric pressure. The fiber tenacity after the plasma treatment was approximately 45 g/d. Thereafter, the fibers were coated with an aliphatic, anionic polyurethane dispersion having a modulus of 1 100 psi. Each ply had a resin content of approximately 16% by weight of the ply. The four plies were oriented at 0°/90 ^ο /0°/90 ^ο relative to the longitudinal fiber direction of each ply. The four- ply composite had a fiber areal density (per ply) of approximately 35 gsm and a total areal density of each ply of approximately 42 gsm, which translates to a final product FAD and TAD of 140 gsm and 167 gsm, respectively.

EXAMPLE 32

The composite of Example 31 was fabricated into a consolidated 2.0 psf sample and tested for backface signature and V50 at room temperature. The average V50 value against a 16-Grain RCC projectile at ambient room temperature was 3621 feet/second. The average BFS at ambient room temperature against the same 16-Grain RCC projectile was 3 mm as measured with a ½ inch air gap between the rear surface of the composite and the clay backing material.

Backface Signature Measurement

Backface signature was measured using an apparatus described in co-pending patent application serial no. 61/531,233. The composite was spaced apart from a clay block by ½ inch (12.7 mm) by inserting a custom machined spacer element between the composite article and the clay block. The custom machined spacer element comprised an element having a border and an interior cavity defined by said border wherein the clay was exposed through the cavity, and wherein the spacer was positioned in direct contact with front surface of the clay. Projectiles were fired at the composite articles at target locations corresponding to the interior cavity of the spacer. The projectiles impacted the composite article at locations corresponding to the interior cavity of the spacer, and each projectile impact caused a measurable depression in the clay. The 3 mm BFS measurement refers to the depth of the depression in the clay as per this method without taking into account the depth of the spacer element, i.e. the BFS measurement does not include the actual distance between the composite and the clay.

V^n measurement

V50 data was acquired taken under conventionally known standardized techniques, particularly per the conditions of Department of Defense Test Method Standard MIL-STD-662F against a 16-Grain RCC projectile.

EXAMPLES 33-38

Examples 31 and 32 were repeated to fabricate additional 2.0 psf samples but with different binder resins. The composites were tested for backface signature and V50 at room temperature, and the results are outlined in Table 6. For examples 36-38, corona treatment was conducted rather than a plasma treatment as in Example 31. Corona treatment was performed by continuously passing a web of washed fibers through a corona treater having 30-inch wide electrodes at a rate of approximately 15 ft/min, with the corona treater set to a power of 2kW. The residence time of the fibers within the corona field was approximately 2 seconds. Treatment was conducted under standard atmospheric pressure. TABLE 6

EXAMPLE 39

A plurality of composites of Example 31 are cut into a plurality of 21 " x 21 " squares. A plurality of the squares are fabricated into one or more ballistic shells, and the ballistic shells are fabricated into Enhanced Combat Helmets. Each ballistic shell weighs approximately 2.8 lbs (-2.24 psf). There is a polymer based outer surface coating or thick film on the outside of the helmet, and a woven polyethylene based fabric on the inside of the helmet (e.g. woven fabric style 903 incorporating 1200 denier, S900 SPECTRA® polyethylene fibers; plain weave with a pick count of 21 x 21 ends/inch (ends/2.54 cm); areal weight of 7 oz yd ² (217 g/m2 (gsm)). The helmets are optionally finished with pads and suspensions.

EXAMPLE 40

A four-ply non-woven composite was fabricated incorporating four plies of unidirectionally oriented, substantially parallel 45 g/d fibers. The fibers were washed to substantially remove their fiber finish and subsequently plasma treated and dried. The fiber tenacity after the plasma treatment was 45 g/d. Thereafter, the fibers were coated with an aliphatic, anionic polyurethane dispersion having a modulus of 1100 psi. Each ply had a resin content of approximately 16% by weight of the ply. The four plies were oriented at 0°/90 ^ο /0°/90 ^ο relative to the longitudinal fiber direction of each ply. The four- ply composite had a fiber areal density (per ply) of approximately 53 gsm and a total areal density of each ply of approximately 64 gsm.

While the present invention has been particularly shown and described with reference to preferred embodiments, it will be readily appreciated by those of ordinary skill in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. It is intended that the claims be interpreted to cover the disclosed embodiment, those alternatives which have been discussed above and all equivalents thereto.