Patent Publication Number: US-2023150240-A1

Title: Biaxially-stretchable barrier laminate fabric composite material and method of manufacture

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims priority to U.S. Provisional Application No. 63/264,267, titled “Biaxially-Stretchable Barrier Laminate Fabric and Method of Manufacture,” filed on Nov. 18, 2021, which is hereby incorporated by reference. 
    
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH 
     This invention was made with government support under Contract No. W911QY20C0022 awarded by the Defense Threat Reduction Agency (DTRA). The government has certain rights in the invention. 
    
    
     TECHNICAL FIELD 
     This application relates generally to personal protective clothing and equipment. 
     BACKGROUND 
     Chemical, biological, radioactive and nuclear (CBRN) protective ensembles are widely used by military and civilian first responders as the first line of defense for protecting personnel working in contaminated environments. Commercial ensembles, such as Tychem® (Dupont Corp.), Trellchem® (Ansell Ltd.), or Onesuit® (Saint Gobain Performance Plastics), are typically constructed using a protective fabric that prevents permeation and breakthrough of toxic chemicals. The main mode of action is to present a physical barrier between the wearer and the toxic environment. This is achieved by constructing the garment using a protective fabric consisting of a base textile material either impregnated with or laminated to a barrier polymer layer. 
     Since most polymers that are good barriers to chemical permeation are usually stiff with low elongation levels, currently-available CBRN ensembles are bulky, preventing the user from unrestricted and agile movement. 
     SUMMARY 
     Example embodiments described herein have innovative features, no single one of which is indispensable or solely responsible for their desirable attributes. The following description and drawings set forth certain illustrative implementations of the disclosure in detail, which are indicative of several exemplary ways in which the various principles of the disclosure may be carried out. The illustrative examples, however, are not exhaustive of the many possible embodiments of the disclosure. Without limiting the scope of the claims, some of the advantageous features will now be summarized. Other objects, advantages and novel features of the disclosure will be set forth in the following detailed description of the disclosure when considered in conjunction with the drawings, which are intended to illustrate, not limit, the invention. 
     An aspect of the invention is directed to a method for forming a biaxially stretchable barrier laminate fabric composite material, comprising: biaxially stretching a substrate fabric from a substrate relaxed state to a biaxially-stretched state; forming individual bond points between a barrier film and the substrate fabric while the substrate fabric is in the biaxially-stretched state and the barrier film is in a flat state to form a laminated fabric composite material; and after forming the bond points: biaxially relaxing the substrate fabric from the biaxially-stretched state to the substrate relaxed state; and while the substrate fabric is biaxially relaxed, forming random folds in the barrier film between the bond points. 
     In one or more embodiments, the step of forming the bond points between the barrier film and the substrate fabric comprises: selectively applying an adhesive to the substrate fabric and/or to the barrier film; after selectively applying the adhesive to the substrate fabric and/or to the barrier film, physically contacting the substrate fabric and the barrier film such that the adhesive is between the substrate fabric and the barrier film; and curing the adhesive. In one or more embodiments, the step of selectively applying the adhesive to the substrate fabric and/or to the barrier film comprises applying adhesive dots to the substrate fabric and/or to the barrier film. In one or more embodiments, each adhesive dot has a respective adhesive dot size of about 0.1 to about 2 microliters. In one or more embodiments, the method further comprises applying the adhesive dots in a regular grid pattern, wherein a straight-line distance between neighboring adhesive dots is greater than or equal to about 0.1 inches and less than or equal to about 2 inches, the straight-line distance measured while the substrate fabric is in the biaxially-stretched state. 
     In one or more embodiments, the step of forming the bond points between the barrier film and the substrate fabric comprises: physically contacting the substrate fabric and the barrier film; and while physically contacting the substrate fabric and the barrier film, selectively applying radio-frequency, ultrasound, and/or heat energy to the substrate fabric and the barrier film to form the bond points. In one or more embodiments, the substrate fabric is a first substrate fabric, the bond points are first bond points, the substrate relaxed state is a first-substrate relaxed state, the biaxially-stretched state is a first biaxially-stretched state, and the method further comprises: biaxially stretching a second substrate fabric from a second-substrate relaxed state to a second biaxially-stretched state; after forming the first bond points between the barrier film and the first substrate fabric, forming second bond points between the barrier film and the second substrate fabric while the second substrate fabric is in the second biaxially-stretched state to form the laminated fabric composite material; and after forming the second bond points: biaxially relaxing the first substrate fabric from the first biaxially-stretched state to the first-substrate relaxed state; and biaxially relaxing the second substrate fabric from the second biaxially-stretched state to the second-substrate relaxed state; and forming the random folds in the barrier film between the first and second bond points. In one or more embodiments, the method further comprises aligning the first and second bond points with respect to each other. 
     Another aspect of the invention is directed to a method for forming a biaxially-stretchable barrier laminate fabric composite material, comprising: forming individually bond points between a barrier film and a substrate fabric while the substrate fabric is in a relaxed state and the barrier film is in a flat state to form a laminated fabric composite material; biaxially stretching the laminated fabric composite material to cause a strain on the barrier film that is greater than a yield strain of the barrier film to permanently increase biaxial dimensions of the barrier film; biaxially relaxing the laminated fabric composite material from a biaxially-strained state to a barrier-film relaxed state; and while the laminated fabric composite material transitions from the biaxially-strained state to the barrier-film relaxed state, forming random folds in the barrier film between the bond points. 
     Another aspect of the invention is directed to a method for forming a stretchable barrier laminate fabric composite material, comprising: biaxially stretching a substrate fabric by a first percentage from a substrate relaxed state to a substrate biaxially-stretched state; forming individual bond points between a barrier film and the substrate fabric while the substrate fabric is in the biaxially-stretched state and the barrier film is in a flat state to form a laminated fabric composite material, the laminated fabric composite material in a first biaxially-stretched state; after forming the bond points between the barrier film and the substrate fabric, biaxially stretching the laminated fabric composite material by a second percentage to transition the laminated fabric composite material to a second biaxially-stretched state, the second percentage determined with respect to the first biaxially-stretched state; after biaxially stretching the laminated fabric composite material by the second percentage: biaxially relaxing the laminated fabric composite material from the second biaxially-stretched state to the first biaxially-stretched state; and biaxially relaxing the substrate fabric from the substrate biaxially-stretched state back to the substrate relaxed state; and while the substrate fabric is biaxially relaxed, forming random folds in the barrier film between the bond points. 
     In one or more embodiments, biaxially stretching the laminated fabric composite material by the second percentage causes a strain on the barrier film that is greater than a yield strain of the barrier film. 
     Another aspect of the invention is directed to a biaxially-stretchable barrier laminate fabric composite material comprising: a biaxially-stretchable substrate fabric having a relaxed state and a biaxially-stretched state, wherein dimensions of the biaxially-stretchable substrate fabric are greater in the biaxially-stretched state than in the relaxed state; a barrier film selectively attached to the biaxially-stretchable substrate fabric at a plurality of individual bond points, the barrier film having unbonded regions between the bond points, wherein the biaxially stretchable barrier laminate fabric is configured such that: when the biaxially-stretchable substrate fabric is in the relaxed state, the barrier film is in a randomly folded state in which random folds are formed in the unbonded regions of the barrier film, the random folds oriented with respect to a machine direction, a cross direction, and an orthogonal direction, wherein the machine direction, the cross direction and the orthogonal direction are mutually orthogonal to one another, and when the biaxially-stretchable substrate fabric is in the biaxially-stretched state, the barrier film is in a flat state in which the random folds are partially or fully unfolded. 
     In one or more embodiments, the biaxially-stretchable substrate fabric is capable of stretching biaxially without substantially stretching the barrier film. In one or more embodiments, the barrier film comprises: first and second outer flexible layers; and a central barrier layer between the first and second outer flexible layers. In one or more embodiments, the central barrier layer comprises an ethylene vinyl alcohol polymer. In one or more embodiments, the first and second outer flexible layers comprise a thermoplastic polyurethane. 
     In one or more embodiments, the bond points comprise adhesive dots. In one or more embodiments, a straight-line distance between neighboring bond points is greater than or equal to about 0.1 inches and less than or equal to about 2 inches, the straight-line distance measured while the substrate fabric is in the biaxially-stretched state. In one or more embodiments, the barrier film is configured to reversibly biaxially stretch within a barrier film elastic region when the biaxially-stretchable substrate fabric is in the biaxially-stretched state. In one or more embodiments, the material is configured to reversibly biaxially stretch and relax for at least 2,000 cycles. In one or more embodiments, the barrier layer functions as a chemical barrier regardless of whether the barrier layer is in the randomly folded state or the flat state. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       For a fuller understanding of the nature and advantages of the concepts disclosed herein, reference is made to the detailed description of preferred embodiments and the accompanying drawings. 
         FIG.  1    is a perspective view of a biaxially stretchable laminated fabric composite material in a relaxed state according to an embodiment. 
         FIG.  2    is a perspective view of the composite material illustrated in  FIG.  1    in a biaxially-stretched state according to an embodiment. 
         FIG.  3    is a perspective view of the composite material illustrated in  FIGS.  1  and  2    reversibly transitioning between a relaxed state, a partially-stretched state, and an optional fully-stretched state. 
         FIG.  4    is a cross-sectional illustration of the barrier film illustrated in  FIGS.  1 - 3    according to an embodiment. 
         FIGS.  5  and  6    are schematic diagrams of the bond points in the composite material illustrated in  FIGS.  1 - 3    according to different embodiments. 
         FIG.  7    is a side view of a biaxially stretchable laminated fabric composite material in a relaxed state according to another embodiment. 
         FIG.  8    is a side view of the composite material illustrated in  FIG.  7    in a biaxially-stretched state according to an embodiment. 
         FIG.  9    is a side view of a biaxially stretchable laminated fabric composite material in a biaxially-stretched state according to another embodiment. 
         FIG.  10    is a side view of a biaxially stretchable laminated fabric composite material in a biaxially-stretched state according to another embodiment. 
         FIG.  11    is a side view of a biaxially stretchable laminated fabric composite material in a relaxed state according to another embodiment. 
         FIG.  12    is a biaxially stretchable laminated fabric composite material illustrated in  FIG.  11    in a biaxially-stretched state according to an embodiment. 
         FIG.  13    is a side view of a biaxially stretchable laminated fabric composite material according to another embodiment. 
         FIG.  14    is a flow chart of a method for manufacturing a biaxially stretchable laminated fabric composite material according to an embodiment. 
         FIG.  15    is a perspective view of a substrate fabric that is stretched from a relaxed state to a biaxially-stretched state. 
         FIG.  16    is a perspective view of a biaxially stretchable laminated fabric composite material in which the substrate fabric is selectively attached to a barrier film at a plurality of individual bond points while the substrate fabric is in the biaxially-stretched state. 
         FIG.  17    is a perspective view of the biaxially stretchable laminated fabric composite material illustrated in  FIG.  16    transitioning from the biaxially-stretched state to a relaxed state. 
         FIG.  18    is a flow chart of the step of forming individual bond points between the substrate fabric and the barrier film according to an embodiment. 
         FIG.  19    illustrates an example of attaching a barrier film and a substrate fabric with adhesive dots according to an embodiment. 
         FIG.  20    is a flow chart of the step of forming individual bond points between the substrate fabric and the barrier film according to another embodiment. 
         FIG.  21    is a flow chart of a method for manufacturing a biaxially stretchable laminated fabric composite material according to another embodiment. 
         FIG.  22    illustrates an example of a biaxially stretchable laminated fabric composite material where the barrier film transitions between a flat state, a strained state, and a randomly folded state. 
         FIG.  23    is a flow chart of a method for manufacturing a biaxially stretchable laminated fabric composite material according to another embodiment. 
         FIG.  24    illustrates an example of a composite material where the fabric substrate transitions between a first biaxially-stretched state, a second biaxially-stretched state, and a relaxed state. 
         FIG.  25    is a flow chart of a method for manufacturing a biaxially stretchable laminated fabric composite material according to another embodiment. 
         FIG.  26    illustrates an example of a composite material formed using method of  FIG.  25   . 
         FIG.  27    illustrates CRBN garments according to an embodiment 
     
    
    
     DETAILED DESCRIPTION 
       FIG.  1    is a perspective view of a biaxially stretchable laminated fabric composite material  10  in a relaxed state according to an embodiment. The composite material  10  includes a four-way stretchable substrate fabric  100  and a barrier film  110 . The stretchable substrate fabric  100  and the barrier film  110  are attached at a series of individual bond points  120 . The bond points  120  can be regularly and/or irregularly spaced with respect to the surface of the substrate fabric  100  and/or the barrier film  110 . In the unbonded regions  112  between the bond points  120 , the barrier film  110  is not bonded and decoupled from the substrate fabric  100 . 
     The substrate fabric  100  can comprise or consist of any woven, knit, or non-woven fabric that is capable of reversibly stretching biaxially (4-way stretch) in the machine direction  141  and in the cross direction  142 . In an embodiment, the substrate fabric  100  can bi-axially stretch up to 30% (e.g., from about 1% to about 30), up to about 50% (e.g., from about 1% to about 50%), up to about 100% (e.g., from about 1% to about 100%), or up to more than 100% from its relaxed state. That is, the dimensions of the substrate fabric  100  with respect to the machine and cross directions  141 ,  142  are up to 50%, up to 100%, or up to more than 100% larger in the biaxially-stretched state ( FIG.  2   ) than in the relaxed state ( FIG.  1   ). Upon removal of the biaxal-stretching force, the substrate fabric  100  returns to at least about 95% and preferably about 100% of its original dimensions, with respect to the machine and cross directions  141 ,  142 , when transitioning back to the relaxed state from the biaxially-stretched state. The original dimensions are the dimensions, with respect to the machine and cross directions  141 ,  142 , of the substrate fabric  100  in the relaxed state before any stretching forces are applied to the substrate fabric  100 . Examples of 4-way stretchable fabrics for substrate fabric  100  include fabrics made by blending spandex (e.g., elastane or Lycra®) fibers along with other textile fibers such as polyester, nylon, nomex, rayon, modal, cotton, Lyocell and/or modacrylic fibers. 
     The barrier film  110  is in a randomly folded state. The random folds  130  in the barrier film  110  are present in three dimensions along the machine direction  141 , the cross direction  142 , and the orthogonal direction  143  of the composite material  10 . The orthogonal direction  143  is the direction perpendicular to both the machine and cross directions  141 ,  142 . The random folds  130  can be randomly oriented and/or multi-directional with respect to the machine direction  141 , the cross direction  142 , and/or the orthogonal direction  143 . The random folds  130  do not have a preferred direction or orientation. The random folds  130  can alternately be referred to and/or can include crumples. 
     The bond points  120  can be formed using adhesive dots. While for the purpose of this disclosure, the shape of the adhesive dots is circular, hemispherical or spherical, the shape of the adhesive dots need not necessarily be one with an aspect ratio (length to width) of 1 and can include any other shape such as short dashes, rectangles, another regular shape, or an irregular shape. The adhesive dots can include any suitable adhesive that can form a bond between the substrate fabric  100  and the barrier film  110 . In an embodiment, the adhesive dots can include an adhesive selected from the family of hot-melt adhesives, the family of ultra-violet (UV)-curable liquid adhesives, the family of heat-curable liquid adhesives, the family of moisture-curable 2-part liquid adhesives, the family of pressure-sensitive adhesives, and/or other adhesive families. The adhesive is preferably suitable to be applied in the form of small dots (or other geometric shape) via any process typically used in the industry such as gravure roll, rotary screen printing, jetting guns, screen printing, and/or another application process. 
     The adhesive can provide a bond strength between the substrate fabric  100  and the barrier film  110  having a range of about 0.1 lb per dot to about 5 lb per dot, including about 0.5 lb per dot, about 1 lb per dot, about 1.5 lb per dot, about 2 lb per dot, about 2.5 lb per dot, about 3 lb per dot, about 3.5 lb per dot, about 4 lb per dot, about 4.5 lb per dot, and any value or range between any two of the foregoing values. For example, the adhesive can provide a bond strength having a range of about 0.1 lb per dot to about 2 lb per dot or a range of about 0.25 lb per dot to about 1.5 lb per dot. The bond strength can be characterized as the raw forced to break the adhesive bond. 
     The adhesive dot size may be in the range of about 0.1 microliters to about 2 microliters (on a volume basis) including about 0.25 microliters, about 0.5 microliters, about 0.75 microliters, about 1 microliter, about 1.25 microliters, about 1.5 microliters, about 1.75 microliters, and any value or range between any two of the foregoing volumes. For example, the adhesive dot size can be in the range of about 0.1 microliters to about 1 microliter or the range of about 0.1 microliters to about 0.5 microliters. In general, the bond strength provided by the adhesive dot should be sufficient to prevent delamination and/or separation of the barrier film  110  and substrate fabric  100  during repeated biaxial stretching of the composite material  10 . Biaxial stretching of the composite material  10  can include flexing, folding, unfolding, relaxing, elongating, twisting and/or crushing of the barrier film  110  and the substrate fabric  100 . Biaxial stretching of the composite material  10  can optionally include biaxial stretching of the barrier film  110 . 
     In an alternative embodiment, the bond points  120  can be formed by direct bonding without using an adhesive. For example, the bond points  120  can be formed using heat, radio-frequency (RF) energy, and/or ultrasonic bonding techniques. The bond strength of the bond points  120  formed without an adhesive can be equal to or about equal to the bond strength of the bond points  120  formed with an adhesive (e.g., with the adhesive dots). For example, the bond strength of the of bond points  120  formed without an adhesive (e.g., using heat, RF energy, and/or ultrasonic bonding techniques) can have a range of about 0.1 lb per bond point  120  to about 5 lb per bond point  120 . 
       FIG.  2    is a perspective view of the composite material  10  in a biaxially-stretched state according to an embodiment. As the composite material  10  is biaxially stretched (i.e., with respect to the machine and cross directions  141 ,  142 ), the random folds  130  flatten without stretching the barrier film  110 . The barrier film  110  is in a flattened state in this figure. The dimensions of the barrier film  110  with respect to the machine and cross directions  141 ,  142  are larger in the flattened state than they are in the randomly folded state ( FIG.  1   ). The dimensions of the barrier film  110  can increase by about the same percentage as the substrate fabric  100 , with respect to the machine and cross directions  141 ,  142 , as the composite material  10  is biaxially stretched. For example, the dimensions of the substrate fabric  100  and the barrier film  110  can increase by about 20-25%, with respect to the machine and cross directions  141 ,  142 , when composite material  10  transitions from a relaxed state ( FIG.  1   ) to a biaxially-stretched state ( FIG.  2   ). 
     Flattening the barrier film  110  allows the composite material  10  to reversibly biaxially elongate while maintaining the chemical barrier performance of the overall composite material  10 . Flattening the barrier film  110  can include extending and/or unfolding (e.g., partially and/or fully) of the random folds  130  in the barrier film  110  to smoothen the unbonded regions  112  as the bond points  120  move while the composite material  10  is biaxially stretched. The barrier film  110  can be flattened without biaxially stretching or without substantially biaxially stretching the barrier film  110 . For example, the barrier film  110  can be flattened while biaxially stretching the barrier film  110  to be between 0% and 5% greater than the dimensions of the barrier film  110  in the flattened state. 
     Further, the composite material  10  in the biaxially-stretched state is capable of returning to the relaxed state ( FIG.  1   ), including the associated dimensions and/or form, when the stresses are removed. The composite material  10  can undergo reversible biaxial stretch and relaxation cycles (i.e., repeatedly transitioning between the relaxed state and the biaxially-stretched state), for example more than 100 cycles, more than 500 cycles, more than 1,000 cycles, more than 2,000 cycles, or more than another number of cycles, which can be greater than 2,000 cycles or less than 100 cycles, without compromising dimensional stability or chemical-barrier properties of the composite material  10 . 
     The barrier film  110  is not stretched during flattening. In some embodiments, the barrier film  110  can reversibly biaxially stretch in addition to flatten. For example, the barrier film  110  can reversibly biaxially stretch up to about 5-8%, within the elastic region of the barrier film  110 , compared to the dimensions of the barrier film  110  before stretching. The barrier film  110  is capable of returning to its original dimensions in the relaxed state (i.e., before being biaxially stretched) when the barrier film  110  is reversibly biaxially stretched. In other words, reversibly biaxially stretching does not include permanent plastic deformation of the barrier film  110 . When the composite material  10  includes a barrier film  110  that can be reversibly biaxially stretched, the composite material  10  reversibly biaxially expand to larger dimensions in the stretched state compared to when the composite material  10  includes a barrier film  110  that cannot be reversibly biaxially stretched. 
     An example illustration of the composite material  10  reversibly transitioning between a relaxed state  31 , a partially-stretched state  32 , and an optional fully-stretched state  33  is illustrated in  FIG.  3   . In the relaxed state  31 , the barrier film  110  is in the randomly folded state. In the partially-stretched state  32 , the composite material  10  is biaxially stretched such that the barrier film  110  is in the flattened or unfolded state. In the optional fully-stretched state  33 , the composite material  10  is further biaxially stretched, compared to the partially-stretched state  32 , such that the barrier film  110  is reversibly biaxially stretched within its elastic region. The dimensions along the machine and cross directions  141 ,  142  are larger when the composite material  10  is in the partially-stretched state  32  than in the relaxed state  31 . The dimensions along the machine and cross directions  141 ,  142  are larger when the composite material  10  is in the fully-stretched state  33  than in the partially-stretched state  32  and the relaxed state  31 . 
     A CBRN garment formed with the composite material  10  is more comfortable to the wearer by stretching and conforming to body movements without degrading chemical-protection properties. The composite material  10  can have a minimum thickness (as measured with respect to the orthogonal axis  143 ) equal to the thickness of the substrate fabric  100  and the barrier film  110  and/or a maximum thickness of about 0.5 inches. In some embodiments, the thickness of the composite material  10  is about 1/16 inches. 
       FIG.  4    is a cross-sectional illustration of the barrier film  110  according to an embodiment. The barrier film  110  includes a central barrier layer  400  sandwiched between outer flexible layers  410 ,  420 . An optional tie layer  431  can be located between the barrier layer  400  and outer flexible layer  410 . Additionally or alternatively, an optional tie layer  432  can be located between the barrier layer  410  and outer flexible layer  420 . 
     The barrier layer  400  can comprise or consist of an ethylene vinyl alcohol (EVOH) polymer, a polyamide, a polyester, polyvinylidene chloride, polyvinyl chloride, polytetrafluoroethylene, chloroprene, or butyl rubber. When the barrier layer  400  comprises or consists of an EVOH polymer, the EVOH polymer can be any grade with an ethylene content ranging from about 24 mol % to about 48 mol %, including about 30 mol %, about 36 mol %, and/or about 42 mol %. In some embodiments, an EVOH barrier polymer with about 44 mol % of ethylene can provide optimum flexibility and chemical-barrier properties. 
     The barrier layer  400  has sufficient resistance to toxic chemicals such that the barrier layer  400  can prevent toxic chemicals from permeating therethrough for at least 60 minutes, including at least 120 minutes, at least 180 minutes, at least 240 minutes, at least 300 minutes, at least 360 minutes, at least 420 minutes, and/or at least 480 minutes, including any time or range between any two of the foregoing times. The time that the barrier layer  400  is resistant to toxic chemical permeating therethrough can be referred to as the breakthrough time of the barrier layer  400 . The barrier layer  400  is resistant to (e.g., to the permeation of) toxic chemicals as listed in the National Fire Protection Association (NFPA) specifications such as the NFPA 1992 and/or the NFPA 1994 specifications. Examples of toxic chemicals to which the barrier layer  400  is resistant include, but not limited to, tetrachloroethylene, toluene, diethylamine, ammonia, chlorine, carbon disulfide, acids such as sulfuric acid and including chemical warfare agents such as sulfur mustard (HD) and nerve agents such as Tabun (GA), Sarin (GB), Soman (GD) and Venomous agent X (VX). The barrier layer  400  has the same resistance to the toxic chemicals regardless of whether the barrier layer  400  is in a randomly folded state, a flat state, or a reversibly-stretched state. 
     The outer flexible layers  410 ,  420  can comprise or consist of a thermoplastic polyurethane (TPU), thermoplastic polyolefin elastomers and/or plastomers, ethylene vinyl acetate copolymers, styrene-butadiene copolymers, and/or elastomers or rubbers such as butyl rubber, halobutyl rubbers, neoprene, nitrile, ethylene propylene diene monomer rubber (EPDM), silicone and the like. The outer flexible layers  410 ,  420  can be any grade that is processable into films via melt extrusion, though softer grades are preferable from the film-flexibility standpoint. The outer flexible layers  410 ,  420  are preferably formed of the same material(s). 
     The optional tie layers  431 ,  432  can comprise or consist of tie polymers such as ethylene methacrylate copolymers, ethylene methacrylic acid copolymers, ethylene acrylic acid copolymers, maleic anhydride or anhydride modified polyolefin polymer, ethylene vinyl acetate copolymer, anhydride modified ethylene vinyl acetate polymer, and/or anhydride modified ethylene acrylate copolymer. 
     The central barrier layer  400  is configured to provide the primary barrier to permeation of toxic chemicals through the barrier film  110 . The outer flexible layers  410 ,  420  are configured to provide flexibility and provide a surface that can be easily bonded to the substrate fabric. The optional tie layer(s)  431 ,  432  can be configured to improve the adhesion between the central barrier layer  400  and either or both outer flexible layers  410 ,  420 . 
     The central barrier layer  400  can have a thickness of about 0.1 mil to about 1 mil, including about 0.25 mil, about 0.5 mil, about 0.75 mil, and any value or range between any two of the foregoing thicknesses. The thickness of each outer flexible layer  410 ,  420  can be about 0.1 mil to about 2 mil, including about 0.5 mil, about 0.75 mil, about 1 mil, about 1.25 mil, about 1.5 mil, about 1.75 mil, and any value or range between any two of the foregoing thicknesses. In one example, the thickness of each outer flexible layer  410 ,  420  can be about 0.1 mil to about 1 mil, including about 0.25 mil, about 0.5 mil, about 0.75 mil, and any value or range between any two of the foregoing thicknesses. 
     The thickness of each optional tie layer  431 ,  432  can be about 0.1 mil to about 0.5 mil, including about 0.2 mil, about 0.3 mil, about 0.4 mil, and any value or range between any two of the foregoing thicknesses. The thickness of a tie layer is 0 mil when that tie layer is not included in the barrier film  110 . The thickness of each layer  400 ,  410 ,  420 ,  431 ,  432  is measured with respect to an axis  440 , which is orthogonal to the machine and cross axes  141 ,  142 . 
       FIGS.  5  and  6    are schematic diagrams of the bond points  120  in the composite material according to different embodiments. In  FIG.  5   , the bond points  120  are arranged in a rectangular grid pattern. In  FIG.  6   , the bond points  120  are arranged in an alternating pattern. The straight-line distance between adjacent bond points  120  (e.g., distances A-C in  FIG.  5    and distances D-G in  FIG.  6   ), as measured when the material  10  is in the biaxially-stretched state, can be at least about 0.1 inches. For example, the straight-line distance between adjacent bond points  120 , as measured when the material  10  is in the biaxially-stretched state, can be about 0.1 inches to about 2 inches, including about 0.25 inches, about 0.5 inches, about 0.75 inches, about 1 inch, about 1.25 inches, about 1.5 inches, about 1.75 inches, and any value or range between any two of the foregoing distances. In another embodiment, the straight-line distance between adjacent bond points  120  can be greater than about 2 inches. The straight-line distance between adjacent bond points  120  is preferably at least large enough that neighboring/adjacent bond points  120  do not touch each other and remain separated and independent when the material  10  is in the relaxed state. The straight-line distance is measured with respect to an axis that lies within or parallel to the plane defined by the machine and cross directions. 
       FIG.  7    is a side view of a biaxially stretchable laminated fabric composite material  70  in a relaxed state according to an embodiment. The composite material  70  is the same as the composite material  10  except that composite material  70  includes two substrate fabric layers while composite material  10  only include one substrate fabric layer. 
     In composite material  70 , the barrier film  110  is attached to a pair of four-way stretchable substrate fabrics  100 ,  700 . The first substrate fabric  100  is attached to the barrier film  110  at a series of individual bond points  120  as in composite material  10 . A second substrate fabric  700  is attached to the barrier film  110  at a series of individual bond points  720 . The bond points  120 ,  720  are aligned with respect to respective axes, such as axis  710 , that are orthogonal to the machine and cross directions  141 ,  142 , such that the bond points  120 ,  720  are located at the same or about the same locations (e.g., within about 0.05 inches or another straight-line distance of each other) relative to the barrier film  110 . The straight-line distance between neighboring bond points  720  is the same as the straight-line distance between neighboring bond points  120 . 
     The second substrate fabric  700  can be the same as or different than the first substrate fabric  100 . The first and second substrate fabrics  100 ,  700  can have the same or similar stretch and relaxation properties. Additionally or alternatively, the bond points  720  can be the same as bond points  120 . 
     The composite material  70  is in the relaxed state in  FIG.  7    such that random folds  130  are formed in the unbonded regions of the barrier film  110  between bond points  120 ,  720 . 
     The composite material  70  is in a biaxially-stretched state in  FIG.  8    such that the random folds  130  are flattened to transition the barrier film  110  to a flattened state. In some embodiments, the barrier film  110  can reversibly biaxially stretch within its elastic region to allow the composite material  70  to be biaxially stretched further. When the barrier film  110  can reversibly biaxially stretch within its elastic region, the composite material  70  can reversibly transition between a flat state, a partially-stretched state, and a fully-stretched state, for example as described above with respect to  FIG.  3   . The partially-stretched and fully-stretched states would appear the same as illustrated in  FIG.  8    except that the dimensions of the composite material  70  with respect to the machine and cross directions  141 ,  142  would be larger when the composite material  70  is in the fully-stretched state than when the composite material  70  is in the partially-stretched state. The alignment of the bond points  120 ,  720  is determined and/or measured when the composite material  70  is in the biaxially-stretched state. 
       FIG.  9    is a side view of a biaxially stretchable laminated fabric composite material  90  in a biaxially-stretched state according to another embodiment. In this embodiment, the bond points  120 ,  720  are offset from each other with respect to respective axes, such as axis  710 . The bond points  120 ,  720  having an alternating pattern where a bond point  120  is located between neighboring bond points  720  and a bond point  720  is located between neighboring bond points  120 . The barrier film  110  is in a flattened state in  FIG.  9   . 
     The straight-line distance (e.g., distance A) between a bond point  120  and a neighboring bond point  720  (or vice versa), as measured when the composite material  70  is in the biaxially-stretched state, can be about 0.1 inches to about 2 inches, including about 0.25 inches, about 0.5 inches, about 0.75 inches, about 1 inch, about 1.25 inches, about 1.5 inches, about 1.75 inches, and any value or range between any two of the foregoing distances. In another embodiment, the straight-line distance between adjacent bond points  120  can be greater than about 2 inches. The straight-line distance is preferably at least large enough that neighboring/adjacent bond points  120 ,  720  do not overlap (e.g., with respect to respective axes, such as axis  710 ) and remain separated and independent when the composite material  90  is in the relaxed state. The straight-line distance is measured with respect to an axis that lies within or parallel to the plane defined by the machine and cross directions  141 ,  142 . In  FIG.  9   , the axis is parallel to the machine direction  141 . 
     The relaxed state of the composite material  90  can appear the same as or similar to the relaxed state of the composite material  70  illustrated in  FIG.  7   . 
       FIG.  10    is a side view of a biaxially stretchable laminated fabric composite material  1000  in a biaxially-stretched state according to another embodiment. The bond points  120 ,  720  in composite material  1000  are in a hybrid configuration of the bond points  120 ,  720  in composite materials  70  and  90 . In composite material  1000 , some of the bond points  120 ,  720  are aligned and some of the bond points  120 ,  720  are offset from each other. As discussed above, the alignment of and straight-line distance between neighboring bond points  120 ,  720  are determined when the composite material is in the biaxially-stretched state and with respect to respective axes, such as axis  710 , that are orthogonal to the machine and cross directions  141 ,  142 . The barrier film  110  is in a flattened state in  FIG.  10   . 
     The relaxed state of the composite material  1000  can appear the same as or similar to the relaxed state of the composite material  70  illustrated in  FIG.  7   . 
       FIG.  11    is a side view of a biaxially stretchable laminated fabric composite material  1100  in a relaxed state according to another embodiment. The composite material  1100  is the same as the composite material  10  except that composite material  1100  includes two barrier film layers while composite material  10  only include one barrier film layer. 
     In composite material  1100 , the substrate fabric  100  is attached to a pair of barrier films  110 ,  1110 . The substrate fabric  100  is attached to the first barrier film  110  at a series of individual bond points  120  as in composite material  10 . The substrate fabric  100  is attached to the second barrier film  1110  at a series of individual bond points  1120 . The bond points  120 ,  1120  are aligned with respect to respective axes, such as axis  1140 , that are orthogonal to the machine and cross directions  141 ,  142 , such that the bond points  120 ,  1120  are located at the same or about the same locations (e.g., within about 0.05 inches or another straight-line distance of each other) relative to the substrate fabric  100 . The straight-line distance between neighboring bond points  1120  is the same as the straight-line distance between neighboring bond points  120 . 
     The second barrier film  1110  can be the same as or different than the first barrier film  110 . In an embodiment, the first barrier film  110  can be configured to provide protection for chemicals (or certain chemicals) and the second barrier film  1110  can be configured to provide protection for other chemicals and/or for biological, radioactive, and/or nuclear agents/toxins. When the first and second barrier films  110 ,  1110  can reversibly biaxially stretch, the first and second barrier films  110 ,  1110  can have the same or similar stretch and relaxation properties. Additionally or alternatively, the bond points  1120  can be the same as bond points  120 . 
     The composite material  1100  is in the relaxed state in  FIG.  11    such that random folds  130 ,  1130  are formed in the unbonded regions of the first and second barrier films  110 ,  1110  between bond points  120 ,  1120 , respectively. Random folds  1130  can be the same as or similar to random folds  130 . 
     The composite material  1100  is in a biaxially-stretched state in  FIG.  12    such that the random folds  130 ,  1130  are flattened to transition the first and second barrier films  110 ,  1110  to a flattened state. In some embodiments, the first and second barrier films  110 ,  1110  can reversibly biaxially stretch within their elastic regions to allow the composite material  1100  to be biaxially stretched further. When the first and second barrier films  110 ,  1110  can reversibly biaxially stretch within their elastic regions, the composite material  1100  can reversibly transition between a flat state, a partially-stretched state, and a fully-stretched state, for example as described above with respect to  FIG.  3   . The partially-stretched and fully-stretched states would appear the same as illustrated in  FIG.  12    except that the dimensions of the composite material  1100  with respect to the machine and cross directions  141 ,  142  would be larger when the composite material  1100  is in the fully-stretched state than when the composite material  1100  is in the partially-stretched state. 
     Combinations of the embodiments illustrated in  FIGS.  7 - 12    are possible. For example, the bond points  120 ,  1120  can be offset with respect to each other. Alternatively, some of the some of the bond points  120 ,  1120  can be aligned with each other and some of the bond points  120 ,  1120  can offset from each other. In another combination, the composite material includes an alternating arrangement of barrier film layers and substrate fabric layers. Each barrier layer film can be configured to provide the same or different CBRN protection. 
       FIG.  13    is a side view of a biaxially stretchable laminated fabric composite material  1300  according to an embodiment. The composite material  1300  is the same as the composite material  1100  except that composite material  1300  includes two barrier film layers  110 ,  1110  and two substrate fabric layers  100 ,  1301  while composite material  1100  includes two barrier film layers  110 ,  1110  and one substrate fabric layer  100 . The composite material  1300  is only illustrated in a biaxially-stretched state where the first and second barrier films  110 ,  1110  are in a flattened state. The composite material  1300  can transition to a relaxed state the first and second barrier films  110 ,  1110  are in a random three-dimensional folded state similar to composite material  1100 . 
     The first and second barrier film layers  110 ,  1110  can be configured to provide the same or different CBRN protection. For example, the first film layer  110  can be configured to provide protection for chemicals (or certain chemicals) and the second barrier film  1110  can be configured to provide protection for other chemicals and/or for biological, radioactive, and/or nuclear agents/toxins. 
     In composite material  1300 , the first substrate fabric  100  is attached to first and second barrier films  110 ,  1110  and the second substrate fabric  1301  is attached to the first barrier film  110 , forming an alternating arrangement of substrate fabrics and barrier films. The second substrate fabric  1301  is attached to the first barrier film  110  at a series of individual bond points  1320 . The substrate fabric  100  is attached to the second barrier film  1110  at a series of individual bond points  1120 . The first substrate fabric  100  is attached to the first barrier film  110  at a series of individual bond points  120  as in composite material  10 . The bond points  120 ,  1120 ,  1320  are aligned with respect to respective axes, such as axis  1330 , that are orthogonal to the machine and cross directions  141 ,  142 , such that the bond points  120 ,  1120 ,  1320  are located at the same or about the same locations (e.g., within about 0.05 inches or another straight-line distance of each other) relative to the substrate fabrics  100 ,  1301 . The straight-line distance between neighboring bond points  1320  is the same as the straight-line distance between neighboring bond points  1120  and the straight-line distance between neighboring bond points  120 . In an alternative embodiment, some or all of the bond points  120 ,  1120 , and/or  1320  are offset from one another, for example similar to composite materials  90  and/or  1000 . 
     The alternating arrangement of barrier film layers and substrate fabric layers can be extended to include a third substrate fabric and/or a third barrier film. The third substrate fabric can be attached to the second barrier film  1110  at individual bond points. The third barrier film can be attached to the second substrate fabric  1301  at individual bond points. Additional barrier film layer(s) and/or substrate fabric layer(s) can be attached at individual bond points in a similar manner an outer substrate fabric layer and/or an outer barrier film layer, respectively. 
     Each barrier film can be configured to provide a different type of protection. For example, the composite material can include a first barrier film that can be configured to provide chemical protection, a second barrier film that can be configured to provide biological protection, a third barrier film that can be configured to provide radioactive protection, and/or a fourth barrier film that can be configured to provide nuclear protection. 
     In another example, the composite material can include a first barrier film that can be configured to provide a first type of chemical protection, a second barrier film that can be configured to provide a second type of chemical protection, a third barrier film that can be configured to provide a third type of chemical protection, and/or a fourth barrier film that can be configured to provide a fourth type of chemical protection. 
     In another example, the composite material can include a first barrier film that can be configured to provide a first type of biological protection, a second barrier film that can be configured to provide a second type of biological protection, a third barrier film that can be configured to provide a third type of biological protection, and/or a fourth barrier film that can be configured to provide a fourth type of biological protection. 
     In another example, the composite material can include a first barrier film that can be configured to provide a first type of radiation protection, a second barrier film that can be configured to provide a second type of radiation protection, a third barrier film that can be configured to provide a third type of radiation protection, and/or a fourth barrier film that can be configured to provide a fourth type of radiation protection. 
     In another example, the composite material can include a first barrier film that can be configured to provide a first type of nuclear protection, a second barrier film that can be configured to provide a second type of nuclear protection, a third barrier film that can be configured to provide a third type of nuclear protection, and/or a fourth barrier film that can be configured to provide a fourth type of nuclear protection. 
     Combinations of any of the foregoing are possible. 
       FIG.  14    is a flow chart of a method  1400  for manufacturing a biaxially stretchable laminated fabric composite material according to an embodiment. Method  1400  can be used to make composite material  10 ,  70 ,  90 ,  1000 ,  1100 ,  1300 , or  1600 . 
     In step  1401 , a substrate fabric is biaxially stretched to the extent of elongation desired or required in the final laminated fabric composite material. The substrate fabric can be the same as substrate fabric  100 . 
     The substrate fabric is preferably stretched equally or approximately equally in all four directions (e.g., in opposite directions in the machine direction and in opposite directions in the cross direction). Approximately the same stretching can mean that the magnitude of the elongation is within plus or minus about 1 to about 10% in each direction, including about 3%, about 5%, about 7%, and about 9%, including any value or range between any two of the foregoing percentages. In one example, the substrate fabric is stretched uniaxially with respect to a first axis (e.g., parallel to the machine direction) and then, while maintaining the stretch with respect to the first axis, the substrate fabric is then stretched with respect to a second axis (e.g., parallel to the cross direction) that is orthogonal to the first axis, such that a biaxal (e.g., four-way) stretch of the substrate fabric is performed. In another example, the substrate fabric is stretched simultaneously with respect to the first and second axes. In this step, the substrate fabric can be biaxially stretched such that the dimensions of the substrate fabric (e.g., in the machine and cross directions) increase by about 30% to about 100%, including about 50%, about 70%, about 90%, or another percentage, compared to the dimensions of the substrate fabric in the relaxed state. In another embodiment, the substrate fabric can be biaxially stretched such that the dimensions of the substrate fabric (e.g., in the machine and cross directions) increase by about 1% to about 30%, including about 5%, about 10%, about 15%, about 20%, about 25%, or another percentage, compared to the dimensions of the substrate fabric in the relaxed state. 
       FIG.  15    is a perspective view of a substrate fabric  1500  that is stretched from a relaxed state  1510  to a biaxially-stretched state  1520 . The dimensions of the substrate fabric  1500  are L′ and L in the machine and cross directions  141 ,  142 , respectively, when the substrate fabric  1500  is in the relaxed state  1510 . The dimensions of the substrate fabric  1500  are L and L′ in the machine and cross directions  141 ,  142 , respectively, when the substrate fabric  1500  is in the relaxed state  1510 . The dimensions of the substrate fabric  1500  are L+% L and L′+% L′ in the machine and cross directions  141 ,  142 , respectively, when the substrate fabric  1500  is in the biaxially-stretched state  1520 . The terms % L and % L′ indicate the percentage increase of the respective dimensions when the substrate fabric  1500  is in the biaxially-stretched state  1520  compared to when the substrate fabric  1500  is in the relaxed state  1510 . The substrate fabric  1500  can be the same as substrate fabric  100 . 
     In step  1402 , a plurality of individual bond points are formed between the substrate fabric and a barrier film to form a biaxially stretchable laminated fabric composite material. The bond points are formed while the substrate fabric is in the biaxially-stretched state and the barrier film is in a flattened or relaxed state. The barrier film can be the same as barrier film  110 . The individual bond points can be formed using adhesive dots and/or by direct bonding (e.g., bonding by applying heat, RF energy, and/or ultrasound energy). 
       FIG.  16    is a perspective view of a biaxially stretchable laminated fabric composite material  1600  in which the substrate fabric  1500  is selectively attached to a barrier film  1610  at a plurality of individual bond points  1620  while the substrate fabric  1500  is in the biaxially-stretched state  1520 . The barrier film  1610  and/or the bond points  1620  can be the same as barrier film  110  and the bond points  120 , respectively. 
     In step  1403 , if additional layers are to be attached to the biaxially stretchable laminated fabric composite material, the flow chart returns to step  1401 . If the additional layer includes another substrate fabric, the second substrate fabric is biaxially stretched in step  1401  and then selectively attached to the barrier film layer in step  1402  at individual bond points while the first and second substrate fabrics are in the biaxially-stretched state and while the barrier film is in the flattened or relaxed state. If the additional layer includes another barrier film layer, the biaxial stretch of the existing substrate fabric is maintained in step  1401  while the second barrier film is selectively attached to the substrate fabric at individual bond points in step  1402  while the first and second barrier films are in the flattened or relaxed state. Steps  1401 - 1403  repeat until all layers (e.g., substrate fabric layers and barrier film layers) are selectively attached to one another at individual bond points in an alternating configuration of substrate and barrier film layers (e.g., as discussed above). 
     When all layers are selectively attached to one another at individual bond points, the flow chart proceeds to step  1404  where the substrate fabric(s) are biaxially relaxed to transition the biaxially stretchable laminated fabric composite material to a relaxed state. The substrate fabric(s) can be relaxed with respect to the machine and cross directions simultaneously or sequentially. When the laminated fabric composite material includes two or more substrate fabrics, all substrate fabrics are preferably relaxed simultaneously. All substrate fabrics can be relaxed together in the machine and cross directions simultaneously or sequentially. 
     As the substrate fabric(s) are biaxially relaxed, in step  1405  the barrier film(s) transition from a flat state to a crumpled/folded state in which random three-dimensional folds or crumples are formed in the barrier film(s) between the individual bond points. This allows the composite laminate material to elongate in all directions either individually, or simultaneously, when the substrate fabric(s) are stretched during use, as discussed above, which improves the overall comfort and flexibility of the composite material. In some embodiments, the barrier film(s) can biaxially stretch within an elastic region to further increase the range of biaxial stretching of the composite material. 
       FIG.  17    is a perspective view of the biaxially stretchable laminated fabric composite material  1600  transitioning from the biaxially-stretched state  1520  to a relaxed state  1700  where random three-dimensional folds  1630  are formed in the barrier film  1610  between bond points  1620 . For illustration purposes only, the composite material  1600  is illustrated as having only one substrate fabric  1500  and only one barrier film  1610 . In the relaxed state, the composite material  1600  has the same or about the same dimensions, as measured in the machine and cross directions  141 ,  142 , as the substrate fabric  1500  in the relaxed state  1510 . The random folds  1630  can be the same as random folds  130 . 
       FIG.  18    is a flow chart of the step  1402  of forming individual bond points between the substrate fabric and the barrier film according to an embodiment. 
     In step  1801 , adhesive dots are applied to the substrate fabric and/or to the barrier film while the substrate fabric is in the biaxially-stretched state and the barrier film is in a flattened or relaxed state. An example of adhesive dots  1920  applied to a barrier film  1910  is illustrated in  FIG.  19   . The adhesive dots  1920  are applied in a regular pattern (e.g., in columns and rows). In other embodiments, the adhesive dots can be applied in a different pattern or irregularly. The barrier film  1910  is in a relaxed or flattened state  1915 . The barrier film  1910  can be the same as the barrier film  110 . 
     The adhesive dots can be applied using a gravure roll, rotary screen printing, jetting guns, screen printing, and/or another application process. In an embodiment, the adhesive dots are applied only to the substrate fabric. In another embodiment, the adhesive dots are applied only to the barrier film. In yet another embodiment, the adhesive dots are applied to both the substrate fabric and to the barrier film. The adhesive dots are spaced apart such that the straight-line distance between neighboring/adjacent adhesive dots is preferably at least large enough that neighboring/adjacent dots do not touch each other and remain separated and independent when the composite material is in the relaxed state. The straight-line distance between neighboring/adjacent adhesive dots can be about 0.1 inches to about 2 inches, including about 0.25 inches, about 0.5 inches, about 0.75 inches, about 1 inch, about 1.25 inches, about 1.5 inches, about 1.75 inches, and any value or range between any two of the foregoing distances. The adhesive dots can form a regular or irregular pattern, for example as discussed above with respect to  FIGS.  5  and  6   . 
     The adhesive dots can be applied to one or both sides of the barrier film and/or of the substrate fabric to selectively adhere multiple barrier film(s) and/or multiple substrate fabric(s) in an alternating arrangement. The adhesive dots can be aligned with respect to each other, for example as discussed above. 
     In step  1802 , the barrier film and the substrate fabric are moved together such that the adhesive dots physically contact both the barrier film and the substrate fabric. When the substrate dots are on the barrier film and on the substrate fabric, the substrate dots can be aligned (e.g., optically) before contact is made. The substrate fabric remains in the biaxially-stretched state and the barrier film remains in the relaxed/flattened state in step  1802 .  FIG.  19    illustrates an example of moving together 1930 the barrier film  1910  and a substrate fabric  1940  to physically contact the adhesive dots  1920  to both the barrier film  1910  and substrate fabric  1940 . The substrate fabric is in a biaxially-stretched state  1950 . The substrate fabric  1940  can be the same as the substrate fabric  100 . 
     In step  1803 , the adhesive dots are cured while the adhesive dots continue to physically contact both the barrier film and the substrate fabric. The adhesive dots can be cured by heating them, adding moisture to them, exposing them to UV light, applying pressure to them, cooling them (or allowing them to cool), and/or or adding a hardener. The barrier film and the substrate fabric can optionally be held together by applying pressure, a vacuum, and/or another means to improve/maintain the physical contact between the barrier film, the substrate fabric, and the adhesive dots. The substrate fabric remains in the biaxially-stretched state and the barrier film remains in the relaxed/flattened state in step  1803 . 
       FIG.  20    is a flow chart of the step  1402  of forming individual bond points between the substrate fabric and the barrier film according to another embodiment. 
     In step  2001 , the barrier film and the substrate fabric are moved together such that the barrier film and the substrate fabric are in physical contact with each other. The substrate fabric is in the biaxially-stretched state and the barrier film is in a flattened or relaxed state during step  2001 . 
     In step  2002 , energy is selectively applied to the barrier film and the substrate fabric, while the barrier film and the substrate fabric are in physical contact with each other and while the substrate fabric is in the biaxially-stretched state and the barrier film is in a flattened or relaxed state, to form individual bond points. The energy can include or consist of thermal energy, ultrasonic energy, and/or RF energy. 
       FIG.  21    is a flow chart of a method  2100  for manufacturing a biaxially stretchable laminated fabric composite material according to another embodiment. Method  2100  is preferred especially when the barrier film has an inherent reversible stretch (e.g., in an elastic region), but can also be used when the barrier film has little to no inherent stretch. Method  2100  can be used to make composite material  10 ,  70 ,  90 ,  1000 ,  1100 , or  1300 . 
     In step  2101 , a plurality of individual bond points are formed between a substrate fabric and a barrier film while both the substrate fabric and the barrier film are in the relaxed state to form a composite material. The barrier film can be the same as barrier film  110 . The individual bond points can be the same as individual bond points  120 . The individual bond points can be formed using adhesive dots and/or by direct bonding (e.g., bonding by applying heat, RF energy, and/or ultrasound energy). 
     The substrate fabric can be the same as the substrate fabric  100 . 
     Step  2101  is the same as step  1402  except that in step  2101  the substrate fabric is in the relaxed state while in step  1402  the substrate fabric is in the biaxially-stretched state. The barrier film is in the relaxed or flattened state in steps  1402  and  2101 . When the bond points are formed with adhesive dots, step  2101  can be performed according to steps  1801 - 1803  except that the barrier film is in the relaxed state during steps  1801 - 1803 . When the bond points are formed by selectively applying energy, step  2101  can be performed according to steps  2001 - 2002  except that the barrier film is in the relaxed state during steps  2001 - 2002 . 
     An example of a composite material  2200  formed in step  2101  is illustrated in  FIG.  22   . The composite material  2200  includes a substrate fabric layer  2201 , a barrier film layer  2210 , and bond points  2220  that selectively attach the substrate fabric layer  2201  and the barrier film layer  2210 . For illustration purposes only, the composite material  2200  is illustrated as having only one substrate fabric layer  2201  and only one barrier film layer  2210 . The composite material  2200  is in a relaxed state and the barrier film layer  2210  is in a flat state  2241  as a result of step  2101 . The substrate fabric layer  2201 , the barrier film layer  2210 , and/or the bond points  2220  can be the same as the substrate fabric  100 , the barrier film  110 , and the bond points  120 , respectively. 
     In step  2102 , if additional layers are to be attached to the composite material, the flow chart returns to step  2101 . If the additional layer includes another substrate fabric, the second substrate fabric is selectively attached to the barrier film layer in step  2101  at individual bond points while the first and second substrate fabrics and the barrier film are in the relaxed state. If the additional layer includes another barrier film layer, the second barrier film is selectively attached to the substrate fabric at individual bond points in step  1001  while the substrate fabric and the first and second barrier films are in the relaxed state. Steps  2101  and  2102  repeat until all layers (e.g., substrate fabric layers and barrier film layers) are selectively attached to one another at individual bond points in an alternating configuration of substrate and barrier film layers (e.g., as discussed above). 
     When all layers are selectively attached to one another at individual bond points, the flow chart proceeds to step  2103  where the barrier film(s) is/are biaxially stretched to cause a strain on the barrier film(s) that is higher than the yield strain of the barrier film(s). The strain causes a permanent deformation in the biaxial direction of the strain barrier film(s) that biaxially increases the dimensions of the barrier film(s) with respect to the machine and cross directions. The strain can also cause the barrier film(s) to be partially reversibly stretched when the barrier film(s) have an elastic region. 
     The barrier film(s) can be biaxially stretched by biaxially stretching the substrate fabric(s), which in turn stretches the barrier film(s) due to the bond points between the substrate fabric(s) and the barrier film(s). Alternatively, the composite material as a whole can be biaxially stretched. Alternatively, the barrier film(s) can be biaxially stretched, which in turn stretches the substrate fabric(s) due to the bond points between the substrate fabric(s) and the barrier film(s). 
     The substrate fabric(s), the barrier film(s), or the composite material is preferably stretched equally or approximately equally in all four directions (e.g., in opposite directions with respect to the machine direction and in opposite directions with respect to the cross direction). Approximately the same stretching can mean that the magnitude of the elongation is within plus or minus about 1 to about 10% in each direction, including about 3%, about 5%, about 7%, and about 9%, including any value or range between any two of the foregoing percentages. In one example, the substrate fabric(s), the barrier film(s), or the composite material is stretched uniaxially with respect to a first axis (e.g., parallel to the machine direction) and then, while maintaining the stretch with respect to the first axis, the respective substrate fabric(s), the barrier film(s), or the composite material is then stretched with respect to a second axis (e.g., parallel to the cross direction) that is orthogonal to the first axis, such that a biaxal (e.g., four-way) stretch of the substrate fabric(s), the barrier film(s), or the composite material, respectively, is performed. In another example, the substrate fabric(s), the barrier film(s), or the composite material is stretched simultaneously with respect to the first and second axes. 
     The substrate fabric can be biaxially stretched such that the dimensions of the substrate fabric(s) or the composite material (e.g., in the machine and cross directions) increase by about 30% to about 100%, including about 50%, about 70%, about 90%, or another percentage, compared to the dimensions of the substrate fabric(s) or the composite material, respectively in the relaxed state. When the composite material includes two or more substrate fabric layers, the substrate fabric layers are preferably biaxially stretched simultaneously. 
     As a result of step  2103 , the barrier film(s) are placed in a biaxially-strained state and the substrate fabric(s) and the composite material are placed in a biaxially-stretched state.  FIG.  22    illustrates the barrier film  2210  transitioning from the flat state  2241  to a strained state  2242  as the composite material  2200  and the substrate fabric  2201  transitions from the relaxed state to a biaxially-strained state. 
     In step  2104 , the barrier film(s) is/are biaxially relaxed. The barrier film(s) can be relaxed by releasing the biaxal stretching force on the substrate fabric(s), the barrier film(s), or the composite material. The biaxal stretching force can be released with respect to the machine and cross directions simultaneously or sequentially. When the laminated fabric composite material includes two or more substrate fabrics and the two or more substrate fabrics are biaxially stretched in step  2103 , the biaxal stretching force on all substrate fabrics is preferably released simultaneously. 
     As the barrier film(s) is/are biaxially relaxed, in step  2105  the barrier film(s) transition to a crumpled/folded state in which random three-dimensional folds or crumples are formed in the barrier film(s) between the individual bond points. This allows the composite laminate material to elongate when the substrate fabric(s) are stretched during use, as discussed above, which improves the overall comfort and flexibility of the composite material. In some embodiments, the barrier film(s) can biaxially stretch within an elastic region to further increase the range of biaxial stretching of the composite material. 
       FIG.  22    illustrates the barrier film  2210  transitioning from the strained state  2242  to a randomly folded state  2243  as the composite material  2200  and the substrate fabric  2201  transitions from the biaxially-strained state to a relaxed state. In the randomly folded state, the barrier film  2210  includes random three-dimensional folds or crumples  2230  between the individual bond points  2220 . The random folds  2230  can be the same as the random folds  130 . The composite material  2200  has the same or about the same dimensions, as measured in the machine and cross directions  141 ,  142 , when the barrier film  2210  is in the flat state  2141  compared to when the barrier film  2210  is in the randomly folded state  2243 . 
       FIG.  23    is a flow chart of a method  2300  for manufacturing a biaxially stretchable laminated fabric composite material according to another embodiment. Method  2300  can be used to make composite material  10 ,  70 ,  90 ,  1000 ,  1100 ,  1300 ,  1600 , or  2200 . 
     In step  2301 , a substrate fabric is biaxially stretched by a first percentage. The substrate fabric can be the same as substrate fabric  100 . Step  2301  can the same as step  1401  except that in step  2301  the substrate fabric is biaxially stretched by a first percentage that is less than or equal to the extent of elongation desired or required in the final laminated fabric composite material. The substrate fabric is in a first biaxially-stretched state as a result of step  2301 . 
     In step  2302 , a plurality of individual bond points are formed between the substrate fabric and a barrier film to form a biaxially stretchable laminated fabric composite material. The bond points are formed while the substrate fabric is in the first biaxially-stretched state and the barrier film is in a flattened or relaxed state. The barrier film can be the same as barrier film  110 . The bond points can be the same as bond points  120 . Step  2302  is the same as step  1402 . 
     An example of a composite material  2400  formed in step  2302  is illustrated in  FIG.  24   . The composite material  2400  includes a substrate fabric layer  2401 , a barrier film layer  2410 , and individual bond points  2420  that selectively attach the substrate fabric layer  2401  and the barrier film layer  2410 . For illustration purposes only, the composite material  2400  is illustrated as having only one substrate fabric layer  2401  and only one barrier film layer  2410 . The substrate fabric layer, the barrier film layer  2410 , and/or the bond points  2420  can be the same as the substrate fabric  100 , the barrier film  110 , and the bond points  120 , respectively. 
     The substrate fabric layer  2401  is in a first biaxially-stretched state  2441  and the barrier film  2410  is in a flattened state as a result of step  2302 . The dimensions of the substrate fabric  2401  are L+% L and L′+% L′ in the machine and cross directions  141 ,  142 , respectively, when the substrate fabric  2401  is in the first biaxially-stretched state  2441 . The terms % L and % L′ indicate the percentage increase of the respective dimensions when the substrate fabric  2401  is in the first biaxially-stretched state  2441  compared to when the substrate fabric  2401  is in a relaxed state. 
     In step  2303 , if additional layers are to be attached to the biaxially stretchable laminated fabric composite material, the flow chart returns to step  2301 . If the additional layer includes another substrate fabric, the second substrate fabric is biaxially stretched by a first percentage in step  2301  and then selectively attached to the barrier film layer in step  2302  at individual bond points while the first and second substrate fabrics are in the first biaxially-stretched state and while the barrier film is in the flattened or relaxed state. If the additional layer includes another barrier film layer, the biaxial stretch of the existing substrate fabric is maintained in step  2301  while the second barrier film is selectively attached to the substrate fabric at individual bond points in step  2302  while the first and second barrier films are in the flattened or relaxed state. Steps  2301 - 2303  repeat until all layers (e.g., substrate fabric layers and barrier film layers) are selectively attached to one another at individual bond points in an alternating configuration of substrate and barrier film layers (e.g., as discussed above). 
     When all layers are selectively attached to one another at individual bond points, the flow chart proceeds to step  2304  where the biaxially stretchable laminated fabric composite material is biaxially stretched by a second percentage. Both the substrate fabric(s) and the barrier film(s) are biaxially stretched and elongated to the same extent in this step. The second percentage of biaxial stretching causes the substrate fabric(s) to be stretched to greater than or equal to the extent of elongation desired or required in the final laminated fabric composite material. The second percentage of biaxial stretching can cause a strain on the barrier film(s) that is greater than its/their yield strain, which can result in permanent deformation and biaxial elongation of the barrier film(s) (e.g., as discussed above with respect to step  2103 ). 
     Alternatively, the substrate fabric(s) can be biaxially stretched by a second percentage in step  2304  instead of biaxially stretching the biaxially stretchable laminated fabric composite material. Biaxially stretching the substrate fabric(s) causes the barrier film(s) to biaxially stretch due to the individual bond points between the substrate fabric(s) and the barrier film(s). Alternatively, the barrier film(s) can be biaxially stretched by a second percentage in step  2304  instead of biaxially stretching the biaxially stretchable laminated fabric composite material. Biaxially stretching the barrier film(s) causes the substrate fabric(s) to biaxially stretch due to the individual bond points between the substrate fabric(s) and the barrier film(s). 
       FIG.  24    illustrates the composite material  2400  transitioning to a biaxially-stretched state as the substrate fabric  2401  transitions from the first biaxially-stretched state  2441  to a second biaxially-stretched state  2442  and the barrier film  2410  transitions to a reversible biaxially-stretched state or a biaxially-strained state, depending on the strain applied to the barrier film  2410 . The dimensions of the substrate fabric  2401  are (L+% L)+% (L+% L) and (L′+% L′)+% (L′+% L′) in the machine and cross directions  141 ,  142 , respectively, when the substrate fabric  2401  is in the second biaxially-stretched state  2442 . The terms % (L+% L) and % (L′+% L′) indicate the percentage increase of the respective dimensions when the substrate fabric  2401  is in the second biaxially-stretched state  2442  compared to when the substrate fabric  2401  is in the first biaxially-stretched state  2441 . 
     In step  2305 , the biaxially stretchable laminated fabric composite material and the substrate fabric(s) are biaxially relaxed. The biaxially stretchable laminated fabric composite material and the substrate fabric(s) can be relaxed simultaneously or sequentially. The biaxially stretchable laminated fabric composite material and/or the substrate fabric(s) can be relaxed with respect to the machine and cross directions simultaneously or sequentially. When the laminated fabric composite material includes two or more substrate fabrics, all substrate fabrics are preferably relaxed simultaneously. Additionally or alternatively, the barrier film(s) can be biaxially relaxed in step  2305  (e.g., when the barrier film(s) are biaxially stretched in step  2304  or step  2301 ). 
     As the biaxially stretchable laminated fabric composite material and the substrate fabric(s) is/are biaxially relaxed, in step  2306  the barrier film(s) transition to a crumpled/folded state in which random three-dimensional folds or crumples are formed in the barrier film(s) between the individual bond points. The random folds/crumples can be smaller when the barrier film(s) are stretched beyond its/their yield strain compared to when the barrier film(s) are not stretched beyond its/their yield strain in step  2304 . 
     The random folds/crumples allows the composite laminate material to elongate when the substrate fabric(s) are stretched during use, as discussed above, which improves the overall comfort and flexibility of the composite material. In some embodiments, the barrier film(s) can biaxially stretch within an elastic region to further increase the range of biaxial stretching of the composite material. 
       FIG.  24    illustrates the composite material  2400  transitioning to a relaxed state as the substrate fabric  2401  transitions from the second biaxially-stretched state  2442  to a relaxed state  2443  and the barrier film  2410  transitions to a randomly folded state. In the randomly folded state, the barrier film  2410  includes a plurality of random three-dimensional folds or crumples  2430  between bond points  2420 . The random folds  2430  can be the same as random folds  130 . The dimensions of the substrate fabric  2401  are L and L′ in the machine and cross directions  141 ,  142 , respectively, when the substrate fabric  2401  is in the relaxed state  2443 . 
       FIG.  25    is a flow chart of a method  2500  for manufacturing a biaxially stretchable laminated fabric composite material according to another embodiment. Method  2500  is preferably used when the barrier film has an inherent reversible stretch (e.g., in an elastic region). 
     In step  2501 , a plurality of individual bond points are formed between a substrate fabric and a barrier film while the substrate fabric is a relaxed state and the barrier film is in a relaxed or flattened state to form a composite material. Step  2501  can be the same as step  2101 . 
     In step  2502 , if additional layers are to be attached to the composite material, the flow chart returns to step  2501 . If the additional layer includes another substrate fabric, the second substrate fabric is selectively attached to the barrier film layer in step  2501  at individual bond points while the first and second substrate fabrics and the barrier film are in the relaxed state. If the additional layer includes another barrier film layer, the second barrier film is selectively attached to the substrate fabric at individual bond points in step  2501  while the substrate fabric and the first and second barrier films are in the flattened or relaxed state. Steps  2501  and  2502  repeat until all layers (e.g., substrate fabric layers and barrier film layers) are selectively attached to one another at individual bond points in an alternating configuration of substrate and barrier film layers (e.g., as discussed above). Step  2502  can be the same as step  2102 . 
     When all layers are selectively attached to one another at individual bond points, the flow chart ends at  2503 . 
     An example of a composite material  2600  formed using method  2500  is illustrated in  FIG.  26   . The composite material  2600  includes a substrate fabric layer  2601 , a barrier film layer  2610 , and bond points  2620  that selectively attach the substrate fabric layer  2601  and the barrier film layer  2610 . For illustration purposes only, the composite material  2600  is illustrated as having only one substrate fabric  2601  and only one barrier film layer  2610 . The composite material  2600  and the substrate fabric layer  2601  are in a relaxed state and the barrier film layer  2610  is in a flat state  2641 . The substrate fabric layer  2601 , the barrier film layer  2610 , and/or the bond points  2620  can be the same as the substrate fabric  100 , the barrier film  110 , and the bond points  120 , respectively. The composite material  2600  can biaxially stretch within the elastic region of the barrier film layer  2610 . 
       FIG.  27    illustrates CRBN garments  2700  according to an embodiment. 
     The garments  2700  are formed using one or more of the composite materials described herein. For example, the garments  2700  can be formed using composite material(s)  10 ,  70 ,  90 ,  1000 ,  1100 ,  1300 ,  1600 ,  2200 ,  2400 , and/or  2600 . The shape of the garments can be changed, as desired. For example, the garments  2700  can comprise a single piece or the top and bottom can be releasably connected such as with a zipper. The end of the arms of the shirt/top can be configured to receive and/or mate with the ends of gloves to form a continuous barrier layer for the user. Likewise, the bottom of the pant legs can be configured to receive and/or mate with boots or booties to form a continuous barrier layer for the user. 
     The invention should not be considered limited to the particular embodiments described above, but rather should be understood to cover all aspects of the invention as fairly set out in the attached claims. Various modifications, equivalent processes, as well as numerous structures to which the invention may be applicable, will be apparent to those skilled in the art to which the invention is directed upon review of this disclosure. The claims are intended to cover such modifications and equivalents. 
     Also, as described, some aspects may be embodied as one or more methods. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.