Method of manufacturing of multilayer and nanolayer materials for high impact applications

Abstract

This disclosure relates to multilayered composite structures having a. plurality of layers, in which each layer comprises a polymer. Each layer has a. thickness, and the multilayered composite structure has ballistic impact resistance, or a V50 ballistic limit of 300 m / s or higher. The composite structures can have at least 50 or at least 300 layers or more depending on the templated use. The disclosure also related, to methods of making such structure by for example extrusion.

Description

METHOD OF MANUFACTURING OF MULTILAYER AND NANOLAYER MATERIALS FOR HIGH IMPACT APPLICATIONS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application 63 / 536,573 (filed on September 5, 2023) which is incorporated by reference in its entirety. FIELD OF THE INVENTION

[0002] This disclosure relates to nanolayer materials for high impact application and methods of manufacturing such materials. BACKGROUND OF THE INVENTION

[0003] Various multilayer ballistic sheets are known. For example, EP 3126135 B1 relates to “multilayer sheets, articles formed therefrom, and their methods of manufacture, and in particular multilayer sheets having flame retardant properties, articles formed therefrom, and their methods of manufacture.” EP 3126135 B1 at

[0001] . The multilayer sheets comprise “a base layer comprising a polycarbonatesiloxane-arylate; and a cap layer disposed on a side of the base layer, wherein the cap layer comprises poly(ethylene terephthalate), poly(vinyl fluoride), poly(vinylidene fluoride), or a combination comprising at least one of the foregoing” with a specific flame time, burn length, and dip extinguishing time. EP 3126135 B1 at claim 1.

[0004] Similarly, claim 1 of EP 3837487 B1 recites “[a] multilayer ballistic protection panel (1) comprising a stack of layers of fabric (2) of woven yarns (4), the weave leaving through-interstices (7) free between the yarns (4) of each layer of fabric (2), and layers of adhesive (3) which are interposed between the layers of fabric (2) in an alternating manner and which provide overall cohesion to the multilayer panel (1).” Claim 8 of EP 3837487 B1 recites such a panel having “between 5 and 120 layers of fabric (2) woven with twisted polyester yarns (4).”

[0005] Furthermore, WO 2023038537 A1 discloses “[a] multilayer ballistic barrier comprising at least one barrier plate (1) having a thickness of up to 250 mm, made of an elastomeric material containing butadiene and a binder, and a fill (2) having a minimum thickness of 50 mm in the form of mineral aggregates of various fractions ranging from 0.5 to 80 mm.” WO 2023038537 A1 at Abstract.4880-0190-9465.1 1

[0006] BR102019012398A2 relates to a composite material formed by an epoxy resin matrix reinforced with curaua fibers (Ananas erectifolius) functionalized with graphene oxide.

[0007] However, the prior disclosures of multilayered constructs do not allow for structurally strong, high performance and tunable ballistic performance materials using one or more polymer materials with distinct material properties.

[0008] Furthermore, the existing solutions include high molecular weight polymers and engineered plastics with inherently high impact properties. These technologies use single materials polymers such as kevlar, polyamides, and high molecular weight polyethylenes. Woven materials are commonly used for improved ballistic performance. Typical structures involve use of polymer materials in combination with other materials such as ceramics, metals, etc.

[0009] The methods and materials of the disclosure solve the problem of creating structurally strong, high performance, and tunable ballistic performance materials using one or more polymer materials with distinct material properties. SUMMARY OF THE INVENTION

[0010] The disclosure provides multilayered composite structures that have high ballistic resistance as well as methods of making such structures.

[0011] One embodiment of the disclosure is a multilayered composite structure having a plurality of layers, whereby each layer comprises a polymer, and whereby the multilayered composite structure has ballistic impact resistance and / or a V50 ballistic limit of 300 m / s or higher.

[0012] In certain embodiments, each layer in the multilayered composite structure has the same thickness. In other embodiments, the thickness of each layer in the multilayered composite structure is different. In alternate embodiments, the thickness of the layers gradually decreases from one side of the multilayered composite to another.

[0013] The multilayered structure can have a variety of different configuration for each polymer layer. For example, at least one layer of the structure may comprise one or more woven polymers. In some embodiments, at least one layer includes a first polymer and a second polymer woven together to form the layer. In certain embodiments, the first polymer is oriented along a horizontal axis of the multilayered structure and the second oriented along the horizontal axis at an approximately 90-degree angle.4880-0190-9465.1 2

[0014] In some embodiments, at least one layer of the multilayered composite structure includes a polymer having a void. In other embodiments, layers of polymer adjacent to the layer of polymer having the having a void also lack a void. In additional embodiments, at least one layer includes a polymer having a filler and / or additive.

[0015] The multilayered composite structure can also have a variety of different stacking arrangements. In one embodiment the multilayered composite structure includes a layer of a first polymer A and a layer of a second polymer B, wherein the layers of the first and second polymer are stacked on top of each other. In some embodiments, the layers are stacked in an A / B arrangement and the composite structure includes more than one stack.

[0016] In further embodiments, the multilayered composite structure includes a third polymer, and the third polymer forms layers surround the layers of polymer A and the layers of polymer B.

[0017] In certain embodiments, the multilayered composite structure includes layers of a first polymer A, a layer of a second polymer B, and a layer of a third polymer C. In some embodiments, the layers are stacked in an A / B / C arrangement and wherein the composite structure contains more than one stack.

[0018] In additional embodiments, the multilayered composite structure have more than three polymers, allowing for complex multilayer configurations. For instance, the structure may include four, five, or more distinct polymers, arranged in a variety of sequences or repeating sequences (e.g., A / B / C / D, A / B / C / D / E, etc.). In certain high-performance applications, the use of up to nine different polymers is feasible, made possible through advanced continuous coextrusion processes. This capability allows for tailored mechanical and ballistic properties by combining polymers with varying characteristics such as modulus, tensile strength, and toughness.

[0019] In some embodiments, a layer of the structure is oriented along a horizontal axis of the composite and wherein a second layer is oriented at a 180-degree angle to the horizontal axis.

[0020] In certain embodiments, the multilayered composite structure is formed by extrusion molding.

[0021] The number of layers in the multilayered composite structure can vary. For example, the composite structure includes at least 50 layers, with the individual thickness of the layers ranging from 100 micrometer to 1000 micrometers. In other embodiments, the composite structure includes at least 300 layers, with the individual thickness of the layers ranging from 25 micrometer to 300 micrometers. In alternative embodiments, the composite4880-0190-9465.1 3structure includes 300 to 500 layers, with the individual thickness of the layers ranging from 5 micrometer to 300 micrometers. In some embodiments, each layer a thickness of between 10 to 100 nm. In alternate embodiments, each layer a thickness of between 10 to 50 nm.

[0022] In certain embodiments, one or more plurality of layers of the multilayered composite structure contains relatively higher modulus, tensile strength, toughness, dielectric constant, molecular weight distributions or stiffness than the other set of plurality of layers.

[0023] The disclosure also includes methods of making these multilayered composite structures. On embodiment is a method of generating a multilayered composite structure by extruding each layer.

[0024] Other features and advantages of the invention will be apparent from the detailed description and examples that follow. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended figures. For the purpose of illustrating the invention, the figures demonstrate embodiments of the present invention. It should be understood, however, that the invention is not limited to the precise arrangements, examples, and instrumentalities shown.

[0026] FIG.1 shows a cross-section of a typical multilayer composite structure according to embodiments of the disclosure. FIG.1A shows a cross-section of multilayered constructs formed of different layers of polymer A and polymer B. FIG. 1B shows cross-sections of different multilayer composite structures of polymer A and B with different starting geometries. FIG.1C shows cross-sections of nanolayered structures.

[0027] FIG.2 shows cross-sections of gradient multilayer composite structures according to embodiments of the disclosure. The gradient multilayer composite structures have various thicknesses of layers of polymer A (gray) and polymer B (shaded). The thickness of the layers decreases from top to bottom or vice versa.

[0028] FIG. 3 shows cross-section of multilayer composite structures with foam layers according to embodiments of the disclosure. The multilayer composite structures with foam layers have multilayer composite structure A / B or A / B / A whereby A is polymer A and B is polymer B. The foam layers shown in FIG.3 can have open cell or closed cell foam structure.

[0029] FIG.4A and FIG.4B show cross-sections of multilayer composite structures with filler and additives according to one embodiment of the disclosure. In FIG.4A and FIG.4B, A is polymer A, B is polymer B, C is polymer C and T is polymer T.4880-0190-9465.1 4

[0030] FIG.5 shows a cross-section of a multilayer composite structure of the disclosure in which there are vertical stack of separated by horizontal layers.

[0031] FIG. 6 shows a cross-section of multilayer composite structures of the disclosure having a woven pattern within the multilayer.

[0032] FIG. 7A to FIG. 7C show cross-sections of multilayer composite structures with more than three different polymers. Each type of shading in FIG.7A to FIG.7C indicates a different polymer. In FIG.7A, H is polymer H and G is polymer G. In FIG.7B, F is polymer F. In FIG.7C, A is polymer A, B is polymer B, D is polymer D, and E is polymer E.

[0033] FIG.8 shows a picture of a multilayer composite structure of the disclosure.

[0034] FIG. 9A to FIG. 9D shows pictures of multilayer composite having a one inch thickness. FIG.9A shows a side view of a multilayer composite after ballistic testing. FIG. 9B shows a top perspective of the composite of FIG. 9A with some layers separate to show penetration of the bullet. Fig.9C shows a side view of the construct with a quarter coin placed on the side. FIG.9 D shows a cross-sectional view of the multilayered construct. DETAILED DESCRIPTION

[0035] This disclosure provides nanolayer materials (multilayer composite structures) for high impact application and methods of manufacturing such materials. The nanolayer materials of the disclosure are formed of polymer layers.

[0036] Using the plurality of the polymer layers with one or more polymers, with individual thicknesses of component materials ranging, for example, from several millimeters down to tens of nanometers, the materials are combined such that the synergistic combination of the starting materials create novel structures with tunable impact performance for ballistic applications. The combination of the polymer components with or without other fillers also leads to improved impact and mechanical performance.

[0037] In one embodiment, the present disclosure provides polymer material-based multi- component structures containing 1s to 100s of layers and a multilayer composite structure with at least one polymer component. The structure is fabricated to create a high impact strength material, where at least polymer material is separated into plurality of polymer layers.

[0038] The multilayer composite structures of the disclosure have micron-, submicron and nano- layer thicknesses that can be used to tune the overall performance of the products. Each set of layers can contain different types of polymers, mixture of polymers or polymers with additives / fillers or combination thereof for property improvements. In some embodiments, the structure can be modified to create vertical stacks in layers separated by4880-0190-9465.1 5horizontal layers in the composite structure. In some embodiments, the structures can also be converted to fiber-like structures to create woven materials.

[0039] In certain embodiments, the methods of the disclosure uniquely utilize coextrusion to create a multilayer composite structure with 10s to 1000s of layers with individual layer thicknesses ranging from a few nanometers to 10s of nanometers.

[0040] In additional embodiments, multilayered composite structures can be combined with other materials to enhance their performance further. Such combinations may include additional materials like polymers, filler-containing polymers, ceramics, metals, or other variable modulus ballistic materials. These additional materials can be used to separate or reinforce multilayered structures within the composite. For example, layers of a high-impact strength material could be strategically incorporated at multiple locations within the multilayered construct to optimize performance in targeted regions. The placement of these layers or constructs can be varied throughout the final structure, depending on the desired mechanical properties and performance characteristics. This approach allows for further customization of the composite structures to meet specific application requirements, such as varying the modulus, toughness, and ballistic resistance across different sections of the composite.

[0041] Without being about by theory, in embodiments of the disclosure, the multilayer materials provide improved impact performance. The multilayered composite structures of the disclosure having plurality of different layers and, optionally. combinations of layered structure created with controlled mechanical properties, provide for improved performance of a broad range of properties such as impact strength, ballistic strength, flexural modulus, and tensile strength.

[0042] The general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Other aspects of the present invention will be apparent to those skilled in the art in view of the detailed description of the invention as provided herein. Definitions

[0043] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, representative illustrative methods, and materials are now described.4880-0190-9465.1 6

[0044] All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and are incorporated herein by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided may be different from the actual publication dates, which may need to be independently confirmed.

[0045] It is noted that, as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as “solely,” “only” and the like in connection with the recitation of claim elements, or use of a “negative” limitation.

[0046] Each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present invention. Any recited method can be carried out in the order of events recited or in any other order which is logically possible.

[0047] It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0048] As used herein, the terms “comprising,” “including,” “containing” and “characterized by” are exchangeable, inclusive, open-ended and do not exclude additional, unrecited elements or method steps. Any recitation herein of the term “comprising,” particularly in a description of components of a composition or in a description of elements of a device, is understood to encompass those compositions and methods consisting essentially of and consisting of the recited components or elements.

[0049] As used herein, the term “consisting of” excludes any element, step, or ingredient not specified in the claim element.

[0050] As used herein, the term “about” when referring to a measurable value such as an amount, a temporal duration, and the like, is meant to encompass variations of ± 20% or ± 10%, more preferably ± 5%, even more preferably ± 1%, and still more preferably ± 0.1% from the specified value, as such variations are appropriate to perform the disclosed methods.4880-0190-9465.1 7

[0051] Before certain embodiments are described in greater detail, it is to be understood that this invention is not limited to certain embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing certain embodiments only, and is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.

[0052] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.

[0053] Before certain embodiments are described in greater detail, it is to be understood that this invention is not limited to certain embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing certain embodiments only, and is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.

[0054] Ranges: throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range.

[0055] For clarity of disclosure, and not by way of limitation, the detailed description of the invention is divided into subsections that describe or illustrate certain features, embodiments, or applications of the present invention.4880-0190-9465.1 8Multilayer composite structures

[0056] One aspect of the disclosure is directed to multilayer composite structures that can be particularly suitable for high impact applications, such as e.g., ballistic performance materials.

[0057] The multilayered composite structures of the disclosure are formed from two or more (i.e., a plurality) of polymers. The multilayered composite structures are characterized in that they have superior V50 ballistic limit of 500 m / s or higher. They also have ballistic impact resistance. In some embodiments, the structures have ballistic impact resistance and / or a 50 ballistic limit of 500 m / s or higher.

[0058] A variety of polymers may be used to form the multilayered composite structures of the disclosure. The polymer used in the layers of the multilayered composite structures of the disclosure are individually selected from the group consisting of a polyethylene, polypropylene, polyethylene naphthalate, an isomer thereof, a polyalkylene terephthalate, a polyimide, a polyetherimide, a styrenic polymer, a polycarbonate, a poly(methyl meth)acrylate derivatives, a cellulose derivative, a polyalkylene polymer, a fluorinated polymer, a chlorinated polymer, a polysulfone, a polyethersulfone, polyacrylonitrile, a polyamide, polyvinylacetate, a polyether-amide, a styrene-acrylonitrile copolymer, a styrene- ethylene copolymer, poly(ethylene-1,4-cyclohexylenedimethylene terephthalate), polyvinylidene difluoride, an acrylic rubber, isoprene, isobutylene-isoprene, butadiene rubber, butadiene-styrene-vinyl pyridine, butyl rubber, polyethylene, chloroprene, epichlorohydrin rubber, ethylene-propylene, ethylene-propylene-diene, nitrile-butadiene, polyisoprene, silicon rubber, styrene-butadiene, urethane rubber, and polyoxyethylene, polyoxypropylene, and tetrafluoroethylene hexafluoropropylene vinylidene (THV), aromatic polyesters, aromatic polyamides, ethylene norbornene copolymers, and combinations thereof. The polymer components can be miscible, immiscible, or partially miscible polymeric materials.

[0059] In other embodiments, plurality of layers of the multilayered composite constructs may contain polymers with aromatic structures comprised of several repeating inter-chain bonds and the polymer chains that cross-linked with hydrogen bonds. The layered structures may be combined with aforementioned aromatic materials directly in a post-production operation via molding, adhesion, sonication, welding, chemical or radiation crosslinking methods.4880-0190-9465.1 9

[0060] The plurality of layers selected preferably have higher interfacial interaction or miscibility parameter with the alternating plurality of layers with the final structure preferentially contains layers in a 2D composite, fiber, or ribbon structures.

[0061] The higher interfacial interaction can be used in some of the structures to modify the material properties of combination of plurality of layers as compared the other set of layers.

[0062] The multilayered composite structures of the disclosure have a plurality of layers. In certain embodiments, the multilayered composite structures have between 2 and 8192 layers, alternatively between 10 to 1000 layers, alternatively at least 200 layers, alternatively at least 300 layers, alternatively at least 500 layers.

[0063] In certain embodiments, the multilayered composite structure of the disclosure contains at least two different layers. The multilayer composite structure can contain more than two pluralities of layers to include new functionalities. For example, in certain embodiments, a third plurality of layers that can act as adhesive layers between the first and second plurality of layers for enhanced properties such as mechanical, barrier, optical properties.

[0064] In certain embodiments, each layer in the multilayered composite structure has a thickness ranging from a few nanometers to tens of nanometers.

[0065] In certain embodiments, the multilayered composite structures are processed using coextrusion processing to create films, sheets, profiles, or molded products.

[0066] In some embodiments, the multilayered composite structure is formed of a plurality of layers that over part, or all of the structure (based on a cross-section) includes alternating patterns between at least one polymer layer A with the other polymer layer B.

[0067] In certain embodiments, one or more (or each) of polymer layers is constructed of a polymer composite. The polymer composite can consist of a mixture of two or more polymers, additives or other fillers or combination thereof. Accordingly, in certain embodiments, the plurality of the layers includes alternating patterns of at least one polymer composite layer stacked on top of another polymer layer or layer of polymer composite.

[0068] One embodiment of the disclosure is directed to a multilayer composite structure having of a plurality of layers of polymer A and a plurality of layers of polymer B, with preferential difference in the modulus of the materials. In some embodiments, each of the layers has a thickness between about 10 nm to about 30 nm, alternatively between 15 nm to about 25 nm. Examples of such structures are shown in FIG.1A to FIG.1C.4880-0190-9465.1 10

[0069] FIG.1A to FIG.1C show cross-sections of some multilayer composite structures according to embodiments of the disclosure. In the embodiments of shown in FIG. 1, the multilayer composite structures are construct of layers of polymer A and polymer B optionally with layers of polymer T and polymer S. The number of layers and number of polymers used in the constructs can vary.

[0070] FIG. 1A shows a cross-section of a multilayered composite structure formed of different layers of polymer A and polymer B. Specifically, FIG.1A shows a construct formed of alternating layers of polymer A and polymer B. In one embodiment, these layers are of equal thickness. In other embodiments, the thickness of the layers varies depending on the use.

[0071] FIG. 1B shows cross-sections of different multilayer composite structures of polymer A and B with different starting geometries. In one embodiment, these layers are of equal thickness. In other embodiments, the thickness of the layers varies depending on the use. In certain embodiments, additional layers may be added.

[0072] FIG. 1B shows a cross-section of an embodiment of a multilayer composite structure having an A / B arrangement in which there are alternating layers of polymer A and polymer B. FIG.1B also shows a cross-section of an embodiment of a multilayer composite structure having an A / B / A arrangement in which a polymer B layer is sandwiched between a two layers of polymer A. In another embodiment, the multilayer has a B / A / B arrangement in which a polymer A layer is sandwiched between two layers of polymer B. FIG. 1B also shows a cross-section of an embodiment of a multilayer composite structure having an A / B / C arrangement, in which a layer of polymer C is stacked on top of a layer of polymer B which is on top of a layer of polymer A and this pattern is repeated.

[0073] FIG.1B further shows a cross-section of an embodiment of a multilayer composite structure having an A / T / B / T / A arrangement, in which a layer of polymer A is stacked on top of a layer of polymer T which in turn is stacked on a layer of polymer B, which in turn is stacked on a layer of polymer T, which in turn is stack on a layer of polymer A. In certain embodiments, additional layers may be added, in increments of A / T / B / T / A. Polymer A may be replaced with polymer B or T etc. In certain embodiments, polymer T is replaced with polymer C thereby giving an A / C / B / C / A arrangement.

[0074] FIG. 1B also shows a cross-section of a multilayer composite structure having S[A / B]nS structure. In this configuration, in certain embodiments, n layers of polymer A / polymer B are sandwiched between outer layers of polymer S. In some embodiments, n is 4, alternatively n is between 5-150, alternatively at least n is 200.4880-0190-9465.1 11

[0075] FIG. 1C shows cross-sections of nanolayered structures. In one embodiment, these layers are of equal thickness. In other embodiments, the thickness of the layers varies depending on the use. In certain embodiments, additional layers may be added. In certain embodiments, these nanolayered structures are nanolayered versions of the structures shown in FIG.1B. In one embodiment as shown in the right-hand panel of FIG.1C, the nanolayered structure has a S[A / B]nS structure as above. In another embodiment, as shown in the center panel of FIG. 1C, the nanolayer structure has an A / B / A structure as above. In another embodiment, as shown in the left-hand panel of FIG.1C, the nanolayer structure has an A / B structure as above.

[0076] Each set of plurality of layers used in the multilayered composite structures of the disclosure may have different functional properties including but not limited to modulus, tensile strength, impact strength, or other mechanical properties.

[0077] In certain embodiments of the disclosure, each layer of the multilayered constructs has the same thickness. In other embodiments, each polymer used in the multilayered construct has the same thickness. In further embodiments, the thickness of each layer varies. Varying layer thickness may be used to improve attributes of the multilayered composite structure such as high impact resistance.

[0078] In certain embodiments, the performance of the materials can further be tuned by changing the orientation direction to parallel or perpendicular or a combination of both.

[0079] In other embodiments of the disclosure, the multilayered constructs of the disclosure can be gradient structures in which the cross-sectional thickness of each layer decreases from, for example, top to bottom or vice versa.

[0080] In alternate embodiments, the plurality of layers selected for inclusion in the multilayer composite structure preferably have higher interfacial interaction or miscibility parameter with the alternating plurality of layers with the final structure preferentially contains layers in a 2D composite, fiber, or ribbon structures.

[0081] The higher interfacial interaction can be used in some of the structures to modify the material properties of combination of plurality of layers as compared the other set of layers.

[0082] The multilayer composite structure can be a gradient structure with two or more plurality of layers with a thickness variation from one side of the structure to the second side. In certain embodiments, the thickness variation can be up to 20X, alternatively up to 15X, alternatively up to 10X. In certain embodiments, the gradient structure contains additional layers on the outside for added functionality. In some embodiments, the multilayer composite4880-0190-9465.1 12structure is a gradient structure in which the plurality of layers has different thicknesses on opposite sides of the composite. The initial performance shows that the variation in thickness allows tunability of the impact performance of the materials perpendicular to the layers.

[0083] FIG.2 shows cross-sections of gradient multilayer composite structures according to embodiments of the disclosure. The gradient multilayer composite structures have various thicknesses of layers of polymer A (gray) and polymer B (shaded). In certain embodiments, additional layers may be added. In other embodiments, additional layers of different polymers may be added. In some embodiments, the layers forming the gradient structure can be nanolayers such as those described above. In other embodiments, the gradient structure can be one of the multilayered composite structures described above. In particular embodiments, the gradient structure can have a S[A / B]nS structure.

[0084] In certain embodiments, the multilayer composite structures of the disclosure contain foamed structures in one or more layer creating voids through, e.g., chemical or gas foaming processes.

[0085] In certain embodiments, the foam structure is found in each layer. In other embodiments, the foam structure is found in a specific type of polymer only (e.g., all layers constructed of polymer A). In further embodiments, the foam structure is found in a subset of a specific layer (e.g., only some layers constructed of polymer A).

[0086] FIG. 3 shows cross-section of multilayer composite structures with foam layers according to embodiments of the disclosure. The multilayer composite structures with foam layers have multilayer composite structure A / B or A / B / A whereby A is polymer A and B is polymer B. The foam layers shown in FIG.3 can have open cell or closed cell foam structure. This foam structure can be used in the various other embodiments of the disclosure in gradient structures and nanolayered structures.

[0087] In other embodiments, the multilayer composite structures include fillers and / or additives in one or more or each of the polymer layers. In certain embodiments, a filler and / or additive is found in each layer of a specific type of polymer (e.g., all layers of polymer A). In other embodiments, a filler and / or additive is found in only certain layers of a specific type of polymer (e.g., one or more specific layer of polymer A).

[0088] Suitable fillers include polymer processing aids, minerals (such as e.g., calcium carbonate, silica, clay, kaolin, or carbon), metals, metal alloys or derivatives thereof. The fillers can have a variety of structural forms such as e.g., spherical, platelets, or powders. In some embodiments, the filler materials in the polymer layer are oriented so to improve mechanical performance.4880-0190-9465.1 13

[0089] In further embodiments, the polymer contains additives, inorganic or organic materials with ability to affect material properties such as modulus.

[0090] FIG.4A and FIG.4B show cross-sections of multilayer composite structures with filler and additives according to one embodiment of the disclosure. In FIG.4A and FIG.4B, A is polymer A, B is polymer B, C is polymer C and T is polymer T. In one embodiment, shown in the left-hand panel of FIG. 4A, the multilayer composite structure has an A / B arrangement with all the fillers and / or additives found in polymer A. In other embodiments, both polymer A and polymer B may have a filler and / or an additive. In another embodiment, shown in the second panel from the left in FIG.4A, the multilayer composite structure has an A / B / A arrangement with all the fillers and / or additives found in polymer A. In other embodiments, both polymer A and polymer B may have a filler and / or an additive. In yet another embodiment, shown in the second panel from the right in FIG. 4A, the multilayer composite structure has an A / B / C arranging with all the fillers and / or additive found in polymer B. Alternatively, all the filler and / or additive are found in the A and / or B layer. Alternatively, each layer has a filler and / or an additive.

[0091] In FIG.4B, shows multilayer composite structures with a filler and / or an additive. hand panel of FIG. 4B shows an embodiment of a multilayer composite structure of the disclosure in which each layer contains a filler and / or additive. The left hand of FIG. 4B shows an embodiment of a multilayer composite structure of the disclosure in which more than one type of filler and / or additive is found in a single polymeric layer.

[0092] In other embodiments, the polymer layer contains fillers that are typically used to enhance material properties such as impact, tensile strength, barrier, etc.

[0093] For example, in certain embodiments, the one or more of the plurality of layers in the multilayer composite structures contain biobased fibers or similar materials, such as e.g., cellulose, starch, or derivatives thereof. In one embodiment, each type of a layer (e.g., all layers of polymer A) contain biobased fibers or similar materials, such as e.g., cellulose, starch, or derivatives thereof. In another embodiment, each type of a layer (e.g. all layers of polymer A) contain biobased fibers or similar materials, such as e.g., cellulose, starch, or derivatives thereof and each type of another layer (e.g. all layers of polymer B) contains similar polymers or their derivatives with different ratios and / or different additives.

[0094] In any of these structures, the second plurality of layers can contain polymer materials with the relative ratio to first plurality of the layers varying from 1 / 99 to 99 / 1.

[0095] Where desired, the structural properties of the multilayered composite structures can be altered by changing the orientation of polymeric layers. This may be particularly4880-0190-9465.1 14useful where the polymeric layer has improved structural property along one axis compared to another.

[0096] Accordingly, in yet another embodiment, the multilayer composite structures of the disclosure contain vertical stacks separated by horizontal layers. The multilayered composite structures with a combination of horizontal and vertical layers can contain stacks of 10,000-to-500,000-layer vertical stacks separated by horizontal layers. In such a combination, the structure may preferentially contain vertical stacks of alternating layers of polymers with different modulus properties separated by the same or a different polymer material as a horizontal layer. An example of such an arrangement is shown in FIG.5, which shows a cross-section of a multilayer composite structure of the disclosure in which there are vertical stacks of polymeric layers separated by horizontal layers.

[0097] In some embodiments, the plurality of layers selected preferably have weaker interfacial interaction or miscibility parameter with the alternating plurality of layers with the final structure preferentially contains layers perpendicular to the impact direction.

[0098] In an alternate embodiment, the multilayer composite structures of the disclosure contain a layer of woven polymer. In certain embodiments, the layer of woven polymer is constructed from one type of polymer (i.e., polymer A only). In certain other embodiments, the layer of woven polymer is constructed from two types of polymers (i.e., polymer A and polymer B only). In further embodiments, three or more different polymers may be used in the woven layer.

[0100] The multilayered composite structures can be split into fiber like structure and woven into an ordered patterns to create fabric-like patterns for use in high impact or ballistic applications. Each fiber structure may contain a layered structures described herein.

[0101] In other embodiments, the FIG. 6 shows a cross-section of multilayer composite structures of the disclosure having a woven pattern within the multilayer. The woven patters can be used in any of the other layered structures described herein, for example in the multilayer composite structure shown in FIG.1 to FIG.5 and FIG.7.

[0102] The multicomponent structures described herein can be used individually or different multicomponent structures are combined through post-production steps. The combination of 2 to 2000 multilayer composite structure can be combined to create a composite structure with several tens of thousands of ordered layers.

[0103] In certain embodiment of the disclosure, the multilayered composite constructs of the disclosure can be combined with other materials. Via the use of these other materials, it is possible to even further enhance the performance of the composites. Such combinations4880-0190-9465.1 15include additional materials such as e.g. polymers, filler-containing polymers, ceramics, metals, or other variable modulus ballistic materials. In certain embodiments, these additional materials can be used to separate or reinforce multilayered structures within the composite. Examples of such structures are shown in FIG.7A to FIG.7C.

[0104] In FIG.7A, H is polymer H and G is polymer G. In FIG.7B, F is polymer F. In FIG. 7C, A is polymer A, B is polymer B, D is polymer D, and E is polymer E. Similar to constructs described above, this type of construct consists of additional polymers identified above. In these examples, polymer D can be a high strength polymer such as nylon, polycarbonate, while polymer E can be a softer polymer. Such constructs allow diffusion of ballistic impact by altering energy diffusion pathways.

[0105] In certain embodiments, layers of a high-impact strength material are strategically incorporated at multiple locations within the multilayered construct to optimize performance in targeted regions. The placement of these layers or constructs can be varied throughout the final structure, depending on the desired mechanical properties and performance characteristics. This approach allows for further customization of the composite structures to meet specific application requirements, such as varying the modulus, toughness, and ballistic resistance across different sections of the composite.

[0106] In additional embodiments, the multilayered composite structure contain more than three polymers, allowing for complex multilayer configurations. For instance, the structure may include four, five, or more distinct polymers, arranged in a variety of sequences or repeating sequences (e.g., A / B / C / D, A / B / C / D / E, etc.). In certain embodiments, for, e.g., high-performance applications, the use of up to nine different polymers is feasible, made possible through advanced continuous coextrusion processes. This capability allows for tailored mechanical and ballistic properties by combining polymers with varying characteristics such as modulus, tensile strength, and toughness.

[0107] The processed structures may be oriented to induce further enhancement in the performance. The orientation can be completed during or after the fabrication of materials. The materials may be oriented in one or more directions depending on the contemplated use.

[0108] In some embodiments of the disclosure, one or more plurality of layers preferably contains relatively higher modulus, tensile strength, toughness, dielectric constant, molecular weight distributions or stiffness than the other set of plurality of layers.

[0109] In other embodiments, the material properties of the one set of plurality of the layers can further be modified using other polymers or aforementioned additives to achieve desired variation in the starting material properties.4880-0190-9465.1 16

[0110] The plurality of the layer thickness can vary between 20 nanometers to 10000 micrometers in structures containing alternating layers, preferably between 10 micrometers to 2000 micrometers. In certain embodiments, the average layer thickness is 80 ± 25 micrometers.

[0111] The plurality of the layer thickness can vary between 20 nanometers to 2000 micrometers in structures containing 2D layered structures, preferably between 100 nm - 1000 micrometers. In certain embodiments, the average layer thickness is 80 ± 25 micrometers. Methods of fabricating the multilayer composite structures

[0112] The multilayer composite structures of the instant disclosure can be fabricated by a variety of methods. In one embodiment, the constructs are generated by coextrusion to create 10s to 1000s of layers with individual layer thicknesses ranging from a few millimeters to 10s of nanometers.

[0113] The multilayer composite structures can also be generated using other polymer processing approaches, including, but not limited to injection molding, compression molding, 3D printing, thermoforming, and custom polymer synthesis.

[0114] In other embodiments, the multilayer composite structures can be combined with aromatic materials described above directly in a post-production operation via molding, adhesion, sonication, welding, chemical or radiation crosslinking methods.

[0115] Without further description, it is believed that one of ordinary skill in the art can, using the preceding description and the following illustrative examples, make and utilize the present invention and practice the claimed methods. The following working examples, therefore, specifically point out the preferred embodiments of the present invention and are not to be construed as limiting in any way the remainder of the disclosure. EXAMPLES Example 1 – Constructions of a Bullet resistance Construct

[0116] A bullet resistant multilayer construct was constructed by co-extruding a multilayered film containing 5 layers with 3 alternating layers of low-density polyethylene (LDPE) and 2 LDPE filled with nickel flakes (LDPE-Ni). The films are stacked in a post- processing experiment to create a stack of 65 films with a total of 325 layers containing 130 layers of nickel filled LDPE. The average starting layer thickness 80 ± 25 micrometers.4880-0190-9465.1 17Thermal treatment of the materials was also completed to further consolidate nickel filler. A picture of a cross-section of this construct is shown in FIG.8.

[0117] In another example, a bullet resistant material was constructed using LDPE and LDPE-Ni multilayered system with 10 films of 3 layered LDPE / polyethylene terephthalate glycol (PETG) / LDPE films were added alternating with 10 layers of LDPE-LDPE-Ni multilayered stack. The system contained a total of 55 films of LDPE / LDPE-Ni and 10 films of LDPE / PETG / LDPE film. The average starting layer thickness 80 ± 25 micrometers. In another example, a bullet resistant material was constructed using LDPE and LDPE-Ni multilayered system with a single layer polycarbonate (PC) sheet. The system contained a total of 50 films of LDPE / LDPE-Ni and 5 sheets of PC. The average starting layer thickness in the multilayer structure was 80 ± 25 micrometers. The PC thickness was 3.175 mm.

[0118] FIG. 8 shows a picture of this film, i.e., an example of a structures made with alternating layers of polymer A alternating with metal-filled polymers are shown in the cross- section image of sheet. Thermal treatment was used to improve modulus different of the plurality of layers. Example 2 – Bullet Resistance Testing of a One-inch Multilayered Composite

[0119] A bullet resistant multilayer construct was constructed by co-extruding a multilayered film containing 5 layers with 3 alternating layers of low-density polyethylene (LDPE) and 2 LDPE filled with nickel flakes (LDPE-Ni). The films are stacked in a post- processing experiment to create a stack 1025 layers with 512 layers filled with nickel filler at loading of 10%. The average starting layer thickness 80 ± 25 micrometers. Thermal treatment of the materials was also completed to further consolidate nickel filler.

[0120] This construct was then subjected to ballistic testing . Specifically, the sample was shot from 49.2 ft distance as per NIJ standard, typically used for level III and IV standards. NIJ Standard-0101.06 is a ballistic resistance standard established by the National Institute of Justice (NIJ) to specify the performance requirements and testing methods for body armor worn by law enforcement and corrections officers. This standard is intended to ensure that body armor provides adequate protection against various ballistic threats, including both handgun and rifle ammunition.

[0121] The results of the ballistic testing are shown in FIG. 9A to FIG. 9D. The bullet was unable to penetrate the composite having a 1 inch thickness. FIG 9A shows a side view of the construct after ballistic testing. The bullet was unable to enter the construct entirely. The construct in FIG.9A was split and a top view was taken as shown in FIG.9B. A picture4880-0190-9465.1 18of a side of the construct is shown in FIG. 9C. A quarter coin is visible to show the size of the construct. A cross-sectional view a cross-sectional view of the multilayered construct is shown in FIG.9D.

[0122] While the invention has been described and illustrated herein by references to various specific materials, procedures, and examples, it is understood that the invention is not restricted to the particular combinations of material and procedures selected for that purpose. Numerous variations of such details can be implied as will be appreciated by those skilled in the art. It is intended that the specification and examples be considered as exemplary, only, with the true scope and spirit of the invention being indicated by the following claims. All references, patents, and patent applications referred to in this application are herein incorporated by reference in their entirety. EMBODIMENTS

[0123] The invention provides also the following non-limiting embodiments.

[0124] Embodiment 1. A multilayered composite structure comprising a plurality of layers, wherein each layer comprises a polymer, wherein each layer has a thickness, and wherein the multilayered composite structure has ballistic impact resistance, or a V50 ballistic limit of 300 m / s or higher.

[0125] Embodiment 2. The multilayered composite structure of embodiment 1, wherein each layer has the same thickness.

[0126] Embodiment 3. The multilayered composite structure of embodiment 1, wherein the thickness of each layer is different.

[0127] Embodiment 4. The multilayered composite structure of embodiment 1, wherein the thickness of the layers gradually decreases from one side of the multilayered composite to another.

[0128] Embodiment 5. The multilayered composite structure of any one of embodiments 1 to 4, wherein at least one layer comprises one or more woven polymers.

[0129] Embodiment 6. The multilayered composite structure of embodiment 5, wherein at least one layer comprises a first polymer and a second polymer woven together to form the layer.

[0130] Embodiment 7. The multilayered composite structure of embodiment 5, wherein the first polymer is oriented along a horizontal axis of the multilayered structure and wherein the second polymer is oriented along the horizontal axis at an approximately 90- degree angle.4880-0190-9465.1 19

[0131] Embodiment 8. The multilayered composite structure of any one of embodiments 1 to 6, wherein at least one layer comprises a polymer having a void.

[0132] Embodiment 9. The multilayered composite structure of embodiment 8, wherein layers of polymer adjacent to the layer of polymer having the having a void lack a void.

[0133] Embodiment 10. The multilayered composite structure of any one of embodiments 1 to 9, wherein at least one layer comprises a polymer having filler and / or additive.

[0134] Embodiment 11. The multilayered composite structure of any one of embodiments 1 to 10, wherein the multilayered composite structure comprises a layer of a first polymer A and a layer of a second polymer B, wherein the layers of the first and second polymer are stacked on top of each other.

[0135] Embodiment 12. The multilayered composite structure of embodiment 11, wherein the layers stacked in an A / B arrangement and wherein the composite structure contains more than one stack.

[0136] Embodiment 13. The multilayered composite structure of any one of embodiments 11 to 12, further comprises a third polymer, wherein the third polymer forms layers surround the layers of polymer A and the layers of polymer B.

[0137] Embodiment 14. The multilayered composite structure of any one of embodiments 1 to10, wherein the multilayered composite structure comprises a layer of a first polymer A, a layer of a second polymer B, and a layer of a third polymer C.

[0138] Embodiment 15. The multilayered composite structure of embodiment 14, wherein the layers are stacked in an A / B / C arrangement and wherein the composite structure contains more than one stack.

[0139] Embodiment 16. The multilayered composite structure of any one of embodiments 1 to 10, wherein a layer of the structure is oriented along a horizontal axis of the composite and wherein a second layer is oriented at a 180-degree angle to the horizontal axis.

[0140] Embodiment 17. The multilayered composite structure of any one of embodiments 1 to 16, wherein the composite structure is formed by extrusion molding.

[0141] Embodiment 18. The multilayered composite structure of any one of embodiments 1 to 17, wherein the composite structure comprises at least 50 layers, with the individual thickness of the layers ranging from 100 micrometer to 1000 micrometers.4880-0190-9465.1 20

[0142] Embodiment 19. The multilayered composite structure of any one of embodiments 1 to 17, wherein the composite structure comprises at least 300 layers, with the individual thickness of the layers ranging from 25 micrometer to 300 micrometers.

[0143] Embodiment 20. The multilayered composite structure of any one of embodiments 1 to 17, wherein the composite structure comprises 300 to 500 layers, with the individual thickness of the layers ranging from 5 micrometer to 300 micrometers.

[0144] Embodiment 21. The multilayered composite structure of any one of embodiments 1 to 17, wherein each layer a thickness of between 10 to 100 nm.

[0145] Embodiment 22. The multilayered composite structure of any one of embodiments 1 to 17, wherein each layer a thickness of between 10 to 50 nm.

[0146] Embodiment 23. The multilayered composite of any one of embodiments 1 to 22, wherein the one or more plurality of layers contains relatively higher modulus, tensile strength, toughness, dielectric constant, molecular weight distributions or stiffness than the other set of plurality of layers.

[0147] Embodiment 24. A method of generating a multilayered composite structure of any one of embodiments 1 to 23, comprising extruding each layer.4880-0190-9465.1 21

Claims

CLAIMS What is claimed is:

1. A multilayered composite structure comprising a plurality of layers, wherein each layer comprises a polymer, wherein each layer has a thickness, and wherein the multilayered composite structure has ballistic impact resistance, or a V50 ballistic limit of 300 m / s or higher.

2. The multilayered composite structure of claim 1, wherein each layer has the same thickness.

3. The multilayered composite structure of claim 1, wherein the thickness of each layer is different.

4. The multilayered composite structure of claim 1, wherein the thickness of the layers gradually decreases from one side of the multilayered composite to another.

5. The multilayered composite structure of claim 1, wherein at least one layer comprises one or more woven polymers.

6. The multilayered composite structure of claim 5, wherein at least one layer comprises a first polymer and a second polymer woven together to form the layer.

7. The multilayered composite structure of claim 5, wherein the first polymer is oriented along a horizontal axis of the multilayered structure and wherein the second polymer is oriented along the horizontal axis at an approximately 90-degree angle.

8. The multilayered composite structure of claim 1, wherein at least one layer comprises a polymer having a void.

9. The multilayered composite structure of claim 8, wherein layers of polymer adjacent to the layer of polymer having the having a void lack a void.

10. The multilayered composite structure of any one of claims 1 to 9, wherein at least one layer comprises a polymer having filler and / or additive.

11. The multilayered composite structure of any one of claims 1 to 9, wherein the multilayered composite structure comprises a layer of a first polymer A and a layer of a4880-0190-9465.1 22second polymer B, wherein the layers of the first and second polymer are stacked on top of each other.

12. The multilayered composite structure of claim 11, wherein the layers stacked in an A / B arrangement and wherein the composite structure contains more than one stack.

13. The multilayered composite structure of claim, further comprising a third polymer, wherein the third polymer forms layers surround the layers of polymer A and the layers of polymer B.

14. The multilayered composite structure of any one of claims 1 to 9, wherein the multilayered composite structure comprises a layer of a first polymer A, a layer of a second polymer B, and a layer of a third polymer C.

15. The multilayered composite structure of claim 14, wherein the layers are stacked in an A / B / C arrangement and wherein the composite structure contains more than one stack.

16. The multilayered composite structure of any one of claims 1 to 9, wherein a layer of the structure is oriented along a horizontal axis of the composite and wherein a second layer is oriented at a 180-degree angle to the horizontal axis.

17. The multilayered composite structure of any one of claims 1 to 9, wherein the composite structure is formed by extrusion molding.

18. The multilayered composite structure of any one of claims 1 to 9, wherein the composite structure comprises at least 50 layers, with the individual thickness of the layers ranging from 100 micrometer to 1000 micrometers.

19. The multilayered composite structure of any one of claims 1 to 9, wherein the composite structure comprises at least 300 layers, with the individual thickness of the layers ranging from 25 micrometer to 300 micrometers.

20. The multilayered composite structure of any one of claims 1 to 9, wherein the composite structure comprises 300 to 500 layers, with the individual thickness of the layers ranging from 5 micrometer to 300 micrometers.

21. The multilayered composite structure of any one of claims 1 to 9, wherein each layer a thickness of between 10 to 100 nm.4880-0190-9465.1 2322. The multilayered composite structure of any one of claims 1 to 9, wherein each layer a thickness of between 10 to 50 nm.

23. The multilayered composite of any one of claims 1 to 9, wherein the one or more plurality of layers contains relatively higher modulus, tensile strength, toughness, dielectric constant, molecular weight distributions or stiffness than the other set of plurality of layers.

24. A method of generating the multilayered composite structure of any one of claims 1 to 9, comprising extruding each layer.4880-0190-9465.1 24

Images