Multi-threat protective article having a multi-layer assembly

Abstract

Traditional protective clothing is usually difficult to balance the anti-puncture and soft comfort. Although the existing materials can provide protection, they may be heavy or insufficient in performance when dealing with different threat conditions. The present application effectively solves the above problems by using a composite material structure, which uses a two-dimensional filler to prepare a brick-like polymer composite, and further spins and weaves into a three-dimensional fabric configuration with a negative poisson's ratio, thereby significantly improving the anti-puncture performance and energy absorption capacity of soft protective clothing.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Patent Application No. 19 / 000,578, filed December 23, 2024, which is incorporated herein by reference in its entirety. Technical Field

[0002] This invention generally relates to protective products, specifically designed to provide resistance to puncture and other threats, including cutting, slashing and impact. Background Technology

[0003] Military personnel, security personnel, and other high-risk workers require protective gear capable of defending against sharp objects, knives, and bullets simultaneously to enhance their safety in various high-risk scenarios. For example, WO 01 / 37691A1 describes a specially engineered material to provide protection against knife attacks and bullet threats. US Patent 6133169 discloses a structure resistant to knife, ice pick, and bullet penetration, comprising a metal chainmail, a tightly woven fabric layer, and a high-toughness ballistic layer.

[0004] However, while existing protective gear offers protection against multiple threats, it still suffers from several common drawbacks. These include weight and comfort issues; the often bulky nature of such gear can cause discomfort and restrict movement during extended wear. Many protective materials also lack breathability, leading to overheating when worn in high-temperature or high-intensity conditions. Furthermore, enhancing protective performance often requires sacrificing flexibility, thus limiting the wearer's agility during critical operations.

[0005] Balancing protection against multiple threats presents another challenge, as some protective gear excels in ballistic protection but is less effective against knives or sharp objects. High-performance protective equipment is often expensive, making it unaffordable for some users or organizations, especially when large-scale deployments are required. These drawbacks highlight the need to improve existing protective gear in certain application scenarios. Summary of the Invention

[0006] The purpose of this invention is to provide a multi-threat protective garment to solve the aforementioned technical problems. The structure is designed to maximize protective effectiveness while maintaining flexibility and comfort. The protective suit is lightweight, durable, and suitable for long-term use in various harsh environments.

[0007] This invention relates to protective fabrics and / or composite materials designed to improve durability and mechanical properties. At a macroscopic level, the material comprises multiple layers of fabric or composite material. Some layers incorporate a negative Poisson's ratio structure to further enhance the material's puncture and impact resistance. A brick-and-mortar microstructure is formed by incorporating peeled two-dimensional fillers into the polymer material. This tightly integrated system not only enhances the fabric's mechanical properties and improves energy absorption but also provides multi-threat protection without compromising comfort and flexibility.

[0008] In a first aspect, the present invention provides a multi-threat protective article having a multi-layer assembly. The multi-layer assembly includes: an outer hard coating for external protection; a negative Poisson's ratio fabric layer; a dense non-woven fabric; and an inner foam layer conforming to the user's body for impact absorption. The negative Poisson's ratio fabric layer has at least two layers of interlaced three-dimensional fabric, the three-dimensional fabric having a raised stripe or sandwich structure, the sandwich structure being a spacer structure with partial connections between two surface fabric layers, the connection areas being distributed in stripes, thereby forming a negative Poisson's ratio structure. The negative Poisson's ratio fabric layer and the dense non-woven fabric are located between the outer hard coating and the inner layer. According to ASTM D4032-08, the stiffness of each layer of the multi-threat protective article ranges from 0.9 N in the inner foam layer to 50 N in the dense non-woven fabric.

[0009] In one embodiment, the multilayer assembly is made of a fabric composite material produced using a masterbatch comprising stripped two-dimensional fillers and a polymer material. The stripped two-dimensional fillers are stripped by compatibilizer intercalation and their surface modification is performed in situ. The polymer material is reinforced by the stripped two-dimensional fillers to form a brick-mortar microstructure with adjacent two-dimensional filler particles interlaced in parallel. The stripped two-dimensional fillers have a width of less than 10 μm and an aspect ratio of at least 50.

[0010] In one embodiment, the stripped two-dimensional filler is stripped by compatibilizer intercalation and in-situ surface modification is completed before blending with the polymer material.

[0011] In one embodiment, the compatibilizer comprises polypropylene-grafted maleic anhydride (PP-g-Ma), polyethylene-grafted maleic anhydride (PE-g-Ma), ethylene-butyl acrylate-grafted methacrylate (EBA-g-Ma), polyethylene glycol-grafted methacrylate (POE-g-Ma), aminosilane, or a combination thereof.

[0012] In one embodiment, the polymer material includes polypropylene (PP), high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), polyamide (PA), polyurethane (PU), silicone rubber, or a combination thereof.

[0013] In one embodiment, the exfoliated two-dimensional filler includes clay, graphene, MXene, zirconium phosphate (ZrP), boron nitride (BN), molybdenum disulfide (MoS), layered double hydroxide (LDH), or combinations thereof.

[0014] In one embodiment, the negative Poisson's ratio fabric layer has a negative Poisson's ratio.

[0015] In one embodiment, the multilayer fabric composite material further comprises a one-dimensional filler that is co-filled with the stripped two-dimensional filler to promote the parallel alignment of the stripped two-dimensional filler.

[0016] In one embodiment, the one-dimensional filler includes carbon nanotubes and carbon nanowires.

[0017] In one embodiment, the length of the one-dimensional packing is greater than 20 μm.

[0018] In one embodiment, the carbon nanotubes include single-walled carbon nanotubes, multi-walled carbon nanotubes, functionalized carbon nanotubes, or doped carbon nanotubes.

[0019] In one embodiment, the carbon nanowires include graphene nanoribbons and carbon nanofibers.

[0020] In one embodiment, the fabric composite material further includes a thixotropic agent comprising Thixatrol Plus, Thixatrol Max, Thixatrol ST, Thixatrol R, PE-WAX, PP-WAX, or a combination thereof.

[0021] In one embodiment, the multiple threats include resistance to puncture, blade, sharp, and blunt impacts.

[0022] In a second aspect, the present invention provides a method for manufacturing a multi-threat protective article, the method comprising preparing a masterbatch and forming a multilayer fabric composite material from the masterbatch. The masterbatch has a two-dimensional filler that has been exfoliated and surface-modified by intercalation with a compatibilizer, and a polymer material. The multilayer fabric composite material is arranged sequentially from the inside out such that the multi-threat protective article comprises: an inner foam layer, a dense non-woven fabric, a negative Poisson's ratio fabric layer, and an outer hard coating. The width of the exfoliated two-dimensional filler is less than 10 μm, and the aspect ratio is at least 50.

[0023] In one embodiment, the stripped two-dimensional filler is blended with the polymer material to form a brick-mortar microstructure in which adjacent two-dimensional filler particles are interlaced in parallel.

[0024] In one embodiment, the method further includes co-filling the one-dimensional filler with the stripped two-dimensional filler to guide the parallel alignment of the two-dimensional filler particles.

[0025] In one embodiment, the method further includes incorporating a thixotropic agent into the masterbatch. Attached Figure Description

[0026] Embodiments of the invention are described in more detail below with reference to the accompanying drawings, in which:

[0027] Figure 1 A schematic diagram of the protective suit is shown, with enlarged areas revealing the structure of each layer;

[0028] Figure 2A A schematic diagram is shown showing a fabric substrate with a raised stripe structure that is stacked in an alternating manner and undergoes negative Poisson's ratio deformation when compressed. Figure 2B A schematic diagram is shown showing a double-layered fabric with a sandwich structure that is stacked in an alternating manner and produces a negative Poisson's ratio deformation when compressed;

[0029] Figure 3A A conventional method for stripping and modifying two-dimensional fillers is shown. Figure 3B The present invention provides a method for stripping and modifying two-dimensional fillers;

[0030] Figure 4A A schematic diagram of a side view of a fiber polymer matrix with a brick-and-mortar structure is shown, and Figure 4B Its top view is shown;

[0031] Figure 5A and Figure 5B Two-dimensional packing materials with different aspect ratios are shown, the different aspect ratios changing the width of the two-dimensional packing material;

[0032] Figure 6 A schematic diagram of a fiber polymer matrix is ​​shown, in which two-dimensional fillers and one-dimensional fillers are mixed together;

[0033] Figure 7 The preparation process of the masterbatch is shown;

[0034] Figure 8A The three-layer structure of the multilayer fabric composite material is shown. Figure 8B The four-layer structure of a multilayer fabric composite material is shown;

[0035] Figure 9A The apparatus used for puncture testing is shown. Figure 9BThe knife puncture test on a multilayer 75gsm nonwoven fabric (61 layers) is shown, in which the penetration depth of all three impacts is <3mm;

[0036] Figure 10 The impact resistance test results of the non-woven fabric + foam combination are shown, where the deformation depth is <9mm; and

[0037] Figure 11 The stiffness of 75gsm nonwoven fabric with different numbers of layers is shown. Detailed Implementation

[0038] In the following description, masterbatch, toughening fibers, and multi-threat protective articles are described as preferred examples. It will be apparent to those skilled in the art that modifications, including additions and / or substitutions, can be made without departing from the scope and spirit of the invention. Certain specific details may be omitted in this invention to avoid confusion; however, the purpose of this disclosure is to enable those skilled in the art to practice the technical solutions described herein without excessive experimentation.

[0039] This invention provides a multi-layered, multi-threat protective product, each layer being composed of a multi-threat resistant fabric composite material. The composite material is made from a masterbatch comprising peeled two-dimensional fillers. These two-dimensional fillers are peeled off using a compatibilizer, undergo in-situ surface modification, and are blended with a polymer material. The two-dimensional fillers form a brick-and-mortar-like microstructure within the fibrous polymer matrix, enhancing the product's impact and puncture resistance.

[0040] Polymer materials can include a variety of polymers, which can be selected based on their mechanical properties, compatibility with fillers, and intended application. Examples of suitable polymer materials include, but are not limited to, polypropylene (PP), high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), polyamide (PA), polyurethane (including PU foam and PU cast rigid sheets), silicone rubber, or combinations thereof.

[0041] In one embodiment, the article comprises at least three layers arranged sequentially from the outermost to the innermost layer: a rigid coating layer, a dense nonwoven fabric, and an inner layer. The rigid coating layer is made of cast PU rigid sheet. The dense nonwoven fabric is made of PP, HDPE, UHMWPE, nylon, or mixtures thereof. The inner layer is made of HDPE, silicone rubber, and PU foam.

[0042] Additionally, the article comprises at least four layers arranged sequentially from the outermost to the innermost layer: a hard coating layer, a dense nonwoven fabric, a negative Poisson's ratio fabric layer, and an inner layer.

[0043] Unrestricted, the articles of the present invention may include five or more layers. For example, the articles of the present invention may include a hard coating, a dense nonwoven fabric, a negative Poisson's ratio fabric layer, an inner layer, and additional functional layers, such as a cushioning layer, an insulating layer, or other layers designed to enhance protective performance. These layers can be combined and arranged according to specific application requirements to achieve optimal protection against multiple threats.

[0044] In one embodiment, the negative Poisson's ratio fabric layer can be formed from multiple layers of woven or knitted fabric. Specifically, the negative Poisson's ratio fabric layer is characterized by consisting of at least two layers of fabric, each layer having a raised stripe or sandwich structure, which are staggered when stacked. The raised stripes or sandwich structures in adjacent layers are offset from each other, thereby helping to improve tensile strength.

[0045] In one embodiment, the inner layer is a cushioning foam.

[0046] A further feature of this invention is the inclusion of raised strips or sandwich structures within the layers, forming a negative Poisson's ratio structure, thereby improving flexibility and toughness. The sandwich structure with raised strips enhances the tensile properties of the material. When subjected to deformation, this structure generates additional energy dissipation points, further improving the fabric's protective capabilities.

[0047] Poisson's ratio is the ratio of the transverse normal strain to the axial normal strain of a material when it is stretched or compressed in one direction. For most materials, when stretched in one direction, they typically contract in the perpendicular direction, thus exhibiting a positive Poisson's ratio. Conversely, when compressed, they expand laterally. However, materials exhibiting a negative Poisson's ratio show different behavior: they expand laterally when stretched and contract laterally when compressed.

[0048] Integrating materials with a negative Poisson's ratio into protective fabrics offers several key advantages, particularly in enhancing impact resistance, flexibility, and energy absorption. These properties are essential for designing high-performance protective gear to defend against a variety of threats, such as punctures, slashing, and blunt force impacts.

[0049] like Figure 2A As shown, each fabric layer contains multiple vertically extending ridges, with the ridges of adjacent layers staggered when multiple layers are stacked. These ridges enhance the structural integrity of the layers, provide additional strength, and generate a negative Poisson's ratio effect, which enhances the material's ability to absorb and dissipate impact energy. During deformation, each layer fits tightly against each other, ensuring a compact and cohesive fit. Figure 2B Another embodiment featuring a sandwich structure is described, wherein there are strip-shaped, locally connected spacer structures between the two surface fabric layers of each fabric layer. When multiple layers are stacked, the strip-shaped spacer structures of adjacent fabric layers are staggered. During deformation, the spacer structure segments interlock with the hollow segments of adjacent layers, thereby producing a tensile effect.

[0050] The fabric composite material of the present invention comprises a two-dimensional filler that has been peeled and in-situ surface modified using a compatibilizer. The compatibilizer promotes effective bonding with the polymer material, producing a homogeneous mixture that assembles into a brick-and-mortar microstructure. Figure 3A A conventional one-step process for exfoliation and surface modification of fillers is illustrated. In traditional two-dimensional filler treatment methods, particles must first be intercalated and exfoliated to expose the inner surface of the plate-like particles before surface modification can be performed. However, this method has several drawbacks. A significant limitation is that small-molecule intercalating agents can lead to incomplete or inconsistent exfoliation, resulting in suboptimal exposure of the inner surface. This causes uneven surface modification, affecting the overall properties of the composite material. Furthermore, small-molecule intercalating agents can occupy the surface active sites of the filler, making subsequent surface modification difficult, thereby reducing the efficiency of compatibilizer modification and affecting the uniformity of the resulting brick-and-mortar microstructure.

[0051] Therefore, as Figure 3B As shown, this invention demonstrates that compatibilizers can simultaneously function as intercalating agents and surface modifiers. This treatment method not only simplifies the pretreatment process but also avoids the negative impacts associated with small molecules involved in intercalation. Furthermore, this method offers several other advantages, including improved filler dispersion within the polymer matrix, enhanced compatibility between the filler and the matrix, and increased interfacial bonding strength, resulting in superior overall composite material properties. Moreover, this method reduces processing complexity by minimizing the number of steps involved, reducing energy consumption and processing time, and making the material easier to manufacture.

[0052] This microstructure plays a crucial role in improving the mechanical properties of materials and providing resistance to various types of threats. Figure 4A The brick-and-mortar microstructure within the fiber polymer matrix is ​​shown, while Figure 4B This displays its top view.

[0053] Examples of two-dimensional fillers include, but are not limited to, clay, graphene, boron nitride (BN), molybdenum disulfide (MoS), MXene, zirconium phosphate (ZrP), and layered double hydroxides (LDH). These fillers can be used alone or in combination, depending on the specific requirements of the protective article.

[0054] For two-dimensional fillers with a small aspect ratio, the particles tend to be randomly dispersed within the polymer matrix. Figure 5A In contrast, two-dimensional fillers with a larger aspect ratio are more likely to exhibit parallel alignment within the polymer matrix due to repeated collisions and tumbling during the mixing process. Figure 5BThe width of the stripped two-dimensional packing is less than 10 μm, and the aspect ratio (width to thickness) is greater than 50. Preferably, the aspect ratio of the stripped two-dimensional packing ranges from 50 to 1000.

[0055] Controlling the aspect ratio of two-dimensional fillers is advantageous because a larger aspect ratio facilitates the parallel alignment of the fillers within the matrix. This parallel alignment promotes more efficient stress transfer between the polymer matrix and the filler, thereby significantly improving mechanical properties such as tensile strength and resistance to puncture and impact. This alignment also contributes to more efficient stress transfer between the polymer matrix and the filler, resulting in composite materials with excellent structural integrity and overall performance.

[0056] Furthermore, in the fabric composite material of the present invention, specific two-dimensional fillers (with a large aspect ratio) are combined with one-dimensional fillers (such as carbon nanotubes and nanowires) to further improve protective capabilities. Figure 6 ).

[0057] The addition of one-dimensional fillers offers several advantages, including enhanced mechanical strength and toughness, as they effectively close microcracks and distribute stress more efficiently throughout the composite. This synergistic combination of two-dimensional and one-dimensional fillers creates a reinforced network within the polymer matrix, which not only increases the composite's resistance to punctures and tears but also improves its overall durability and lifespan, making it highly suitable for protective applications.

[0058] During the mixing and post-stretching of fiber composites, the traction applied to the one-dimensional filler can induce the two-dimensional filler to align in parallel, thereby promoting a more efficient filler dispersion network and enhancing the overall properties of the composite.

[0059] Suitable one-dimensional fillers such as carbon nanotubes (CNTs) and carbon nanowires are chosen because they can significantly improve the strength and impact resistance of composite materials. These one-dimensional fillers (such as CNTs) are much longer than the width of two-dimensional fillers, typically exceeding 20 μm in length, to ensure sufficient reinforcement.

[0060] During the manufacturing process, one-dimensional and two-dimensional packings can form a one-dimensional-two-dimensional packing dispersion network through several mechanisms:

[0061] (1) Melt Blending / Extrusion: During melt blending or extrusion, both one-dimensional and two-dimensional fillers are mixed with the polymer matrix. The one-dimensional filler is dispersed throughout the polymer matrix. The shear forces generated during blending help induce the one-dimensional filler to align in parallel. Simultaneously, the two-dimensional filler is also dispersed and tends to align in parallel.

[0062] (2) Stretching: Post-stretching of polymer composites can further align the one-dimensional fillers parallel to the stretching direction. When the polymer matrix is ​​stretched, the one-dimensional fillers further induce the two-dimensional fillers to form parallel arrangements, thereby forming a well-structured filler network.

[0063] Optionally, the composite material may also include a thixotropic agent to further improve the rheological properties of the material, ensuring ease of handling and application during manufacturing. Examples of thixotropic agents may include Thixatrol Plus, Thixatrol Max, Thixatrol ST, Thixatrol R, PE-WAX, PP-WAX, and mixtures thereof.

[0064] Example

[0065] Example 1

[0066] Preparation of fabric composite materials

[0067] First, a specific amount of compatibilizer was selected. This compatibilizer acts as an intercalating agent and surface modifier for the two-dimensional filler. 5 g of montmorillonite (MMT) was added to 150 g of xylene. The mixture was subjected to ultrasonic treatment or high-shear mixing for 1 hour to achieve thorough dispersion. 25 g of polypropylene-grafted maleic anhydride (PP-g-Ma) was added to the mixture. The mixture was magnetically stirred at 125°C for 6 hours to achieve complete dissolution and homogeneous mixing of PP-g-Ma. The mixture was added to an equal volume of ethanol and then centrifuged. The precipitate was washed three times with ethanol to remove excess xylene. The precipitate was then dried overnight in an oven at 80°C to obtain the MMT / PP-g-Ma compound.

[0068] Then, intercalated and surface-modified MMT (5g MMT and 25g PP-g-Ma) was blended with 75g PP at 180°C and 100rpm for 30 minutes to form a masterbatch, as follows: Figure 7 As shown, the ratio of the two-dimensional filler to the polymer material is 5:100. During the high-temperature mixing process, the interlayer compatibilizer molecules (PP-g-Ma) exfoliate the MMT into monolayer particles under shear force. This compatibilizer thus completes the intercalation, surface modification, and exfoliation of the MMT, enhancing its compatibility with the polymer matrix and promoting better dispersion within the matrix. When the exfoliated two-dimensional filler is mixed into the polymer matrix, the filler naturally forms a discrete, parallel plate-like structure within the matrix. The polymer matrix acts as "mortar," filling the spaces between these plate-like two-dimensional fillers, which act as "bricks." The brick-and-mortar microstructure generated within the polymer matrix significantly enhances puncture resistance and overall toughness.

[0069] Once a brick-and-mortar-like microstructure is formed within the polymer matrix, the masterbatch can be further processed through melt spinning to produce toughened fibers.

[0070] The aforementioned material was added to a melt spinning machine to obtain toughened fibers at a spinning temperature of 220°C and a winding speed of 50 rpm.

[0071] In the control experiment, 5g of MMT and 25g of PP-g-Ma were directly mixed in an internal mixer at 180°C and 100rpm for 30 minutes, but PP-g-Ma could not be intercalated into the MMT layers. Only when the ratio of PP-g-Ma to MMT was increased to above 25:1 could PP-g-Ma be intercalated into the MMT interlayer using this direct mixing method. However, excessive PP-g-Ma can damage the mechanical properties of PP composites.

[0072] Example 2

[0073] Multi-layer structural configuration

[0074] Multi-threat protection products consist of multiple layers, each specifically designed to provide maximum protection against different threats while ensuring flexibility and comfort.

[0075] In one embodiment, the article comprises at least three layers arranged sequentially from the outermost to the innermost layer: a hard coating layer, a dense nonwoven fabric, and an inner layer ( Figure 8A The hard coating provides initial resistance to sharp and high-speed impacts, while the dense non-woven fabric enhances the overall tensile strength and tear resistance of the garment. An inner foam layer close to the user's body provides cushioning and shock absorption, ensuring comfort during extended use.

[0076] In another embodiment, the article comprises at least four layers arranged sequentially from the outermost to the innermost layer: a hard coating layer, a dense nonwoven fabric, a negative Poisson's ratio fabric layer, and an inner layer ( Figure 8B In negative Poisson's ratio fabric layers, fabrics with raised stripes or sandwich structures are bonded together by adhesives to ensure their offset alignment, and there is no connection between the negative Poisson's ratio fabric layer and adjacent layers or any other layers.

[0077] Example 3

[0078] Characterization of multilayer fabric composites

[0079] Puncture tests were conducted according to the KR1 and SP1 levels of the 2017 UK Home Office Body Armour Standard (CAST Home Office Body Armour Standard). The tests involved multiple layers of 75gsm and 120gsm nonwoven fabric under conditions simulating a real puncture threat. Additional performance information for the sharps puncture tests is summarized in Table 1. The apparatus used for the puncture tests was... Figure 9A It is displayed in the middle.

[0080] like Figure 9B As observed, during the knife puncture test on the 61-layer 75gsm nonwoven fabric, the penetration depth of the three impacts was consistently less than 3mm.

[0081] Table 1 - Sharp instrument puncture test results of multilayer nonwoven fabric

[0082] For 75gsm nonwoven fabric (0.1mm thick per layer, 66 layers), the penetration depth of the first impact was approximately 9mm, with subsequent impacts showing penetration depths of less than 1mm, 0mm, and 0mm respectively. 120gsm nonwoven fabric (0.2mm thick per layer, 41 layers) exhibited even stronger puncture resistance, with 0mm penetration on the first and second impacts and approximately 3mm penetration on the third impact. The combined testing of the nonwoven fabric and foam layers further enhanced performance, particularly in sharps tests, where no penetration was observed at various angles and under different impacts (Table 2).

[0083] Table 2 – Puncture test results of non-woven fabric + foam combination *Impact angle is only applicable to knife penetration testing; *PD is an abbreviation for penetration depth (mm).

[0084] Impact resistance tests conducted according to W5 level of the VPAM KDIW 2004 standard showed that the deformation depth of the non-woven fabric and foam combination was less than 9 mm. Figure 10 As shown.

[0085] Additionally, the stiffness of the fabric is evaluated using the circular bending method according to ASTM D4032 standard. Figure 11 As shown, this provides a comprehensive overview of the structural elasticity and flexibility of composite materials, making them ideal for multi-threat protection applications.

[0086] Example 4

[0087] Application of multilayer fabric composites in multi-threat protection products

[0088] Multi-layered fabric composites are designed to be incorporated into protective garments to counter a variety of threat types, including knife, sharp, and blunt weapon attacks.

[0089] The foregoing description of the invention has been provided for purposes of illustration and description. The foregoing description is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations will be apparent to those skilled in the art.

[0090] Examples have been selected and described in order to best explain the principles of the invention and its practical application, thereby enabling others skilled in the art to understand the invention with respect to the various embodiments and with various modifications suitable for the particular intended use.

[0091] definition

[0092] Throughout this specification, unless the context otherwise requires, the word “comprise” or variations such as “comprises” or “comprising” should be understood to imply inclusion of the stated whole or group of wholes, but not to exclude any other whole or group of wholes. It should also be noted that in this disclosure and particularly in the claims and / or paragraphs, terms such as “comprises,” “comprised,” and “comprising” may have the meaning attributed to them under U.S. patent law, for example, allowing elements not expressly listed but excluding elements found in the prior art or elements affecting the essential or novel characteristics of the invention.

[0093] Furthermore, throughout this specification and claims, unless the context otherwise requires, the word "include" or variations thereof, such as "includes" or "including," shall be understood to imply inclusion of the stated whole or group of wholes, but not to exclude any other whole or group of wholes.

[0094] References to "an embodiment," "an example embodiment," "exemplary embodiment," etc., in this specification indicate that the described embodiment may include specific features, structures, or characteristics, but not every embodiment necessarily includes specific features, structures, or characteristics. Furthermore, such phrases do not necessarily refer to the same embodiment. Additionally, when a specific feature, structure, or characteristic is described in connection with an embodiment, it is assumed that the effect of such feature, structure, or characteristic in conjunction with other embodiments is within the knowledge of those skilled in the art, whether explicitly described or not.

[0095] As used herein, the terms “approximately,” “basically,” “substantially,” and “about” are used to describe and explain small variations. When used in conjunction with an event or situation, the terms can refer to the exact occurrence of the event or situation as well as the approximate occurrence of the event or situation. As used herein with respect to a given value or a given range, the term “about” generally means within ±10%, ±5%, ±1%, or ±0.5% of the given value or given range. A range may be indicated herein as from one endpoint to another or between two endpoints. Unless otherwise specified, all ranges disclosed in this disclosure include endpoints. When referring to the same numerical value or characteristic, the term can refer to a value within ±10%, ±5%, ±1%, or ±0.5% of the average of the values.

[0096] A "brick-and-mortar structure" refers to a material arrangement in which alternating layers mimic the organization of bricks and mortar in construction. In this structure, strong, hard layers ("bricks") are arranged alternately with softer, more flexible layers ("mortar"). This configuration enhances mechanical properties such as toughness and strength by combining rigidity with the ability to absorb and distribute stress, thereby reducing the likelihood of fracture.

[0097] The term "negative Poisson's ratio" refers to a material property in which the lateral strain is in the same direction as the applied axial strain. In other words, when a material with a negative Poisson's ratio is stretched in one direction, it will expand in the other direction; and when it is compressed, it will contract laterally.

[0098] A thixotropic agent is a substance added to a material to impart thixotropic properties. Thixotropy refers to the property of a material to decrease in viscosity when subjected to shear forces (such as stirring or shaking) and then return to a more viscous state when at rest. This behavior makes handling and application during manufacturing easier because the material can flow more freely during processing and maintains its shape and stability once the force is removed.

[0099] The term "MXene" refers to a class of two-dimensional inorganic compounds, which are atomically thin sheets composed of transition metal carbides, nitrides, or carbonitrides. The surface of MXene is composed of hydrophilic functional groups.

[0100] Other definitions of the selected terms used herein may be found in specific embodiments of the invention and apply throughout. Unless otherwise defined, all other technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

Claims

1. A multi-layered composite component for multi-threat protection, characterized in that, The multi-layer assembly includes: An external hard coating, which is used for external protection; A negative Poisson's ratio fabric layer having at least two layers of staggered three-dimensional fabric, the three-dimensional fabric having a raised stripe or sandwich structure, the sandwich structure being a spacer structure with partial connection between two surface fabrics, the connection area being distributed in strips, thereby forming a negative Poisson's ratio structure; Dense non-woven fabric; as well as An inner foam layer that conforms to the user's body for shock absorption. The negative Poisson's ratio fabric layer and the dense nonwoven fabric are located between the outer hard coating layer and the inner foam layer, and the stiffness range of each layer of the multi-threat protective article, according to ASTM D4032-08, is from 0.9N in the inner foam layer to 50N in the dense nonwoven fabric.

2. The multi-threat protection article of claim 1, wherein the multi-layer assembly is made of a fabric composite material produced using a masterbatch comprising: The exfoliated two-dimensional filler, wherein the exfoliated two-dimensional filler is exfoliated by compatibilizer intercalation, and the surface modification of the two-dimensional filler is completed in situ to improve its compatibility with the polymer; and A polymer material, wherein the polymer material is reinforced by the exfoliated two-dimensional filler, the exfoliated two-dimensional filler exhibiting a parallel staggered brick-and-mortar microstructure within the polymer matrix. The stripped two-dimensional filler has a width of less than 10 μm and an aspect ratio of at least 50.

3. The multi-threat protection article according to claim 2, wherein the stripped two-dimensional filler is stripped by the compatibilizer and undergoes in-situ surface modification before being blended with the polymer material.

4. The multi-threat protection article according to claim 2, wherein the compatibilizer comprises polypropylene-grafted maleic anhydride (PP-g-Ma), polyethylene-grafted maleic anhydride (PE-g-Ma), ethylene-butyl acrylate-grafted methacrylate (EBA-g-Ma), polyethylene glycol-grafted methacrylate (POE-g-Ma), aminosilane, or a combination thereof.

5. The multi-threat protection product according to claim 2, wherein the polymer material comprises polypropylene, high-density polyethylene, ultra-high molecular weight polyethylene, polyamide, polyurethane, silicone rubber, or a combination thereof.

6. The multi-threat protection article according to claim 1, wherein the stripped two-dimensional filler comprises clay, graphene, MXene, zirconium phosphate, boron nitride, molybdenum disulfide, layered double hydroxide, or a combination thereof.

7. The multi-threat protection article according to claim 1, wherein the negative Poisson's ratio fabric layer has a negative Poisson's ratio.

8. The multi-threat protective article of claim 1, wherein the multilayer fabric composite material further comprises a one-dimensional filler that is co-filled with the stripped two-dimensional filler to promote the parallel alignment of the stripped two-dimensional filler.

9. The multi-threat protection article according to claim 8, wherein the one-dimensional filler comprises carbon nanotubes and carbon nanowires.

10. The multi-threat protection article according to claim 9, wherein the length of the one-dimensional filler is greater than 20 μm.

11. The multi-threat protection article according to claim 9, wherein the carbon nanotubes comprise single-walled carbon nanotubes, multi-walled carbon nanotubes, functionalized carbon nanotubes, or doped carbon nanotubes.

12. The multi-threat protection product according to claim 9, wherein the carbon nanowires comprise graphene nanoribbons and carbon nanofibers.

13. The multi-threat protection article of claim 2, wherein the fabric composite material further comprises a thixotropic agent, the thixotropic agent comprising Thixatrol Plus, Thixatrol Max, Thixatrol ST, Thixatrol R, PE-WAX, PP-WAX, or a combination thereof.

14. The multi-threat protective article according to claim 1, wherein the multi-threat includes resistance to puncture, blade, sharp and blunt impacts.

15. A method for manufacturing a multi-threat protection article, the method comprising: Prepare a masterbatch, wherein the masterbatch comprises a two-dimensional filler that has been exfoliated and surface-modified by compatibilizer intercalation, and a polymer material; The masterbatch is used to form a multilayer fabric composite material, wherein the multilayer fabric composite material is arranged sequentially from the inside to the outside, so that the multi-threat protection article includes: Inner foam layer, dense non-woven fabric, negative Poisson's ratio fabric layer, and outer hard coating. The stripped two-dimensional filler has a width of less than 10 μm and an aspect ratio of at least 50.

16. The method of claim 15, wherein the stripped two-dimensional filler is blended with the polymer material to form a brick-mortar microstructure in which adjacent two-dimensional filler particles are interlaced in parallel.

17. The method of claim 15, wherein the method further comprises co-filling the one-dimensional filler with the stripped two-dimensional filler, guiding the particles of the stripped two-dimensional filler to be arranged in parallel.

18. The method of claim 15, wherein the method further comprises incorporating a thixotropic agent into the masterbatch.

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