Composite material for manufacturing bulletproof helmet and preparation method thereof

Abstract

The invention relates to the field of bulletproof and explosion-proof materials, and discloses a composite material for manufacturing a bulletproof helmet and a preparation method of the composite material, the material is composed of an inner layer made of modified PBO fiber cloth, a middle layer made of a resin-based bulletproof composite material, and an outer layer made of a graphene-reinforced Al2O3 ceramic composite material. The inner layer is formed by adding dispersed graphene in a PBO monomer polymerization process, and generating PBO / graphene composite polymer fibers through a condensation polymerization reaction; the middle layer is a weftless sheet obtained by taking a thermoplastic styrene block copolymer as a matrix of a composite material, dissolving the thermoplastic styrene block copolymer in a solvent, adding nano graphene for uniform dispersion, and performing fiber impregnation and solvent volatilization; and the outer layer is prepared by the following steps: uniformly dispersing 3-6 parts by weight of graphene, 60-80 parts by weight of Al2O3, 10-20 parts by weight of silicon carbide and 5-10 parts by weight of titanium carbide in a DMSO solution through high-speed shearing, concentrating, evaporating to dryness, grinding in a grinding machine for 58-65 minutes, and sintering the ground mixture through spark plasma.

Description

Technical Field

[0001] The invention relates to bulletproof and explosion-proof materials, and in particular to a composite material for making a bulletproof helmet and a preparation method thereof. Background Art

[0002] Traditional bulletproof materials are mostly made of high-strength metals, ceramics, fiberglass, etc. If these materials are to achieve good bulletproof effects, they generally need to be thick enough, which results in a heavy weight of the bulletproof device, which has an adverse effect on the design and manufacture of the bulletproof device and brings various restrictions to the design of the bulletproof device.

[0003] Aramid fiber has good impact resistance and fatigue resistance, good dielectric and chemical stability, resistance to organic solvents, fuels, organic acids and dilute strong acids and alkalis, good bending resistance and processing performance. It can be woven into fabrics on ordinary looms, and its strength after weaving is not less than 90% of the original fiber strength. However, aramid fiber has poor UV resistance and lacks active groups on the surface, making it difficult to modify, which limits its application in various fields.

[0004] Graphene is an atomically thick two-dimensional material with ultra-high specific surface area, excellent mechanical properties, high electrical conductivity, high thermal conductivity and high barrier properties. Moreover, adding a small amount of graphene can improve many properties of the material at the same time, with ultra-high cost performance, which has made it widely studied in composite materials. Patent 201410269027.0 "A method for modifying aramid fiber by surface grafting of graphene oxide" uses dopamine-modified aramid fiber and amino-modified graphene oxide to react to obtain modified aramid fiber. Although uniform coverage of graphene oxide is achieved, graphene oxide itself has many defects. Compared with graphene, its mechanical properties, electrical properties, thermal conductivity and other properties are significantly reduced, and it cannot effectively enhance aramid fiber.

[0005] PBO fiber has the characteristics of high strength, high modulus, heat resistance, and flame retardancy. Its strength and modulus are twice that of Kevlar fiber, and it has the highest flame retardancy among organic fibers. PBO fiber has good softness, and the softness of the woven fabric is similar to that of polyester fiber fabric, which is extremely beneficial for textile weaving processing. The aging performance, heat resistance and combustion resistance of PBO fiber are better than those of aramid fiber, and its impact resistance is much higher than that of aramid fiber and carbon fiber.

[0006] Ceramic materials are widely used in the design of composite armor due to their good dynamic mechanical properties such as high melting point, high hardness, high wear resistance and oxidation resistance. However, ceramic materials also have shortcomings such as poor molding plasticity and low fracture strength, which make ceramics unable to be used alone as a homogeneous bulletproof material. Summary of the invention

[0007] Purpose of the invention: The purpose of the present invention is to provide a composite material for making a bulletproof helmet, so as to solve the problem that the current ceramic material cannot be used alone as a homogeneous bulletproof material.

[0008] Technical solution: A composite material for making bulletproof helmets, with an inner layer of modified PBO fiber cloth, a middle layer of resin-based bulletproof composite material, and an outer layer of graphene-reinforced Al 2 O 3 Ceramic composites; The modified PBO fiber cloth is formed by weaving modified PBO fibers; the modified PBO fibers are prepared by adding 0.5-2wt% dispersed graphene during the polymerization of PBO monomers, and then reacting at a temperature of 200-220° C. to generate a PBO / graphene composite polymer; The resin-based bulletproof composite material is a thermoplastic styrene block copolymer as the matrix of the composite material, which is dissolved in a solvent, and nanographene is added and evenly dispersed. After the fiber is dipped in the resin, the solvent is evaporated to obtain a non-weft sheet; Nanographene is a graphene sheet surface modified by aminopropyltrimethoxysilane compound, and high-speed shearing at 40000~50000rpm in DMSO solution for 90~120min. 2 O 3 The ceramic composite material is composed of 3-6 parts of graphene, 60-80 parts of Al 2 O 3 , 10-20 parts of silicon carbide and 5-10 parts of titanium carbide are uniformly dispersed in a DMSO solution by high-speed shearing, concentrated and evaporated to dryness, and then put into a grinder for 58-65 minutes, and then the ground mixture is prepared by spark plasma sintering.

[0009] Preferably, the thickness of the inner layer is 2-3 mm, the thickness of the middle layer is 1-3 mm, and the thickness of the outer layer is 2-3 mm.

[0010] Preferably, the resin-based bulletproof composite material comprises 80-100 parts of thermoplastic styrene block copolymer, 10-20 parts of nanographene, and 400-500 parts of solvent in parts by weight; the solvent is one of DMSO and DMF or a mixed solvent of the two.

[0011] Preferably, the spark plasma sintering (SPS) temperature is 1400-1500° C., the pressure is 40-50 MPa, and the heating rate is 150-250° C. / min.

[0012] A method for preparing a composite material for making a bulletproof helmet comprises the following steps: S1, applying epoxy resin glue on the inner side of the middle layer resin-based bulletproof composite material to fix the inner layer composed of modified PBO fiber cloth to the middle layer; S2, coating the outer side of the middle layer resin-based bulletproof composite material with epoxy resin glue, 2 O 3 The outer layer and the middle layer composed of ceramic composite materials are fixed.

[0013] Beneficial effects:

[0014] (1) The present invention modifies PBO fibers to weave PBO fiber cloth. The fiber surface modification increases the interfacial shear strength, enhances its UV resistance, and increases the friction coefficient of the fibers in the fabric to improve the ballistic performance of the material.

[0015] (2) The resin-based bulletproof composite material adopts a thermoplastic elastomer composite material, and nano-graphene is added and evenly dispersed to effectively enhance its anti-ballistic performance and energy absorption performance.

[0016] (3) Graphene enhanced Al 2 O 3 Ceramic composite materials can be modified by adding graphene to effectively improve their shortcomings of high brittleness and low toughness. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a performance test comparison diagram of the embodiment and the comparative example. DETAILED DESCRIPTION

[0018] In order to make the technical solution of the present invention clearer, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0019] Example 1

[0020] A composite material for making a bulletproof helmet is obtained by the following preparation method: (1) Preparation of modified PBO fiber cloth: During the polymerization of 1000g of PBO monomer, 12g of dispersed graphene was added, and the polycondensation temperature was 210°C to generate a PBO / graphene composite polymer, which was then woven into cloth after fiber formation; (2) Preparation of resin-based bulletproof composite materials: 150 g of modified graphene was added with 600 g of DMSO and high-speed shearing was performed at 45,000 rpm for 110 min; 3,600 g of DMF was added to 900 g of thermoplastic styrene block copolymer and stirred to dissolve, and high-speed shearing graphene solution was added and stirred evenly. After fiber dipping, the solvent was evaporated to obtain a weft-free sheet; (3) Graphene enhanced Al 2 O 3 Preparation of ceramic composite materials: 45g of graphene, 700g of Al 2 O 3150g of silicon carbide and 75g of titanium carbide were uniformly dispersed in 3000g of DMSO solution by high-speed shearing for 120min, concentrated under reduced pressure and evaporated to dryness, and then ground in a grinder for 60min. The ground mixture was then subjected to spark plasma sintering at a sintering temperature of 1450°C, a pressure of 45Mpa, and a heating rate of 195°C / min. (4) coating the inner side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and fixing it with the modified PBO fiber cloth in step (1); (5) coating the outer side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and the graphene-reinforced Al in step (3) 2 O 3 Ceramic composite fixation.

[0021] Example 2

[0022] A composite material for making a bulletproof helmet is obtained by the following preparation method: (1) Preparation of modified PBO fiber cloth: During the polymerization of 1000g of PBO monomer, 20g of dispersed graphene was added, and the polycondensation temperature was 220°C to generate a PBO / graphene composite polymer, which was then woven into cloth after fiber formation; (2) Preparation of resin-based bulletproof composite materials: 200 g of modified graphene was added with 700 g of DMSO and high-speed shearing was performed at 50,000 rpm for 120 min; 4000 g of DMSO was added to 1000 g of thermoplastic styrene block copolymer and stirred to dissolve, and high-speed shearing graphene solution was added and stirred evenly. After fiber dipping, the solvent was evaporated to obtain a non-woven sheet; (3) Graphene enhanced Al 2 O 3 Preparation of ceramic composite materials: 60g of graphene, 800g of Al 2 O 3 200g of silicon carbide and 100g of titanium carbide were uniformly dispersed in 4000g of DMSO solution by high-speed shearing for 120min, concentrated and evaporated under reduced pressure, and then ground in a grinder for 65min. The ground mixture was then subjected to spark plasma sintering at a sintering temperature of 1500°C, a pressure of 50Mpa, and a heating rate of 250°C / min. (4) coating the inner side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and fixing it with the modified PBO fiber cloth in step (1); (5) coating the outer side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and the graphene-reinforced Al in step (3) 2 O 3 Ceramic composite fixation.

[0023] Example 3

[0024] A composite material for making a bulletproof helmet is obtained by the following preparation method: (1) Preparation of modified PBO fiber cloth: During the polymerization of 1000g of PBO monomer, 12g of dispersed graphene was added, and the polycondensation temperature was 210°C to generate a PBO / graphene composite polymer, which was then woven into cloth after fiber formation; (2) Preparation of resin-based bulletproof composite materials: 50 g of modified graphene was added with 600 g of DMSO and high-speed shearing was performed at 40,000 rpm for 90 min; 3200 g of DMF was added to 800 g of thermoplastic styrene block copolymer and stirred to dissolve, and high-speed shearing graphene solution was added and stirred evenly. After fiber dipping, the solvent was evaporated to obtain a non-woven sheet; (3) Graphene enhanced Al 2 O 3 Preparation of ceramic composite materials: 30g of graphene, 800g of Al 2 O 3 200g of silicon carbide and 100g of titanium carbide were uniformly dispersed in 3000g of DMSO solution by high-speed shearing for 120min, concentrated under reduced pressure and evaporated to dryness, and then put into a grinder for 58-65min, and then the ground mixture was subjected to spark plasma sintering at a sintering temperature of 1400°C, a pressure of 40Mpa, and a heating rate of 150°C / min; (4) coating the inner side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and fixing it with the modified PBO fiber cloth in step (1); (5) coating the outer side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and the graphene-reinforced Al in step (3) 2 O 3 Ceramic composite fixation.

[0025] Comparative Example 1

[0026] A composite material for making a bulletproof helmet is obtained by the following preparation method: (1) Preparation of resin-based bulletproof composite materials: 150 g of modified graphene was added with 600 g of DMSO and high-speed shearing was performed at 45,000 rpm for 110 min; 3,600 g of DMF was added to 900 g of thermoplastic styrene block copolymer and stirred to dissolve, and high-speed shearing graphene solution was added and stirred evenly. After fiber dipping, the solvent was evaporated to obtain a weft-free sheet; (2) Graphene enhanced Al 2 O 3 Preparation of ceramic composite materials: 45g of graphene, 700g of Al 2 O 3150g of silicon carbide and 75g of titanium carbide were uniformly dispersed in 3000g of DMSO solution by high-speed shearing for 120min, concentrated under reduced pressure and evaporated to dryness, and then ground in a grinder for 60min. The ground mixture was then subjected to spark plasma sintering at a sintering temperature of 1450°C, a pressure of 45Mpa, and a heating rate of 195°C / min. (3) coating the inner side of the resin-based bullet-proof composite material in step (1) with epoxy resin glue and fixing it with PBO fiber cloth; (4) coating the outer side of the resin-based bulletproof composite material in step (1) with epoxy resin glue and the graphene-reinforced Al in step (2) 2 O 3 Ceramic composite fixation.

[0027] Comparative Example 2

[0028] A composite material for making a bulletproof helmet is obtained by the following preparation method: (1) Preparation of modified PBO fiber cloth: During the polymerization of 1000g of PBO monomer, 12g of dispersed graphene was added, and the polycondensation temperature was 210°C to generate a PBO / graphene composite polymer, which was then woven into cloth after fiber formation; (2) Preparation of resin-based bulletproof composite materials: 3600 g of DMF was added to 900 g of thermoplastic styrene block copolymer and stirred to dissolve, and the fibers were impregnated with the resin, and the solvent was evaporated to obtain a non-woven sheet; (3) Graphene enhanced Al 2 O 3 Preparation of ceramic composite materials: 45g of graphene, 700g of Al 2 O 3 150g of silicon carbide and 75g of titanium carbide were uniformly dispersed in 3000g of DMSO solution by high-speed shearing for 120min, concentrated under reduced pressure and evaporated to dryness, and then ground in a grinder for 60min. The ground mixture was then subjected to spark plasma sintering at a sintering temperature of 1450°C, a pressure of 45Mpa, and a heating rate of 195°C / min. (4) coating the inner side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and fixing it with the modified PBO fiber cloth in step (1); (5) coating the outer side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and the graphene-reinforced Al in step (3) 2 O 3 Ceramic composite fixation.

[0029] Comparative Example 3

[0030] A composite material for making a bulletproof helmet is obtained by the following preparation method: (1) Preparation of modified PBO fiber cloth: During the polymerization of 1000g of PBO monomer, 12g of dispersed graphene was added, and the polycondensation temperature was 210°C to generate a PBO / graphene composite polymer, which was then woven into cloth after fiber formation; (2) Preparation of resin-based bulletproof composite materials: 150 g of modified graphene was added with 600 g of DMSO and high-speed shearing was performed at 45,000 rpm for 110 min; 3,600 g of DMF was added to 900 g of thermoplastic styrene block copolymer and stirred to dissolve, and high-speed shearing graphene solution was added and stirred evenly. After fiber dipping, the solvent was evaporated to obtain a weft-free sheet; (3) coating the inner side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and fixing it with the modified PBO fiber cloth in step (1); (4) Coat the outer side of the resin-based bulletproof composite material in step (2) with epoxy resin glue and Al 2 O 3 Ceramic composite fixation.

[0031] Comparative Example 4

[0032] (1) Ballistic Helmet Test Standards GA 293-2012 and GJB5115A-2012; (2) Limit ballistic velocity V50: refers to the bullet's velocity when the probability of the helmet being penetrated is 50%; (3) Back Face Depth (BFS): refers to the maximum deformation depth of the back surface padding of the bulletproof material when the bullet effectively hits but does not penetrate.

[0033] The performance test comparison results of the above embodiments and comparative examples are as follows: Figure 1 As shown. The results show that the composite material for making a bulletproof helmet provided by the present invention has excellent performance in ultimate ballistic velocity V50 and back concave depth (BFS). It can be seen from Examples 1 to 3 and Comparative Examples 1 to 3 that the modified PBO fiber cloth, the resin-based bulletproof composite material, and the graphene-reinforced Al 2 O 3 Ceramic composite materials can effectively improve ballistic performance.

[0034] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A composite material for making a bulletproof helmet, characterized in that: The inner layer is a modified PBO fiber cloth, the middle layer is a resin-based bulletproof composite material, and the outer layer is a graphene-reinforced Al2O3 ceramic composite material; The modified PBO fiber cloth is formed by weaving modified PBO fibers; the modified PBO fibers are prepared by adding 0.5-2 wt% of dispersed graphene during the polymerization of PBO monomers, and then undergoing polycondensation reaction at a reaction temperature of 200-220° C. to generate a PBO / graphene composite polymer; The resin-based bulletproof composite material is a thermoplastic styrene block copolymer as a matrix of the composite material, which is dissolved in a solvent, and nanographene is added and evenly dispersed, and the fiber is dipped in the resin, and the solvent is volatilized to obtain a non-weft sheet; wherein the nanographene is an aminopropyltrimethoxysilane compound to modify the surface of the graphene sheet, and the high-speed shearing is performed at 40000-50000 rpm in a DMSO solution for 90-120 minutes; The graphene-enhanced Al2O3 ceramic composite material is prepared by uniformly dispersing 3-6 parts of graphene, 60-80 parts of Al2O3, 10-20 parts of silicon carbide and 5-10 parts of titanium carbide in a DMSO solution by high-speed shearing, concentrating and evaporating to dryness, grinding the mixture in a grinder for 58-65 minutes, and then subjecting the ground mixture to spark plasma sintering to obtain the composite material.

2. The composite material for making a bulletproof helmet according to claim 1, characterized in that: The thickness of the inner layer is 2~3mm, the thickness of the middle layer is 1~3mm, and the thickness of the outer layer is 2~3mm.

3. The composite material for making a bulletproof helmet according to claim 1, characterized in that: The resin-based bulletproof composite material comprises 80-100 parts of thermoplastic styrene block copolymer, 10-20 parts of nanographene and 400-500 parts of solvent in parts by weight.

4. The composite material for making a bulletproof helmet according to claim 3, characterized in that: The solvent is DMSO, DMF or a mixture of the two.

5. The composite material for making a bulletproof helmet according to claim 1, characterized in that: The spark plasma sintering temperature is 1400~1500℃, the pressure is 40~50Mpa, and the heating rate is 150~250℃ / min.

6. A method for preparing a composite material for making a bulletproof helmet according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, applying epoxy resin glue on the inner side of the middle layer resin-based bulletproof composite material to fix the inner layer composed of modified PBO fiber cloth to the middle layer; S2. Apply epoxy resin glue on the outside of the middle layer of resin-based bulletproof composite material to fix the outer layer composed of graphene-reinforced Al2O3 ceramic composite material to the middle layer.

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