Heavy bulletproof material with low density and high energy absorption capacity and preparation method thereof

Abstract

The invention belongs to the field of bulletproof material preparation, and particularly relates to a heavy bulletproof material with low density and high energy absorption capacity and a preparation method thereof. The preparation method of the heavy bulletproof material comprises the following preparation steps: carrying out sizing, weaving, desizing and heat treatment on ultra-high molecular weight polyethylene fiber bundles, and then carrying out gum dipping treatment to obtain the heavy bulletproof material, a sizing agent used for sizing is a polyurethane sizing agent; a glue solution used for glue dipping is prepared from the following raw materials in parts by mass: 50 to 60 parts of polyurethane resin, 50 to 60 parts of NMP, 10 to 15 parts of a curing agent, 10 to 18 parts of light filler, 10 to 20 parts of a toughening agent, 10 to 20 parts of composite ceramic particles, 1 to 3 parts of a dispersing agent, 2 to 6 parts of a coupling agent and 1 to 3 parts of carbon fiber powder. The researched and developed composite ceramic particles are applied to the bulletproof material, and the bulletproof material with excellent bulletproof performance is obtained through raw material selection and formula optimization.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of bulletproof materials, and particularly relates to a heavy bulletproof material with low density and high energy absorption capacity and a preparation method thereof. Background Art

[0002] Although traditional metal bulletproof materials such as high-strength alloy steel and titanium alloy have relatively high strength and can withstand the impact of bullets, their densities are generally high. For example, the density of high-strength alloy steel is generally about 7.8 - 8.0 g / cm 3 or so, and the density of titanium alloy is also about 4.5 g / cm 3 or so. This makes bulletproof equipment made of metal materials often heavy. For personnel who need to wear or carry bulletproof equipment for a long time (such as soldiers, security personnel, etc.), it will greatly reduce their mobility and comfort. Long-term load-bearing may even affect combat or work efficiency and physical health. Common ceramic bulletproof materials such as alumina ceramics and silicon carbide ceramics have the characteristic of high hardness and can effectively consume the energy of bullets through the fragmentation mechanism. However, ceramic materials themselves also have some limitations. On the one hand, the density of ceramics is also relatively high. For example, the density of alumina ceramics is about 3.9 - 4.0 g / cm 3 or so, and the density of silicon carbide ceramics is about 3.2 g / cm 3 or so, which makes bulletproof products made of ceramic materials not light. On the other hand, although ceramic materials can break and consume energy after being hit by bullets, the broken ceramic fragments may cause secondary injuries to the human body, and the toughness of ceramic materials is poor. When used alone, their overall bulletproof performance may not be ideal in the face of some complex situations (such as multiple impacts, impacts at different angles, etc.).

[0003] Patent CN 116968217 A discloses a preparation method of a polyarylate fiber prepreg and a bulletproof helmet, which includes steps: S1, drying; S2, melt spinning; S3, storage; S4, bundling; S5, hot drawing; S6, sizing treatment; S7, weaving; S8, desizing treatment; S9, heat treatment; S10, making prepreg. By adding a toughening agent during melt spinning and performing sizing treatment on the polyarylate fiber bundle, the present invention improves the wear resistance, bundling property and weaving performance of the polyarylate fiber bundle, and enhances the mechanical properties of the polyarylate fiber fabric; pressing the polyarylate fiber prepreg to obtain a polyarylate fiber bulletproof helmet with high protective performance. However, the bulletproof performance of the polyarylate fiber bulletproof helmet is not disclosed in this invention, and its bulletproof performance cannot be judged.

[0004] Therefore, researching and developing ceramic particles with excellent performance and applying them to bulletproof materials is beneficial to the development of the bulletproof material field. Summary of the Invention

[0005] The present invention discloses a heavy-duty bulletproof material with low density and high energy absorption capacity and a preparation method thereof. By developing a composite ceramic particle and applying it to the bulletproof material, through the selection of raw materials and the optimization of the formula, a bulletproof material with excellent bulletproof performance is obtained.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] The first aspect of the present invention provides a preparation method of a heavy-duty bulletproof material with low density and high energy absorption capacity, including the following preparation steps:

[0008] Perform sizing, weaving, desizing, and heat treatment on the ultra-high molecular weight polyethylene fiber bundle, and then perform impregnation treatment to obtain the heavy-duty bulletproof material;

[0009] The sizing agent used for sizing is a polyurethane-based sizing agent;

[0010] The sizing solution used for impregnation includes the following raw materials by mass fraction: 60-80 parts of polyurethane resin, 50-60 parts of NMP, 5-30 parts of curing agent, 12-28 parts of light filler, 10-20 parts of toughening agent, 5-16 parts of composite ceramic particles, 1-3 parts of dispersant, 2-6 parts of coupling agent, and 1-3 parts of carbon fiber powder.

[0011] In some embodiments, the preparation steps of the sizing solution are as follows:

[0012] After dissolving the polyurethane resin in NMP, add the curing agent, toughening agent, dispersant, and coupling agent thereto, mix evenly, and then add the light filler, composite ceramic particles, and carbon fiber powder one by one, and disperse each added raw material evenly at high speed to finally obtain the sizing solution.

[0013] In some embodiments, the number average molecular weight of the polyurethane resin is 20,000-50,000.

[0014] In some embodiments, the preparation steps of the composite ceramic particles are as follows:

[0015] (1) Mix the reinforcing aid, albite, titanium dioxide powder, and graphene evenly and perform ball milling to obtain a mixture;

[0016] (2) Mix the mixture in step (1) with deionized water, add a dispersant, perform heat treatment, cool down, then add polyethylene glycol, fatty acid, and laurylamide, freeze, and naturally return to room temperature to obtain a mixed slurry;

[0017] (3) Granulate, prepare a green body, and sinter the mixed slurry in step (2) to obtain the composite ceramic particles.

[0018] In some embodiments, the preparation steps of the reinforcing aid are as follows:

[0019] S1: Take a quaternary ammonium salt cationic surfactant and dopamine hydrochloride and completely dissolve them in a buffer solution. Adjust its pH to 8.5 - 10.5. Add silicon carbide thereto, stir evenly, stir at 75 - 85 °C for 6 - 10 h. After the reaction is completed, cool to room temperature, separate, wash the obtained solid until neutral, then dry and grind to obtain solid 1;

[0020] S2: Disperse solid 1 obtained in step S1 in deionized water, adjust the pH value, add an anionic surfactant under stirring conditions, stir evenly, heat and stir for 3 - 4 h, then separate, wash, dry and grind to obtain the reinforcing aid.

[0021] In some embodiments, the mass ratio of dopamine hydrochloride to silicon carbide in step S1 is 1:(20 - 30).

[0022] Preferably, the mass ratio of dopamine hydrochloride to silicon carbide in step S1 is 1:26.

[0023] In some embodiments, the quaternary ammonium salt cationic surfactant in step S1 is an alkyl quaternary ammonium salt surfactant; the dosage of the quaternary ammonium salt cationic surfactant is 10 - 20 wt% of dopamine hydrochloride.

[0024] Preferably, the dosage of the quaternary ammonium salt cationic surfactant is 15 wt% of dopamine hydrochloride.

[0025] In some embodiments, the anionic surfactant in step S2 is selected from alkyl sulfate surfactants, and the dosage of the anionic surfactant is 1 - 1.5 wt% of solid 1.

[0026] Preferably, the dosage of the anionic surfactant is 1.2 wt% of solid 1.

[0027] In some embodiments, the mass ratio of the reinforcing aid, albite, titanium dioxide powder and graphene in step (1) is (85 - 90):(10 - 15):(1.5 - 2.5):1.

[0028] Preferably, the mass ratio of the reinforcing aid, albite, titanium dioxide powder and graphene in step (1) is 88:12:2:1.

[0029] In some embodiments, the mass ratio of the mixture, fatty acid and laurylamide in step (2) is (40 - 50):(1 - 1.5):1.

[0030] Preferably, in the step (2), the mass ratio of the mixture, fatty acid and laurylamide is 45:1.3:1.

[0031] In some embodiments, the light filler is at least one of aerogel and hollow glass microspheres.

[0032] In some embodiments, the dispersant is at least one of BYK-9076, HY-9070, and polyethylene glycol dispersants.

[0033] In some embodiments, the diameter of the carbon fiber powder is 1-50 μm.

[0034] Preferably, the diameter of the carbon fiber powder is 1-20 μm.

[0035] The second aspect of the present invention provides a heavy bulletproof material prepared by the preparation method of the heavy bulletproof material described in the above scheme.

[0036] The present invention develops a composite ceramic particle and applies it to bulletproof materials. Through the selection of raw materials and the optimization of the formula, a bulletproof material with excellent bulletproof performance is obtained.

[0037] The applicant found that applying special reinforcing aids to ceramic particles can improve the comprehensive performance of ceramic particles. In the present invention, through process control, polydopamine coating is formed on the surface of silicon carbide by hydrochloric acid dopamine. Polydopamine has abundant active groups, such as hydroxyl groups, amino groups, etc., which can interact with the surface of ceramic particles, enhance the interfacial bonding force between the reinforcing aids and the ceramic particle raw materials, contribute to the effective transmission of stress, and when subjected to external forces, can better disperse stress and improve the mechanical properties of ceramic particles; in addition, the present invention also selects quaternary ammonium salt cationic surfactants as an auxiliary. On the one hand, it can interact with the surface of ceramic particle raw materials through electrostatic interaction, hydrophobic interaction, etc., further enhancing the binding with ceramic particles. On the other hand, quaternary ammonium salt cationic surfactants may also modify the surface of ceramic particles to a certain extent during the reaction process, improve the surface properties of ceramic particles, and enhance the compatibility with reinforcing aids and other components; finally, the present invention also adds anionic surfactants in the second step of the reaction. It can interact with the positively charged complex to form a structure similar to a "double electric layer", which can improve its dispersibility in the ceramic raw material system, avoid particle agglomeration, make the performance of the material more stable and consistent, and improve the overall performance of the ceramic material. The structure of the prepared reinforcing aids can improve the microstructure of ceramic particles, increase the density of ceramic materials, reduce internal defects, thereby improving the properties such as strength, hardness, and wear resistance of ceramic particles; and each component in the reinforcing aids can, through synergistic effects, enable ceramic particles to better absorb and disperse energy when subjected to external impact or energy input, improving the impact resistance and anti-destruction ability of ceramic particles.

[0038] The present invention tightly combines the above-mentioned reinforcing aids with albite, titanium dioxide powder, graphene, etc., promotes stress transfer, and improves the mechanical properties of composite ceramic particles. Albite provides basic skeletal support for the composite ceramic particles. After sintering, the crystal structure may form a relatively dense arrangement, increasing the density of the composite ceramic particles and thus improving the hardness. Titanium dioxide powder can, on the one hand, increase the whiteness and gloss of the particles and improve their appearance properties. On the other hand, titanium dioxide also interacts with other raw materials during the high-temperature sintering process, affecting the microstructure and properties of the ceramic particles. The high strength and high modulus of graphene can enhance the overall strength of the composite ceramic particles. It can form a structure similar to "reinforcing ribs" inside the ceramic particles. When subjected to external forces, it can effectively share the stress and improve the anti-deformation ability of the particles. At the same time, the high thermal conductivity of graphene also helps the rapid transfer of heat inside the composite ceramic particles, improving the thermal performance. After cooling, a certain amount of polyethylene glycol, fatty acid, and laurylamide are added, which may form a special coating on the surface of the above components or introduce some special structures, affecting the wettability and surface energy of the composite ceramic particles, improving their compatibility with other materials, and improving their performance in specific environments. Finally, the obtained mixed slurry is granulated, the green body is prepared, and sintered to obtain composite ceramic particles with excellent performance. These composite ceramic particles are used together with polyurethane resin, curing agent, light filler, toughening agent, dispersant, coupling agent, and carbon fiber powder, and the formulation dosage is optimized. The obtained glue solution is impregnated to make it distributed on the surface of polyethylene fibers, and the obtained bulletproof material has excellent bulletproof performance.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] 1. The present invention has developed a kind of composite ceramic particles and applied them to bulletproof materials. Through the selection of raw materials and the optimization of the formulation, a bulletproof material with excellent bulletproof performance is obtained.

[0041] 2. The present invention prepares and synthesizes a reinforcing aid and applies the reinforcing aid to composite ceramic particles. The reinforcing aid is tightly combined with albite, titanium dioxide powder, graphene, etc., promotes the stress transfer of the ceramic particles, and strictly controls the preparation process to improve the mechanical properties of the composite ceramic particles. Specific embodiments

[0042] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and implementation schemes of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0043] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. Without departing from the scope or spirit of the present invention, various improvements and variations can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of this application are merely exemplary.

[0044] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0045] It should be noted that the post-treatment steps such as "extraction", "vacuum distillation", "stirring", etc. that appear in the following examples are conventional operations of those skilled in the art and can be selected according to actual operations.

[0046] The ultra-high molecular weight polyethylene fiber bundles used in the present invention are purchased from Asahi Kasei, with the model UH901; the number average molecular weight of the polyurethane resin used is 40000; the particle size of the titanium dioxide powder used is 1 μm; the particle size of the graphene used is 100 nm; the number average molecular weight of the polyethylene glycol used is 2000; the polyurethane sizing agent used is purchased from HYCOMMA, with the model R025; the particle size of the hollow glass microspheres used is 50 μm; the number average molecular weight of the polyimide used is 20000; the diameter of the carbon fiber powder used is 20 μm.

[0047] Preparation Example 1

[0048] The preparation steps of the reinforcing additive are as follows:

[0049] S1: Dissolve 0.15 g of cetyltrimethylammonium chloride and 1 g of dopamine hydrochloride completely in 50 mL of Tris buffer solution, adjust its pH to 9.5, add 26 g of silicon carbide thereto, stir evenly, stir at 80 °C for 8 h, after the reaction is completed, cool to room temperature, carry out centrifugal separation, wash the obtained solid with deionized water until it is neutral, then dry it to constant weight at 60 °C and grind it through a 100-mesh sieve to obtain Solid 1;

[0050] S2: Disperse 25 g of Solid 1 obtained in Step S1 in 50 mL of deionized water, adjust the pH value, under stirring conditions, add 0.5 g of sodium dodecyl sulfate, stir evenly, heat and stir at 70 °C for 3.5 h, then carry out centrifugal separation, wash with deionized water until it is neutral, dry it to constant weight at 60 °C and grind it through a 100-mesh sieve to obtain the reinforcing additive.

[0051] Preparation Example 2

[0052] The preparation steps of the reinforcing additive are the same as those in Preparation Example 1, the difference being that 0.3 g of cetyltrimethylammonium chloride is used.

[0053] Preparation Example 3

[0054] The preparation steps of the reinforcing additive are the same as those in Preparation Example 1, the difference being that 0.5 g of sodium dodecyl sulfate is used.

[0055] Preparation Example 4

[0056] The preparation steps of the reinforcing additive are as follows:

[0057] Take 0.15 g of cetyltrimethylammonium chloride and 1 g of dopamine hydrochloride and dissolve them completely in 50 mL of Tris buffer solution, adjust its pH to 9.5, add 26 g of silicon carbide thereto, stir evenly, stir at 80 °C for 8 h, after the reaction is completed, cool to room temperature, carry out centrifugal separation, wash the obtained solid with deionized water until it is neutral, then dry it to constant weight at 60 °C and grind it through a 100-mesh sieve to obtain the reinforcing additive.

[0058] Preparation Example 5

[0059] The preparation steps of the reinforcing additive are the same as those in Preparation Example 1, the difference being that dopamine hydrochloride is not added during the preparation process.

[0060] Preparation Example 6

[0061] The preparation steps of the composite ceramic particles are as follows:

[0062] (1) Mix 88 g of the reinforcing additive, 12 g of albite, 2 g of titanium dioxide powder and 1 g of graphene evenly, carry out ball milling (the ball-to-material ratio is 7:1, the rotation speed is 700 rpm, the ball milling time is 4 h, and the ball milling temperature is 70 °C) to obtain a mixture;

[0063] (2) Mix 45 g of the mixture from step (1) with 100 mL of deionized water, add 0.5 g of carboxymethyl cellulose, heat at 70 °C for 2 h, then cool to 45 °C, and then add 0.5 g of polyethylene glycol, 1.3 g of stearic acid and 1 g of lauroylamide, freeze at 0 °C for 2 h, and naturally return to room temperature to obtain a mixed slurry;

[0064] (3) Spray-dry and granulate the mixed slurry from step (2) (the inlet temperature of spray drying is 210 °C, the outlet temperature is 100 °C, and the temperature of the granulator is 140 °C), prepare a green body (inject and mold the obtained granulate at 135 °C and 50 MPa, cool, degrease in a vacuum furnace, control the vacuum degree to be 100 Pa, the degreasing time is 3 h, and the degreasing temperature is 350 °C), sinter (first pre-sinter the obtained green body in a nitrogen atmosphere, the sintering temperature is 1000 °C, the sintering time is 2 h, then reduce the temperature to 10 °C at a rate of 5 °C / min; then perform secondary sintering in a nitrogen atmosphere again, the sintering temperature is 800 °C, the sintering time is 2 h, then increase the temperature to 1650 °C at a rate of 5 °C / min, sinter for 1.5 h, then reduce the temperature to 850 °C at a rate of 5 °C / min, sinter for 1.5 h, and naturally cool to room temperature) to obtain composite ceramic particles.

[0065] The reinforcing auxiliary agent used is obtained from Preparation Example 1.

[0066] Preparation Example 7

[0067] The preparation steps of the composite ceramic particles are the same as those of Preparation Example 6, except that the reinforcing auxiliary agent used is obtained from Preparation Example 2.

[0068] Preparation Example 8

[0069] The preparation steps of the composite ceramic particles are the same as those of Preparation Example 6, except that the reinforcing auxiliary agent used is obtained from Preparation Example 3.

[0070] Preparation Example 9

[0071] The preparation steps of the composite ceramic particles are the same as those of Preparation Example 6, except that the reinforcing auxiliary agent used is obtained from Preparation Example 4.

[0072] Preparation Example 10

[0073] The preparation steps of the composite ceramic particles are the same as those of Preparation Example 6, except that the reinforcing auxiliary agent used is obtained from Preparation Example 5.

[0074] Preparation Example 11

[0075] The preparation steps of the composite ceramic particles are as follows:

[0076] (1) Mix 88 g of reinforcing agent, 12 g of albite, 2 g of titanium dioxide powder, and 1 g of graphene evenly, and perform ball milling (the ball-to-material ratio is 7:1, the rotation speed is 700 rpm, the ball milling time is 4 h, and the ball milling temperature is 70 °C) to obtain a mixture;

[0077] (2) Mix 45 g of the mixture from step (1) with 100 mL of deionized water, add 0.5 g of carboxymethyl cellulose, heat at 70 °C for 2 h, and then cool to 45 °C to obtain a mixed slurry;

[0078] (3) Spray dry and granulate the mixed slurry from step (2) (the inlet temperature of spray drying is 210 °C, the outlet temperature is 100 °C, and the temperature of the granulator is 140 °C), prepare a green body (inject mold the obtained granulate at 135 °C and 50 MPa, cool, degrease in a vacuum furnace, control the vacuum degree to be 100 Pa, the degreasing time is 3 h, and the degreasing temperature is 350 °C), and sinter (first pre-sinter the obtained green body in a nitrogen atmosphere, the sintering temperature is 1000 °C, the sintering time is 2 h, then lower the temperature to 1℃ at a rate of 5 °C / min; then perform secondary sintering in a nitrogen atmosphere again, the sintering temperature is 800 °C, the sintering time is 2 h, then raise the temperature to 1650 °C at a rate of 5 °C / min, sinter for 1.5 h, then lower the temperature to 850 °C at a rate of 5 °C / min, sinter for 1.5 h, and naturally cool to room temperature) to obtain composite ceramic particles.

[0079] The reinforcing agent used is obtained from Preparation Example 1.

[0080] Preparation Example 12

[0081] The preparation steps of the composite ceramic particles are the same as those of Preparation Example 6, except that graphene is not added.

[0082] Preparation Example 13

[0083] The preparation steps of the composite ceramic particles are the same as those of Preparation Example 6, except that the amount of the reinforcing agent used is 80 g.

[0084] Example 1

[0085] A preparation method of a heavy-duty bulletproof material with low density and high energy absorption capacity, comprising the following preparation steps:

[0086] The ultra-high molecular weight polyethylene fiber bundles are sized by dipping them through guide rollers and pressure sizing rollers into a polyurethane sizing agent (containing 1.5 wt% KH550), and then the ultra-high molecular weight polyethylene fiber bundles are introduced from another guide roller into a drying roller, and are wound after drying at 100 °C; a spinning machine is used to weave the sized ultra-high molecular weight polyethylene fiber bundles into a fabric, and the warp and weft densities of the fabric are both 80 threads / 10 cm; the obtained fabric is padded into a 10 wt% NaOH aqueous solution and steamed at 75 °C for 15 min, and washed three times with water; then, it is heat-treated for 2 h under a nitrogen gas flow at 100 °C; and then it is immersed in a sizing solution and treated at 60 °C for 30 min, separated, and cured at 80 °C for 3 h to obtain the heavy-duty bulletproof material.

[0087] The sizing solution used for sizing comprises the following raw materials by mass fraction: 60 parts of polyurethane resin, 60 parts of NMP, 15 parts of 4,4-diaminodiphenylmethane, 10 parts of hollow glass microspheres, 10 parts of polyimide, 20 parts of composite ceramic particles, 1 part of BYK-9076, 2 parts of KH560, and 1 part of carbon fiber powder; the preparation steps of the sizing solution are the same as those in Example 1.

[0088] The composite ceramic particles used are obtained from Preparation Example 6.

[0089] Example 2

[0090] A preparation method of a heavy-duty bulletproof material with low density and high energy absorption capacity comprises the following preparation steps:

[0091] The ultra-high molecular weight polyethylene fiber bundles are sized by dipping them through guide rollers and pressure sizing rollers into a polyurethane sizing agent (containing 1 wt% KH550), and then the ultra-high molecular weight polyethylene fiber bundles are introduced from another guide roller into a drying roller, and are wound after drying at 100 °C; a spinning machine is used to weave the sized ultra-high molecular weight polyethylene fiber bundles into a fabric, and the warp and weft densities of the fabric are both 90 threads / 10 cm; the obtained fabric is padded into a 10 wt% NaOH aqueous solution and steamed at 70 °C for 15 min, and washed three times with water; then, it is heat-treated for 1.5 h under a nitrogen gas flow at 120 °C; and then it is immersed in a sizing solution and treated at 70 °C for 15 min, separated, and cured at 85 °C for 2.5 h to obtain the heavy-duty bulletproof material.

[0092] The sizing solution used for sizing comprises the following raw materials by mass fraction: 50 parts of polyurethane resin, 50 parts of NMP, 30 parts of 10,4-diaminodiphenylmethane, 18 parts of hollow glass microspheres, 20 parts of polyimide, 10 parts of composite ceramic particles, 3 parts of BYK-9076, 6 parts of KH560, and 3 parts of carbon fiber powder; the preparation steps of the sizing solution are the same as those in Example 1.

[0093] The composite ceramic particles used are obtained from Preparation Example 6.

[0094] Example 3

[0095] A preparation method of a heavy-duty bulletproof material with low density and high energy absorption capacity, comprising the following preparation steps:

[0096] Immerse the ultra-high molecular weight polyethylene fiber bundle in polyurethane sizing agent (containing 2wt% KH550) through guide rollers and pressure sizing rollers, introduce the ultra-high molecular weight polyethylene fiber bundle from another guide roller into the drying roller, wind the fiber after drying at 100 °C; use a spinning machine to weave the sized ultra-high molecular weight polyethylene fiber bundle into a fabric with a warp and weft density of 85 threads / 10 cm; immerse the obtained fabric in 10wt% NaOH aqueous solution and steam at 65 °C for 20 min, wash it three times with water; then heat-treat it in a nitrogen gas stream at 110 °C for 2 h; then immerse it in the sizing solution and treat it at 65 °C for 20 min, separate and cure it at 90 °C for 2 h to obtain the heavy-duty bulletproof material.

[0097] The sizing solution used for sizing, calculated by mass fraction, comprises the following raw materials: 55 parts of polyurethane resin, 55 parts of NMP, 12 parts of 4,4-diaminodiphenylmethane, 15 parts of hollow glass microspheres, 15 parts of polyimide, 15 parts of composite ceramic particles, 2 parts of BYK-9076, 4 parts of KH560 and 2 parts of carbon fiber powder; the preparation steps of the sizing solution are the same as those in Example 1.

[0098] The composite ceramic particles used are obtained from Preparation Example 6.

[0099] Comparative Example 1

[0100] A preparation method of a heavy-duty bulletproof material with low density and high energy absorption capacity, the specific implementation manner is the same as that in Example 3, except that an aqueous epoxy resin is used instead of the polyurethane sizing agent.

[0101] Comparative Example 2

[0102] A preparation method of a heavy-duty bulletproof material with low density and high energy absorption capacity, the specific implementation manner is the same as that in Example 3, except that composite ceramic particles are not added to the sizing solution.

[0103] Performance Test

[0104] 1. Conduct the following performance tests on the composite ceramic particles obtained from Preparation Examples 6-13:

[0105] 1.1 Detect the density and relative density of the composite ceramic particles according to the test standard of GB / T 25995-2010.

[0106] 1.2 Detect the hardness, flexural strength and fracture toughness of the composite ceramic particles according to the test standards of GB / T 16534-2009, GB / T 6569-2006 and GB / T 23806-2009 respectively.

[0107] 1.3. Oxidize the composite ceramic particles of each preparation example at 1350 °C for 7 days, and then detect their hardness, flexural strength and fracture toughness according to the test standards of GB / T 16534-2009, GB / T 6569-2006, and GB / T 23806-2009 respectively.

[0108] The specific test results are shown in Table 1.

[0109] Table 1

[0110]

[0111] As can be seen from Table 1, the composite ceramic particles obtained in Preparation Example 6 have excellent comprehensive properties, good density and mechanical properties, and are oxidation-resistant. Compared with Preparation Example 6, the preparation of the reinforcing additives used in Preparation Examples 7-10 has changed, affecting the internal structure of the ceramic particles, resulting in varying degrees of reduction in the properties of the obtained composite ceramic particles; in Preparation Examples 11-13, the composition or dosage of the raw materials has been changed, which will also change the internal structure of the ceramic particles, thereby affecting their mechanical properties.

[0112] Therefore, the composite ceramic particles of Preparation Example 6 are selected in the present invention for use in the examples.

[0113] 2. Bulletproof performance

[0114] Make the heavy bulletproof materials obtained in each example into materials with a thickness of 50 mm and apply them to the bullet-facing surface of the bulletproof plate for live firing target testing. The bullet model is the 53rd type 7.62 mm armor-piercing incendiary bullet, and the firing distance is 15 meters for each test. Each test is repeated three times and the average value is taken. The specific test data are shown in Table 2.

[0115] Table 2

[0116] Number Impact velocity m / s Indentation mm Example 1 875 10.5 Example 2 874 10.3 Example 3 877 9.9 Comparative Example 1 876 22.8 Comparative Example 2 877 39.5

[0117] As can be seen from Table 2, the heavy bulletproof materials prepared in Examples 1-3 have good bulletproof performance. However, compared with Example 3, in Comparative Example 1, water-based epoxy resin is used instead of polyurethane sizing agent, and the adhesion of water-based epoxy resin to the adhesive solution of the present invention is weaker than that of polyurethane sizing agent; in Comparative Example 2, the adhesive solution used does not contain composite ceramic particles, which affects the performance of the bulletproof layer after curing and significantly reduces the bulletproof performance of the heavy bulletproof material.

[0118] As described above, it is only the preferred embodiment of the present invention and does not impose any form of limitation on this application. Although this application is disclosed as the preferred embodiment above, it is not intended to limit this application. Any person skilled in the art, without departing from the technical solution of this application, making some changes or modifications using the disclosed technical content is equivalent to equivalent implementation cases. However, as long as it does not depart from the technical solution content of the present invention, any simple modification, equivalent change, and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution.

Claims

1. A preparation method of a heavy-duty bulletproof material with low density and high energy absorption capacity, characterized in that, It includes the following preparation steps: Perform sizing, weaving, desizing, and heat treatment on the ultra-high molecular weight polyethylene fiber bundle, and then perform impregnation treatment to obtain a heavy-duty bulletproof material; The sizing agent used for sizing is a polyurethane-based sizing agent; The sizing solution used for impregnation includes the following raw materials by mass fraction: 50-60 parts of polyurethane resin, 50-60 parts of NMP, 10-15 parts of curing agent, 10-18 parts of light filler, 10-20 parts of toughening agent, 10-20 parts of composite ceramic particles, 1-3 parts of dispersant, 2-6 parts of coupling agent, and 1-3 parts of carbon fiber powder.

2. The preparation method of the heavy-duty bulletproof material according to claim 1, characterized in that The number average molecular weight of the polyurethane resin is 20,000-50,000.

3. The preparation method of the heavy-duty bulletproof material according to claim 1, characterized in that, The preparation steps of the composite ceramic particles are as follows: (1) Mix the reinforcing assistant, albite, titanium dioxide powder, and graphene evenly, and perform ball milling to obtain a mixture; (2) Mix the mixture in step (1) with deionized water, add a dispersant, after heat treatment, cool down, then add polyethylene glycol, fatty acid, and laurylamide, freeze, and naturally return to room temperature to obtain a mixed slurry; (3) Granulate, prepare a green body, and sinter the mixed slurry in step (2) to obtain composite ceramic particles.

4. The preparation method of the heavy-duty bulletproof material according to claim 3, characterized in that, The preparation steps of the reinforcing assistant are as follows: S1: Take a quaternary ammonium salt cationic surfactant and dopamine hydrochloride and completely dissolve them in a buffer solution, adjust its pH to 8.5-10.5, add silicon carbide to it, stir evenly, stir at 75-85 °C for 6-10 h, after the reaction ends, cool to room temperature, separate, wash the obtained solid to neutral, then dry and grind to obtain solid 1; S2: Disperse solid 1 in step S1 in deionized water, adjust the pH value, under stirring conditions, add an anionic surfactant, stir evenly, heat and stir for 3-4 h, then separate, wash, dry, and grind to obtain the reinforcing assistant.

5. The preparation method of the heavy-duty bulletproof material according to claim 4, characterized in that, The mass ratio of dopamine hydrochloride to silicon carbide in step S1 is 1:(20-30).

6. The preparation method of the heavy-duty bulletproof material according to claim 4, wherein, The quaternary ammonium salt cationic surfactant in step S1 is an alkyl quaternary ammonium salt surfactant; the dosage of the quaternary ammonium salt cationic surfactant is 10-20 wt% of dopamine hydrochloride.

7. The preparation method of the heavy-duty bulletproof material according to claim 1, characterized in that, The light filler is at least one of aerogel and hollow glass microspheres.

8. The preparation method of the heavy-duty bulletproof material according to claim 1, characterized in that, The dispersant is at least one of BYK-9076, HY-9070, and polyethylene glycol-based dispersants.

9. The preparation method of the heavy-duty bulletproof material according to claim 1, wherein The diameter of the carbon fiber powder is 1-50 μm.

10. A heavy-duty bulletproof material prepared by the preparation method of the heavy-duty bulletproof material according to any one of claims 1-9.

Images