Preparation method of bulletproof ceramic lining

Abstract

The invention discloses a preparation method of a bulletproof ceramic lining, which belongs to the technical field of bulletproof ceramic composite materials, and comprises the following steps: the bulletproof ceramic lining comprises a modified polyurea elastomer, a ceramic matrix and aramid III fibers; the composite material obtained by dipping, bonding and the like of the three-layer structure including the bullet facing surface modified polyurea elastomer, the middle layer ceramic matrix and the bullet backing surface aramid III fiber has good mechanical property and bulletproof property, meets the protection effect of bulletproof armor, and is high in practicability.

Description

Technical Field

[0001] The present invention belongs to the technical field of bulletproof ceramic composite materials, and particularly relates to a preparation method of a bulletproof ceramic liner. Background Art

[0002] Bulletproof materials have evolved from bulletproof materials mainly based on hard metals to high molecular bulletproof materials such as aramid fibers and nylon fibers, and then to composite systems of metal materials and ceramic materials, composite systems of ceramic materials and high molecular materials, and bulletproof materials of composite systems including the combination of organic materials and inorganic materials. Metal bulletproof materials have advantages such as high strength, strong toughness, and large elastic modulus, but disadvantages such as large density or high price limit the mobility and flexibility of equipment; high molecular bulletproof materials have advantages such as small density, high strength, high temperature resistance, corrosion resistance, heat insulation, and insulation, but disadvantages such as complex molding processes, high cost, and low hardness also limit their use; due to poor plasticity and high brittleness of ceramic materials, the protection effect is poor when used alone as a protective armor. Therefore, improving the mechanical properties of bulletproof ceramic composites has become an urgent problem to be solved. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation method of a bulletproof ceramic liner to solve problems such as poor mechanical properties in existing bulletproof ceramic liners.

[0004] The purpose of the present invention can be achieved through the following technical solutions: A preparation method of a bulletproof ceramic liner, the bulletproof ceramic liner includes a modified polyurea elastomer, a ceramic matrix, and aramid III fibers; for the ceramic matrix, prepare the following raw materials in parts by weight: 45 - 65 parts of boron carbide, 2 - 3 parts of titanium oxide, 8 - 20 parts of alumina, and 30 - 55 parts of silicon carbide whiskers; the bulletproof ceramic liner is a three-layer structure, including a modified polyurea elastomer on the bullet-facing surface, a ceramic matrix in the middle layer, and aramid III fibers on the back bullet-facing surface; The preparation method of the bulletproof ceramic liner includes the following steps: S1. Mix boron carbide, titanium oxide, alumina, silicon carbide whiskers, silane coupling agent KH-792, and toluene, and carry out ball milling. The ball-to-material ratio is 10:1, the rotation speed is 200 - 400 r / min, the ball milling time is 5 - 8 h, then sieve through 200 - 400 meshes to obtain a powder. Then, put the powder, resorcinol, and formaldehyde into a reaction base solution and stir at room temperature for 20 - 40 h, filter to obtain a filter cake, dry, press into shape, the pressing pressure is 15 - 20 MPa, the pressing time is 15 - 30 min, sinter, and cool to obtain a ceramic matrix; S2. Immerse the bullet-facing surface of the ceramic matrix into the modified polyurea elastomer, perform hot pressing, then wash the ceramic matrix with an ethanol solution of 70 - 80 wt% by ultrasound for 2 - 4 h, and perform acid etching with a phosphoric acid solution with a concentration of 0.2 - 0.5 mol / L to obtain a composite ceramic material; S3. Wrap the back bullet-facing surface of the composite ceramic material with aramid III fibers, then add a thermoplastic binder, and seal the wrapped composite ceramic into a dot polyimide high-temperature vacuum bag for hot pressing and compounding to obtain a bulletproof ceramic liner.

[0005] Preferably, in step 1, 10 - 20 parts of silane coupling agent KH-792 and 100 parts of toluene are used.

[0006] Preferably, 40 - 50 parts of resorcinol, 50 - 60 parts of formaldehyde, and 100 parts of reaction base liquid are used; the reaction base liquid includes 30 - 35 parts of absolute ethanol, 1 - 2 parts of ammonia water, and 100 parts of deionized water.

[0007] Preferably, the sintering is as follows: heat up to 850 - 950 °C at a temperature of 5 - 8 °C / min, hold for 40 - 100 min, then rise to 1150 - 1250 °C, and hold for 2 - 4 h.

[0008] Preferably, the preparation method of the modified polyurea elastomer includes the following steps: First step: Prepare the following raw materials in parts by weight: 10 - 20 parts of isocyanate prepolymer, 10 - 20 parts of polycaprolactone diol, 2 - 5 parts of chain extender 4-aminophenylboronic acid, 10 - 25 parts of N,N-dimethylformamide, 5 - 10 parts of amino-terminated polypropylene oxide, 1 - 5 parts of stannous octoate, and 10 - 20 parts of silicone-acrylic emulsion.

[0009] Second step: First, perform vacuum dehydration treatment on polycaprolactone diol and amino-terminated polypropylene oxide, maintain at 100 - 120 °C for 2 - 4 h. Then, under nitrogen conditions, mix the isocyanate prepolymer and polycaprolactone diol, stir at 60 - 80 °C for 30 - 50 min, then add stannous octoate and continue to react for 1 - 2 h to obtain a prepolymer containing terminal -NCO groups. Then cool the prepolymer containing terminal -NCO groups to 38 - 50 °C, add the chain extender 4-aminophenylboronic acid and N,N-dimethylformamide, react for 2 - 3 h, then add amino-terminated polypropylene oxide and stir for 30 - 50 min. Finally, add the silicone-acrylic emulsion and stir at 15 - 30 °C, with a stirring rate of 600 - 1000 rpm and a stirring time of 30 - 60 min to obtain the modified polyurea elastomer.

[0010] Preferably, the preparation method of the isocyanate prepolymer includes the following steps: Under nitrogen conditions, polycaprolactone diol was added to a reaction kettle and stirred. The stirring temperature was 95 - 105 °C, and the stirring time was 1 - 3 h. After cooling, diphenylmethane diisocyanate was added, and the reaction was carried out at 75 - 85 °C for 2 - 3 h to obtain an isocyanate prepolymer. The mass ratio of polycaprolactone diol to diphenylmethane diisocyanate was 2:3 - 3.4, and the relative molecular mass of polycaprolactone diol was 1000.

[0011] Preferably, the thermoplastic binder includes one or more of ethyl acetate-based waterborne adhesives, polyvinyl alcohol-based adhesives, or polyurethane-based waterborne adhesives, and the thickness is 0.1 - 0.5 mm.

[0012] Preferably, the temperature of hot pressing and compounding is 240 - 280 °C, and the pressure of hot pressing and compounding is 1 - 3 MPa.

[0013] Advantages of the present invention: 1. The present invention provides a preparation method of a bulletproof ceramic lining. The bulletproof ceramic lining is a three-layer structure, including a composite material obtained by impregnation, bonding, etc. from raw materials such as a modified polyurea elastomer on the bullet-facing surface, a ceramic matrix in the middle layer, and aramid III fibers on the back bullet-facing surface, which has good mechanical properties and bulletproof performance, meets the protection effect of bulletproof armor, and has strong practicability.

[0014] 2. In the present invention, the modified polyurea elastomer is used as the bullet-facing surface, and its strain rate effect at high strain rates is utilized to absorb energy and improve its anti-bullet effect; the ceramic matrix in the middle layer synergistically improves the anti-penetration ability through boron carbide, titanium oxide, alumina, and silicon carbide whiskers; and the heterocyclic structure of aramid III fibers on the back bullet-facing surface can inhibit the molecular chain breakage and interface microcrack propagation under multiple impacts.

[0015] 3. In the present invention, the chain extender 4-aminophenylboric acid is introduced by chemical means during the formation of the modified polyurea elastomer. On the one hand, due to the high thermal stability of the formed boron-oxygen six-membered ring, the modified polyurea elastomer reduces molecular chain breakage at high temperatures. On the other hand, its rigid structure is combined with the polyurea main chain through covalent bonds, improving the crosslinking density and mechanical properties of the elastomer and forming a denser three-dimensional network. In addition, due to the dynamic reversibility of the B-O bond and B-N coordination bond, the material has certain self-healing ability.

[0016] 4. In the present invention, by using a polyimide vacuum bag for encapsulation, the close fitting of aramid III fibers and ceramics can be achieved in a high-temperature vacuum environment, improving the interfacial bonding strength. Specific embodiments

[0017] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0018] Example 1;

[0019] A method for preparing an isocyanate prepolymer, comprising the following steps: Under nitrogen conditions, 4 g of polycaprolactone diol is added to a reaction kettle and stirred. The stirring temperature is 95 °C, the stirring time is 1 h, and then it is cooled. Then 6 g of diphenylmethane diisocyanate is added and reacted at 75 °C for 2 h to obtain an isocyanate prepolymer. The relative molecular mass of the polycaprolactone diol is 1000.

[0020] A method for preparing a modified polyurea elastomer, comprising the following steps: First step: Prepare the following raw materials in parts by weight: 10 parts of isocyanate prepolymer, 10 parts of polycaprolactone diol, 2 parts of chain extender 4-aminophenylboronic acid, 10 parts of N,N-dimethylformamide, 5 parts of amino-terminated polypropylene oxide, 1 part of stannous octoate, and 10 parts of silicone-acrylic emulsion.

[0021] Second step: First, vacuum dehydrate the polycaprolactone diol and amino-terminated polypropylene oxide at 100 °C for 2 h. Then, under nitrogen conditions, mix the isocyanate prepolymer and polycaprolactone diol, stir at 60 °C for 30 min, then add stannous octoate and continue to react for 1 h to obtain a prepolymer containing terminal -NCO groups. Then cool the prepolymer containing terminal -NCO groups to 38 °C, add the chain extender 4-aminophenylboronic acid and N,N-dimethylformamide, react for 2 h, then add amino-terminated polypropylene oxide and stir for 30 min. Finally, add the silicone-acrylic emulsion and stir at 15 °C. The stirring rate is 600 rpm and the stirring time is 30 min to obtain a modified polyurea elastomer.

[0022] An anti-ballistic ceramic lining, the anti-ballistic ceramic lining comprising a modified polyurea elastomer, a ceramic matrix, and aramid III fibers; for the ceramic matrix, prepare the following raw materials in parts by weight: 45 parts of boron carbide, 2 parts of titanium oxide, 8 parts of alumina, and 30 parts of silicon carbide whiskers; the anti-ballistic ceramic lining is a three-layer structure, including a modified polyurea elastomer on the bullet-facing surface, a ceramic matrix in the middle layer, and aramid III fibers on the back bullet-facing surface; A method for preparing an anti-ballistic ceramic lining, comprising the following steps: S1. Mix boron carbide, titanium oxide, aluminum oxide, silicon carbide whiskers, silane coupling agent KH-792 and toluene, and then conduct ball milling with a ball-to-material ratio of 10:1, a rotation speed of 200 r / min, and a ball milling time of 5 h. Then, sieve through a 200-mesh sieve to obtain powder. Next, put the powder, resorcinol, and formaldehyde into the reaction base solution and stir at 25°C for 20 h. Filter to obtain a filter cake, dry it, press it into shape with a pressing pressure of 15 MPa and a pressing time of 15 min, and then sinter it. Heat it up to 850°C at a rate of 5°C / min, hold for 40 min, then rise to 1150°C and hold for 2 h, and then cool to obtain a ceramic matrix; S2. Immerse the bullet-facing surface of the ceramic matrix into the modified polyurea elastomer and conduct hot pressing. Then, wash the ceramic matrix with a 70 wt% ethanol solution by ultrasound for 2 h, and conduct acid etching with a 0.2 mol / L phosphoric acid solution to obtain a composite ceramic material; S3. Wrap the back bullet-facing surface of the composite ceramic material with aramid III fibers, and then add polyvinyl alcohol adhesive with a thickness of 0.1 mm. Seal the wrapped composite ceramic into a dot polyimide high-temperature vacuum bag for hot pressing and compounding. The temperature of the hot pressing and compounding is 240°C, and the pressure is 1 MPa to obtain a bulletproof ceramic liner.

[0023] The silane coupling agent KH-792 is 10 parts, toluene is 100 parts, resorcinol is 40 parts, formaldehyde is 50 parts, and the reaction base solution is 100 parts; the reaction base solution includes 30 parts of absolute ethanol, 1 part of ammonia water, and 100 parts of deionized water.

[0024] Example 2;

[0025] A preparation method of an isocyanate prepolymer includes the following steps: Under nitrogen conditions, add 4 g of polycaprolactone diol to a reaction kettle and stir at a stirring temperature of 105°C for 3 h. Cool it, and then add 6.8 g of diphenylmethane diisocyanate and react at 85°C for 3 h to obtain an isocyanate prepolymer. The relative molecular mass of the polycaprolactone diol is 1000.

[0026] A preparation method of a modified polyurea elastomer includes the following steps: The first step: Prepare the following raw materials in parts by weight: 20 parts of isocyanate prepolymer, 20 parts of polycaprolactone diol, 5 parts of chain extender 4-aminophenylboronic acid, 25 parts of N,N-dimethylformamide, 10 parts of amino-terminated polypropylene oxide, 5 parts of stannous octoate, and 20 parts of silicone-acrylic emulsion.

[0027] Step 2: First, vacuum dehydrate polycaprolactone diol and amino-terminated poly(propylene oxide) at 120°C for 4 h. Then, under nitrogen, mix the isocyanate prepolymer and polycaprolactone diol, stir at 80°C for 50 min, add stannous octoate, and continue reacting for 2 h to obtain a prepolymer containing terminal -NCO groups. Next, cool the prepolymer containing terminal -NCO groups to 50°C, add the chain extender 4-aminophenylboronic acid and N,N-dimethylformamide, react for 3 h, add amino-terminated poly(propylene oxide) and stir for 50 min. Finally, add the silicone-acrylic emulsion at 30°C and stir at a stirring rate of 1000 rpm for 60 min to obtain the modified polyurea elastomer.

[0028] A bulletproof ceramic liner, the bulletproof ceramic liner comprising a modified polyurea elastomer, a ceramic matrix, and aramid III fibers; for the ceramic matrix, prepare the following raw materials in parts by weight: 65 parts of boron carbide, 3 parts of titanium oxide, 20 parts of alumina, and 55 parts of silicon carbide whiskers; the bulletproof ceramic liner is a three-layer structure, including a modified polyurea elastomer on the bullet-facing surface, a ceramic matrix in the middle layer, and aramid III fibers on the back bullet-facing surface. A preparation method of a bulletproof ceramic liner, comprising the following steps: S1: Mix boron carbide, titanium oxide, alumina, silicon carbide whiskers, silane coupling agent KH-792, and toluene, and perform ball milling. The ball-to-material ratio is 10:1, the rotation speed is 400 r / min, and the ball milling time is 8 h. Then, screen through a 400-mesh sieve to obtain a powder. Next, put the powder, resorcinol, and formaldehyde into the reaction base solution and stir at 25°C for 40 h, filter to obtain a filter cake, dry it, press it into shape, with a pressing pressure of 20 MPa and a pressing time of 30 min, and sinter it. Heat it to 950°C at a rate of 8°C / min, hold for 100 min, then rise to 1250°C, hold for 4 h, and cool to obtain the ceramic matrix. S2: Immerse the bullet-facing surface of the ceramic matrix into the modified polyurea elastomer, perform hot pressing, then wash the ceramic matrix with an 80 wt% ethanol solution by ultrasound for 4 h, and perform acid etching with a 0.5 mol / L phosphoric acid solution to obtain a composite ceramic material. S3: Wrap the back bullet-facing surface of the composite ceramic material with aramid III fibers, then add polyvinyl alcohol adhesive with a thickness of 0.5 mm, and seal the wrapped composite ceramic into a dot polyimide high-temperature vacuum bag for hot pressing and compounding. The temperature of the hot pressing and compounding is 280°C, and the pressure of the hot pressing and compounding is 3 MPa to obtain the bulletproof ceramic liner.

[0029] The silane coupling agent KH-792 is 20 parts, toluene is 100 parts, resorcinol is 50 parts, formaldehyde is 60 parts, and the reaction base solution is 100 parts. The reaction base solution includes 35 parts of absolute ethanol, 2 parts of ammonia water, and 100 parts of deionized water.

[0030] Example 3

[0031] A method for preparing an isocyanate prepolymer, comprising the following steps: Under nitrogen conditions, 4 g of polycaprolactone diol was added to a reaction kettle and stirred. The stirring temperature was 105 °C, and the stirring time was 3 h. After cooling, 6.8 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 85 °C for 3 h to obtain an isocyanate prepolymer. The relative molecular mass of the polycaprolactone diol was 1000.

[0032] A method for preparing a modified polyurea elastomer, comprising the following steps: First step, prepare the following raw materials in parts by weight: 15 parts of isocyanate prepolymer, 18 parts of polycaprolactone diol, 4 parts of chain extender 4-aminophenylboronic acid, 20 parts of N,N-dimethylformamide, 8 parts of amino-terminated poly(propylene oxide), 2 parts of stannous octoate, and 12 parts of silicone-acrylic emulsion.

[0033] Second step, first perform vacuum dehydration treatment on polycaprolactone diol and amino-terminated poly(propylene oxide) at 110 °C for 3 h. Then, under nitrogen conditions, mix the isocyanate prepolymer and polycaprolactone diol, stir at 70 °C for 40 min, add stannous octoate, and continue the reaction for 1.5 h to obtain a prepolymer containing terminal -NCO groups. Then, cool the prepolymer containing terminal -NCO groups to 42 °C, add the chain extender 4-aminophenylboronic acid and N,N-dimethylformamide, react for 1.5 h, add amino-terminated poly(propylene oxide) and stir for 40 min. Finally, add the silicone-acrylic emulsion at 20 °C and stir. The stirring rate is 800 rpm, and the stirring time is 40 min to obtain a modified polyurea elastomer.

[0034] An anti-ballistic ceramic liner, the anti-ballistic ceramic liner comprising a modified polyurea elastomer, a ceramic matrix, and aramid III fibers; for the ceramic matrix, prepare the following raw materials in parts by weight: 50 parts of boron carbide, 2.4 parts of titanium oxide, 12 parts of alumina, and 40 parts of silicon carbide whiskers; the anti-ballistic ceramic liner has a three-layer structure, including a modified polyurea elastomer on the bullet-facing surface, a ceramic matrix in the middle layer, and aramid III fibers on the back bullet-facing surface; A method for preparing an anti-ballistic ceramic liner, comprising the following steps: S1. Mix boron carbide, titanium oxide, alumina, silicon carbide whiskers, silane coupling agent KH-792 and toluene, and put them into ball milling. The ball-to-material ratio is 10:1, the rotation speed is 300 r / min, the ball milling time is 6 h, then sieve through 300 meshes to obtain powder. Then put the powder, resorcinol and formaldehyde into the reaction base solution and stir at 25 °C for 30 h, filter to obtain a filter cake, dry it, press it into shape, the pressing pressure is 18 MPa, the pressing time is 20 min, sinter it, heat it up to 900 °C at a rate of 6 °C / min, keep it warm for 80 min, then raise the temperature to 1200 °C and keep it warm for 3 h, and cool it to obtain a ceramic matrix; S2. Immerse the bullet-facing surface of the ceramic matrix into the modified polyurea elastomer, perform hot pressing, then wash the ceramic matrix with 76 wt% ethanol solution by ultrasound for 3 h, and perform acid etching with a phosphoric acid solution with a concentration of 0.4 mol / L to obtain a composite ceramic material; S3. Wrap the back bullet-facing surface of the composite ceramic material with aramid III fiber, then add polyvinyl alcohol adhesive with a thickness of 0.2 mm, and seal the wrapped composite ceramic into a dot polyimide high-temperature vacuum bag for hot pressing and compounding. The temperature of the hot pressing and compounding is 260 °C, and the pressure of the hot pressing and compounding is 2 MPa to obtain a bulletproof ceramic liner.

[0035] The silane coupling agent KH-792 is 12 parts, toluene is 100 parts, resorcinol is 44 parts, formaldehyde is 54 parts and the reaction base solution is 100 parts. The reaction base solution includes 32 parts of absolute ethanol, 1.5 parts of ammonia water and 100 parts of deionized water.

[0036] Comparative Example 1 A preparation method of an isocyanate prepolymer includes the following steps: Under nitrogen conditions, add 4 g of polycaprolactone diol to the reaction kettle and stir. The stirring temperature is 100 °C, the stirring time is 2 h, cool it, then add 7.6 g of diphenylmethane diisocyanate and react at 80 °C for 2.5 h to obtain an isocyanate prepolymer. The relative molecular mass of polycaprolactone diol is 1000.

[0037] A preparation method of a polyurea elastomer includes the following steps: The first step: Prepare the following raw materials in parts by weight: 15 parts of isocyanate prepolymer, 18 parts of polycaprolactone diol, 4 parts of chain extender diethyltoluenediamine, 8 parts of amino-terminated polyoxypropylene, 2 parts of stannous octoate, and 12 parts of silicone-acrylic emulsion.

[0038] Step 2: First, perform vacuum dehydration treatment on polycaprolactone diol and amino-terminated polypropylene oxide, maintain it at 110 °C for 3 h. Then, under nitrogen conditions, mix the isocyanate prepolymer and polycaprolactone diol, stir at 70 °C for 40 min, add stannous octoate, and continue to react for 1.5 h to obtain a prepolymer containing terminal -NCO groups. Then, cool the prepolymer containing terminal -NCO groups to 42 °C, add the chain extender diethyltoluenediamine, react for 1.5 h, add amino-terminated polypropylene oxide and stir for 40 min. Finally, add the silicone-acrylic emulsion and stir at 20 °C, with a stirring rate of 800 rpm and a stirring time of 40 min to obtain the polyurea elastomer.

[0039] A bulletproof ceramic lining, the bulletproof ceramic lining includes a polyurea elastomer, a ceramic matrix, and aramid III fibers; for the ceramic matrix, prepare the following raw materials in parts by weight: 50 parts of boron carbide, 2.4 parts of titanium oxide, 12 parts of alumina, and 40 parts of silicon carbide whiskers; the bulletproof ceramic lining is a three-layer structure, including a polyurea elastomer on the bullet-facing surface, a ceramic matrix in the middle layer, and aramid III fibers on the back bullet-facing surface; A preparation method of a bulletproof ceramic lining, comprising the following steps: S1: Mix boron carbide, titanium oxide, alumina, silicon carbide whiskers, silane coupling agent KH-792, and toluene, and carry out ball milling. The ball-to-material ratio is 10:1, the rotation speed is 300 r / min, and the ball milling time is 6 h. Then, screen through 300 meshes to obtain a powder. Then, put the powder, resorcinol, and formaldehyde into the reaction base solution and stir at 25 °C for 30 h, filter to obtain a filter cake, dry it, press it into shape, with a pressing pressure of 18 MPa and a pressing time of 20 min, sinter it, heat it up to 900 °C at a temperature of 6 °C / min, keep it warm for 80 min, then raise it to 1200 °C, keep it warm for 3 h, and cool it to obtain the ceramic matrix; S2: Immerse the bullet-facing surface of the ceramic matrix into the polyurea elastomer, perform hot pressing, then wash the ceramic matrix with 76 wt% ethanol solution by ultrasound for 3 h, and perform acid etching with a phosphoric acid solution with a concentration of 0.4 mol / L to obtain a composite ceramic material; S3: Wrap the back bullet-facing surface of the composite ceramic material with aramid III fibers, then add polyvinyl alcohol adhesive with a thickness of 0.2 mm, seal the wrapped composite ceramic into a dot polyimide high-temperature vacuum bag for hot pressing and compounding. The temperature of the hot pressing and compounding is 260 °C, and the pressure of the hot pressing and compounding is 2 MPa to obtain the bulletproof ceramic lining.

[0040] The silane coupling agent KH-792 is 12 parts, toluene is 100 parts, resorcinol is 44 parts, formaldehyde is 54 parts, and the reaction base solution is 100 parts. The reaction base solution includes 32 parts of absolute ethanol, 1.5 parts of ammonia water, and 100 parts of deionized water.

[0041] Comparative Example 2 A bulletproof ceramic lining, the bulletproof ceramic lining includes a modified polyurea elastomer and a ceramic matrix; for the ceramic matrix, the following raw materials in parts by weight are prepared: 50 parts of boron carbide, 2.4 parts of titanium oxide, 12 parts of aluminum oxide, and 40 parts of silicon carbide whiskers; the bulletproof ceramic lining is a two-layer structure, including an intermediate layer of modified polyurea elastomer and a ceramic matrix; A preparation method of a bulletproof ceramic lining, comprising the following steps: S1. Mix boron carbide, titanium oxide, aluminum oxide, silicon carbide whiskers, silane coupling agent KH-792 and toluene, and carry out ball milling. The ball-to-material ratio is 10:1, the rotation speed is 300 r / min, the ball milling time is 6 h, and then it is sieved through 300 meshes to obtain a powder. Then, the powder, resorcinol and formaldehyde are put into a reaction base solution and stirred at 25 °C for 30 h, filtered to obtain a filter cake, dried, press-molded, the pressing pressure is 18 MPa, the pressing time is 20 min, sintered, heated to 900 °C at a temperature of 6 °C / min, held for 80 min, then raised to 1200 °C, held for 3 h, and cooled to obtain a ceramic matrix; S2. Immerse the bullet-facing surface of the ceramic matrix into the modified polyurea elastomer, carry out hot pressing, and then wash the ceramic matrix with a 76 wt% ethanol solution by ultrasound for 3 h, and carry out acid etching with a phosphoric acid solution with a concentration of 0.2 - 0.5 mol / L to obtain a bulletproof ceramic lining.

[0042] The silane coupling agent KH-792 is 12 parts, toluene is 100 parts, resorcinol is 44 parts, formaldehyde is 54 parts, and the reaction base solution is 100 parts. The reaction base solution includes 32 parts of absolute ethanol, 1.5 parts of ammonia water, and 100 parts of deionized water.

[0043] Comparative Example 3 A bulletproof ceramic lining, the bulletproof ceramic lining includes a ceramic matrix and aramid III fibers; for the ceramic matrix, the following raw materials in parts by weight are prepared: 50 parts of boron carbide, 2.4 parts of titanium oxide, 12 parts of aluminum oxide, and 40 parts of silicon carbide whiskers; the bulletproof ceramic lining is a two-layer structure, including a ceramic matrix and aramid III fibers; A preparation method of a bulletproof ceramic lining, comprising the following steps: S1. Mix boron carbide, titanium oxide, aluminum oxide, silicon carbide whiskers, silane coupling agent KH-792 and toluene, and then conduct ball milling with a ball-to-material ratio of 10:1, a rotation speed of 300 r / min, and a ball milling time of 6 h. Then, sieve through 300 meshes to obtain powder. Next, put the powder, resorcinol and formaldehyde into the reaction base solution and stir at 25 °C for 30 h, filter to obtain a filter cake, dry it, press it into shape with a pressing pressure of 18 MPa and a pressing time of 20 min, and sinter it. Heat it up to 900 °C at a rate of 6 °C / min, hold for 80 min, then raise the temperature to 1200 °C and hold for 3 h, and then cool it to obtain a ceramic matrix; S2. Wrap the back impact surface of the composite ceramic material with aramid III fiber, and then add polyvinyl alcohol adhesive with a thickness of 0.2 mm. Seal the wrapped composite ceramic into a dot polyimide high-temperature vacuum bag for hot pressing and compounding. The temperature of the hot pressing and compounding is 260 °C, and the pressure of the hot pressing and compounding is 2 MPa to obtain a bulletproof ceramic lining.

[0044] The silane coupling agent KH-792 is 12 parts, toluene is 100 parts, resorcinol is 44 parts, formaldehyde is 54 parts and the reaction base solution is 100 parts. The reaction base solution includes 32 parts of absolute ethanol, 1.5 parts of ammonia water and 100 parts of deionized water.

[0045] Perform performance tests on the ceramic matrices impregnated with the modified polyurea elastomers obtained in Examples 1 - 3 and Comparative Examples 1 - 3. Among them, the flexural strength refers to the standard of GB / T6569-2006, and the fracture toughness refers to the test standard of GB / T23806-2009. The results are shown in Table 1: Table 1

[0046] It can be seen from Table 1 that compared with Comparative Examples 1 - 3, the flexural strength of the ceramic matrices impregnated with the modified polyurea elastomers prepared in Examples 1 - 3 is 670 - 685 MPa, and the fracture toughness is 7.74 - 7.96 MPa·m 1 / 2 , indicating that it has excellent mechanical properties.

[0047] Perform performance tests on the bulletproof ceramic linings obtained in Examples 1 - 3 and Comparative Examples 1 - 3. Among them, the protection performance refers to the standard of GJB59.18-88. At normal temperature and normal humidity, fire 3 rounds of 54-type 12.7 mm bullets with a bullet speed of 840 m / s. The results are shown in Table 2: Table 2

[0048] It can be seen from Table 2 that compared with Comparative Examples 1 - 3, the bulletproof ceramic linings prepared in Examples 1 - 3 show no penetration, and the maximum depression is 8 - 11 mm, and their bulletproof effect is better.

[0049] It should be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device.

[0050] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a bulletproof ceramic lining sheet, characterized in that, The bulletproof ceramic liner described above comprises a modified polyurea elastomer, a ceramic matrix, and aramid III fibers; for the ceramic matrix, the following raw materials in parts by weight are prepared: 45-65 parts of boron carbide, 2-3 parts of titanium oxide, 8-20 parts of aluminum oxide, and 30-55 parts of silicon carbide whiskers; the bulletproof ceramic liner has a three-layer structure, including a modified polyurea elastomer on the bullet-facing surface, a ceramic matrix in the middle layer, and aramid III fibers on the back bullet-facing surface; The preparation method of the bulletproof ceramic liner comprises the following steps: S1. Mix boron carbide, titanium oxide, aluminum oxide, silicon carbide whiskers, silane coupling agent KH-792, and toluene, and carry out ball milling. The ball-to-material ratio is 10:1, the rotation speed is 200-400 r / min, the ball milling time is 5-8 h, then sieve through 200-400 meshes to obtain a powder. Then, put the powder, resorcinol, and formaldehyde into a reaction base solution and stir at room temperature for 20-40 h, filter to obtain a filter cake, dry, press into shape, with a pressing pressure of 15-20 MPa and a pressing time of 15-30 min, sinter, and cool to obtain a ceramic matrix; S2. Immerse the bullet-facing surface of the ceramic matrix into the modified polyurea elastomer, carry out hot pressing, then wash the ceramic matrix with a 70-80 wt% ethanol solution by ultrasonic for 2-4 h, and carry out acid etching with a phosphoric acid solution with a concentration of 0.2-0.5 mol / L to obtain a composite ceramic material; S3. Wrap the back bullet-facing surface of the composite ceramic material with aramid III fibers, then add a thermoplastic binder, and seal the wrapped composite ceramic into a dot polyimide high-temperature vacuum bag for hot pressing and compounding to obtain a bulletproof ceramic liner.

2. The preparation method of the bulletproof ceramic lining according to claim 1, wherein In S1, 10-20 parts of silane coupling agent KH-792 and 100 parts of toluene are used.

3. The preparation method of the bulletproof ceramic lining sheet according to claim 1, characterized in that, In S1, 40-50 parts of resorcinol, 50-60 parts of formaldehyde, and 100 parts of reaction base solution; the reaction base solution comprises 30-35 parts of absolute ethanol, 1-2 parts of ammonia water, and 100 parts of deionized water.

4. The preparation method of the bulletproof ceramic lining according to claim 1, characterized in that, The sintering in S1 is as follows: heat up to 850-950 °C at a temperature of 5-8 °C / min, hold for 40-100 min, then rise to 1150-1250 °C and hold for 2-4 h.

5. The preparation method of the bulletproof ceramic lining according to claim 1, characterized in that The preparation method of the modified polyurea elastomer comprises the following steps: The first step. Prepare the following raw materials in parts by weight: 10-20 parts of isocyanate prepolymer, 10-20 parts of polycaprolactone diol, 2-5 parts of chain extender 4-aminophenylboronic acid, 10-25 parts of N,N-dimethylformamide, 5-10 parts of amino-terminated polyoxypropylene, 1-5 parts of stannous octoate, and 10-20 parts of silicone-acrylic emulsion; Step 2: First, perform vacuum dehydration on polycaprolactone diol and amino-terminated polyoxypropylene, maintain at 100 - 120 °C for 2 - 4 h. Then, under nitrogen conditions, mix the isocyanate prepolymer and polycaprolactone diol, stir at 60 - 80 °C for 30 - 50 min, add stannous octoate, and continue to react for 1 - 2 h to obtain a prepolymer containing terminal -NCO groups. Then, cool the prepolymer containing terminal -NCO groups to 38 - 50 °C, add the chain extender 4 - aminophenylboronic acid and N,N - dimethylformamide, react for 2 - 3 h, add amino - terminated polyoxypropylene and stir for 30 - 50 min. Finally, add the silicone - acrylic emulsion and stir at 15 - 30 °C, with a stirring rate of 600 - 1000 rpm and a stirring time of 30 - 60 min to obtain the modified polyurea elastomer.

6. The preparation method of the bulletproof ceramic lining according to claim 5, characterized in that, The preparation method of the isocyanate prepolymer includes the following steps: Under nitrogen conditions, add polycaprolactone diol to the reaction kettle and stir, with a stirring temperature of 95 - 105 °C and a stirring time of 1 - 3 h. Cool, then add diphenylmethane diisocyanate, and react at 75 - 85 °C for 2 - 3 h to obtain the isocyanate prepolymer. The mass ratio of polycaprolactone diol to diphenylmethane diisocyanate is 2:3 - 3.4, and the relative molecular mass of polycaprolactone diol is 1000.

7. The preparation method of the bulletproof ceramic lining according to claim 1, characterized in that, The thermoplastic binder includes one or more of ethyl acetate - based water - borne adhesives, polyvinyl alcohol - based adhesives, or polyurethane - based water - borne adhesives.

8. The preparation method of the bulletproof ceramic lining sheet according to claim 1, characterized in that, The temperature of the hot - press lamination is 240 - 280 °C, and the pressure of the hot - press lamination is 1 - 3 MPa.

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