Multi-impact-resistant ceramic composite material and preparation method thereof

Abstract

The invention provides a multi-impact-resistant ceramic composite material and a preparation method thereof, and relates to the field of ceramic materials. The preparation method of the multi-impact-resistant ceramic composite material comprises the following steps of 3D printing forming, glue discharging treatment, infiltration dipping and hot isostatic pressing sintering. According to the preparation method of the multi-impact-resistant ceramic composite material, the problem that after an existing metal ceramic composite material is subjected to multi-impact, a ceramic layer is prone to damage and failure is solved in a targeted mode, and the multi-impact-resistant performance of the material is further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of ceramic materials, in particular to a ceramic composite material resistant to multiple impacts and a preparation method thereof. BACKGROUND

[0002] Bulletproof ceramics are widely used in personal protection, armored vehicles and aerospace fields due to their high hardness, low density and excellent bulletproof performance. However, pure ceramic bulletproof materials have the disadvantages of high brittleness and insufficient resistance to multiple impacts. Metal-ceramic composite bulletproof materials significantly improve the bulletproof performance of the materials by combining the toughness of metal and the high hardness of ceramic. Specifically, the basic structure of the metal-ceramic composite bulletproof material is generally a double-layer structure or a multi-layer structure. The double-layer structure is usually composed of a ceramic faceplate and a tough metal backplate, and the multi-layer structure is usually composed of the aforementioned double-layer structure and an intermediate polymer composite buffer layer. The main composite methods of the double-layer structure or the multi-layer structure include mechanical bonding, adhesive bonding, hot pressing and hot isostatic pressing. Among them, adhesive bonding is the most popular composite method. In the working process of the metal-ceramic composite bulletproof material, the metal-ceramic composite bulletproof material achieves the anti-impact (bulletproof) effect through the layered synergistic mechanism of the ceramic faceplate fragmenting and passivating the projectile, the intermediate polymer composite buffer layer buffering, and the tough metal backplate absorbing the remaining energy, restraining the fragments and preventing penetration.

[0003] However, the existing metal-ceramic composite bulletproof material still has the following problems: in the working process of the metal-ceramic composite bulletproof material, although the tough metal backplate can delay the collapse of the ceramic faceplate, the ceramic layer will inevitably be damaged and fail after multiple impacts, losing the expected bulletproof ability, and the ceramic faceplate needs to be replaced more frequently (such as B4C ceramic plate cracking after resisting 1-2 armor-piercing projectile impacts).

[0004] Therefore, the present application provides a ceramic composite material resistant to multiple impacts and a preparation method thereof, which specifically overcomes the problem that the ceramic layer of the existing metal-ceramic composite material is easily damaged and fails after multiple impacts, and further improves the multiple impact resistance of the ceramic composite material, which has important technical significance and research value. SUMMARY

[0005] To solve the technical problems in the prior art, the present application provides a preparation method of a ceramic composite material resistant to multiple impacts, which specifically overcomes the problem that the ceramic layer of the existing metal-ceramic composite material is easily damaged and fails after multiple impacts, and further improves the multiple impact resistance of the material. The present application also provides a ceramic composite material resistant to multiple impacts prepared by the aforementioned method.

[0006] To solve the above technical problems, the technical solutions adopted by the present application are as follows: A method for preparing a ceramic composite material resistant to multiple impacts, comprising the steps of: 3D printing forming, degassing treatment, infiltration impregnation, hot isostatic pressing sintering; The method for 3D printing forming is that ceramic slurry and metal slurry are simultaneously 3D printed, the ceramic slurry is 3D printed into a plurality of ceramic spring reinforcements, and the metal slurry is 3D printed into a niobium-zirconium alloy matrix; each ceramic spring reinforcement is embedded in the niobium-zirconium alloy matrix to obtain a composite material green body block; The ceramic slurry comprises β-silicon nitride powder and boron carbide powder; The metal slurry comprises niobium-zirconium alloy, β-silicon carbide powder and alumina powder; After the degassing treatment of the composite material green body block, a porous preform is obtained; The method for infiltration impregnation is that the porous preform is contacted with an alloy melt of Al-7Si alloy for pressure infiltration, and then contacted with a polysilicocarbosane solution for vacuum impregnation; the pressure infiltration-vacuum impregnation is repeated until the porous preform reaches a constant weight, to obtain an infiltration impregnated body; The infiltration impregnated body is subjected to hot isostatic pressing sintering to obtain a ceramic composite material resistant to multiple impacts.

[0007] Further, the niobium-zirconium alloy matrix of the composite material green body block is embedded with a plurality of ceramic spring reinforcements in uniform distribution or non-uniform distribution; each ceramic spring reinforcement is coaxial with the impact-approaching direction of the composite material green body block; The weight percentage of the ceramic spring reinforcements in the composite material green body block is 30-50%.

[0008] Preferably, the weight ratio of β-silicon nitride powder to boron carbide powder in the ceramic slurry is 85-90:8-10; The weight ratio of niobium-zirconium alloy to β-silicon carbide powder to alumina powder in the metal slurry is 85-90:8-10:4-5.

[0009] Further, the degassing treatment is performed at a temperature increasing rate of 2-5 ℃ / min, the composite material green body block is heated from room temperature to 600-650 ℃, and the porous preform is obtained after heat preservation and degassing.

[0010] Preferably, the temperature for pressure infiltration is 720-750 ℃, the pressure is 60-100 MPa, and the pressure infiltration time is 15-30 min; The vacuum degree for vacuum impregnation is 0.080-0.099 MPa, and the vacuum impregnation time is 12-24 h.

[0011] Preferably, the volume ratio of the alloy melt to the porous preform used in the pressure infiltration is 1:2-3. The volume ratio of the polysilicocarbide solution to the porous preform in the vacuum impregnation is 1:2-3; The concentration of the polysilicocarbide solution is 60-70wt%.

[0012] Further, the method for hot isostatic sintering is as follows: under the protection of nitrogen atmosphere, the infiltrated body is heated to 1400-1460℃ under the pressure of 100-200MPa, and is kept for 2-6h to obtain the ceramic composite material resistant to multiple impacts.

[0013] Further, the preparation method of the ceramic slurry is as follows: 85-90 parts of β-silicon nitride powder, 8-10 parts of boron carbide powder and 1-3 parts of oleyl alcohol are uniformly mixed to obtain a first powder; 40-50 parts of the first powder, 1-2 parts of No.58 paraffin and 2-3 parts of No.70 paraffin are uniformly mixed to obtain a first premix; 40-50 parts of the first powder, 3-5 parts of polyethylene oxide, 3-8 parts of polypropylene and 0.5-3 parts of thermoplastic butadiene rubber are added into 30-50 parts of the first premix, and the mixture is uniformly heated to obtain the ceramic slurry.

[0014] Further, the preparation method of the metal slurry is as follows: 85-90 parts of niobium-zirconium alloy, 8-10 parts of β-silicon carbide powder and 4-5 parts of aluminum oxide powder are uniformly mixed to obtain a second powder; 40-50 parts of the second powder, 1-2 parts of No.58 paraffin and 2-3 parts of No.70 paraffin are uniformly mixed to obtain a second premix; 40-50 parts of the second powder, 3-5 parts of polyethylene oxide, 3-8 parts of polypropylene and 0.5-3 parts of thermoplastic butadiene rubber are added into 30-50 parts of the second premix, and the mixture is uniformly heated to obtain the metal slurry.

[0015] A ceramic composite material resistant to multiple impacts prepared by the preparation method.

[0016] Compared with the prior art, the present application has the following beneficial effects: (1) The preparation method of the anti-multiple impact ceramic composite material of the present application adopts ceramic slurry containing beta-silicon nitride powder and boron carbide powder, and metal slurry containing niobium-zirconium alloy, beta-silicon carbide powder and aluminum oxide powder, and cooperates with 3D printing to embed the ceramic spring reinforcing body in the niobium-zirconium alloy matrix to obtain a composite blank block, and then performs degassing treatment, to obtain a porous preform with multiple channels inside, which provides a densification path for the subsequent alloy melt and polysilicon alkane solution infiltration impregnation, and is beneficial to the densification of the ceramic composite material. Then, the porous preform is subjected to multiple pressure infiltration-vacuum impregnation processes of the alloy melt and polysilicon alkane solution of Al-7Si alloy, the alloy melt and polysilicon alkane solution of Al-7Si alloy are introduced into the porous preform, and a melt-impregnated body is obtained. Then, in the hot isostatic pressing sintering process, the polysilicon alkane in the melt-impregnated body is converted into silicon carbide ceramic, and the metal alloy is chemically bonded with the ceramic material under the action of high temperature, to form a composite structure of metal-ceramic-metal-ceramic spring, which effectively improves the interfacial shear strength between the metal and the ceramic in the ceramic composite material, and simultaneously improves the hardness, fracture toughness and density thereof; at the same time, the buffering and energy absorption effect of the ceramic spring reinforcing body in the ceramic composite material is cooperated, to further improve the anti-multiple impact performance of the ceramic composite material; the above-mentioned comprehensive effects effectively prevent the ceramic composite material from being damaged and cracked after suffering multiple impacts, and losing the bulletproof ability.

[0017] (2) The hardness of the anti-multiple impact ceramic composite material of the present application is > 200HB, the density is > 99%, the fracture toughness is > 10MPa·m 1 / 2 ; the interfacial shear strength between the metal and the ceramic in the ceramic composite material is > 320MPa; the anti-multiple impact ceramic composite material can still maintain the bulletproof ability without destructive cracking after 5 impacts. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 It is a schematic diagram of the impact direction cross section (transverse cross section) of the composite blank block of the embodiment of the present application; 1-ceramic spring reinforcing body, 2-niobium-zirconium alloy matrix. DETAILED DESCRIPTION

[0019] In order to have a clearer understanding of the technical features, objects and effects of the present application, the specific embodiments of the present application will be described. It should be pointed out that the following detailed description is exemplary and is intended to provide further description of the present application. Unless otherwise specified, all technical and scientific terms used in the present application have the same meaning as generally understood by those skilled in the art to which the present application belongs.

[0020] It is to be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, "first," "second," and the like are used merely as labels, and are not intended to impose ordinal or positional requirements on the items to which they are applied, and further, are not intended to denote specific order or sequence, except where explicitly so indicated. Also, it is to be understood that the use of the terms "comprise", "comprises", "comprising", "include", "includes", "including", or the like, are not intended to exclude or exclude the possibility of one or more additional features, steps, operations, members, components, and / or groups thereof.

[0021] The embodiment of the application provides a preparation method of ceramic composite material resistant to multiple impacts, comprising the following steps: raw material preparation, 3D printing forming, glue removal treatment, infiltration impregnation and hot isostatic pressing sintering.

[0022] The raw material preparation comprises the following steps: ceramic slurry preparation and metal slurry preparation.

[0023] The method for preparing the ceramic slurry comprises the following steps: 85-90 parts of beta-silicon nitride powder, 8-10 parts of boron carbide powder and 1-3 parts of oleyl alcohol are uniformly ground after mixing to prepare a first powder; 40-50 parts of the first powder, 1-2 parts of No.58 paraffin and 2-3 parts of No.70 paraffin are uniformly mixed after being heated to 100-110 DEG C to prepare a first premix, and the first premix is kept warm; 40-50 parts of the first powder, 3-5 parts of polyethylene oxide, 3-8 parts of polypropylene and 0.5-3 parts of thermoplastic butadiene rubber are added into 30-50 parts of the first premix, and the mixture is uniformly mixed after being continuously heated to 200-230 DEG C, and then the mixture is cooled to room temperature to prepare the ceramic slurry.

[0024] The method for preparing the metal slurry comprises the following steps: 85-90 parts of niobium-zirconium alloy, 8-10 parts of beta-silicon carbide powder and 4-5 parts of aluminum oxide powder are uniformly ground after mixing to prepare a second powder; 40-50 parts of the second powder, 1-2 parts of No.58 paraffin and 2-3 parts of No.70 paraffin are uniformly mixed after being heated to 100-110 DEG C to prepare a second premix, and the second premix is kept warm; 40-50 parts of the second powder, 3-5 parts of polyethylene oxide, 3-8 parts of polypropylene and 0.5-3 parts of thermoplastic butadiene rubber are added into 30-50 parts of the second premix, and the mixture is uniformly mixed after being continuously heated to 200-230 DEG C, and then the mixture is cooled to room temperature to prepare the metal slurry.

[0025] The method for 3D printing forming comprises the following steps: the ceramic slurry and the metal slurry are 3D printed by a fused deposition 3D printing device with double spray heads, the ceramic slurry is 3D printed into a plurality of ceramic spring reinforcing bodies 1, the metal slurry is 3D printed into a niobium-zirconium alloy base 2, each ceramic spring reinforcing body 1 is inlaid in the niobium-zirconium alloy base 2, and a composite material blank block with the ceramic spring reinforcing body 1 inlaid in the niobium-zirconium alloy base 2 is prepared.

[0026] In the embodiments of the present application, in the direction of the composite blank block body, a plurality of ceramic spring reinforcements 1 are embedded in the composite blank block body; and each of the ceramic spring reinforcements is coaxial with the direction of the composite blank block body. Preferably, a plurality of ceramic spring reinforcements 1 are uniformly embedded in the composite blank block body.

[0027] In the embodiments of the present application, in any direction of the composite blank block body, at least one row of ceramic spring reinforcements 1 is embedded in the composite blank block body; preferably, two rows of ceramic spring reinforcements 1 are uniformly embedded in the composite blank block body.

[0028] The schematic diagram of the cross-sectional view (transverse section) of the composite blank block body with the Nb-Zr alloy matrix 2 embedded with the ceramic spring reinforcements 1 is shown in Figure 1 .

[0029] In the embodiments of the present application, the weight percentage of the ceramic spring reinforcements in the composite blank block body is 30-50%.

[0030] The method of the degassing treatment is to perform the degassing treatment on the composite blank block body formed by the 3D printing, specifically, starting from room temperature, heating at a heating rate of 2-5 ℃ / min, heating to 600-650 ℃, and keeping the temperature for 60-120 min to perform the high-temperature degreasing and degassing treatment to obtain a porous preform.

[0031] In the foregoing step, the 3D printing of the composite blank block body with the Nb-Zr alloy matrix embedded with the ceramic spring reinforcements is performed by using the ceramic slurry containing the β-silicon nitride powder and the boron carbide powder, and the metal slurry containing the Nb-Zr alloy, the β-silicon carbide powder, and the alumina powder, and then the degassing treatment is performed to obtain a porous preform with multiple channels inside, which provides a densification path for the subsequent alloy melt and polysilicocarbalkane solution infiltration impregnation, and is beneficial to the densification of the ceramic composite material.

[0032] The method of the infiltration impregnation is to melt the Al-7Si alloy, control the melting temperature to be 720-750 ℃ to obtain an alloy melt; under the temperature condition of 720-750 ℃, the alloy melt is contacted with the porous preform, the alloy melt enters into the porous preform along the channels after the degassing through the pressure infiltration; after the pressure infiltration is completed, the polysilicocarbalkane solution (concentration of 60-70 wt%, solvent is n-hexane) is contacted with the porous preform, and the polysilicocarbalkane solution is impregnated into the porous preform through the vacuum impregnation; the foregoing pressure infiltration-vacuum impregnation-pressure infiltration-vacuum impregnation treatment is repeatedly performed until the weight of the porous preform no longer increases to obtain an infiltration impregnated body.

[0033] In the embodiment of the present application, the pressure infiltration process is controlled at a pressure of 60-100 MPa, and the pressure holding time is 15-30 min.

[0034] In the embodiment of the present application, the vacuum infiltration process is controlled at a vacuum degree of 0.08-0.1 MPa, and the vacuum infiltration time is 12-24 h.

[0035] In the embodiment of the present application, the concentration of the polysilicocarbane solution is 60-70 wt%, and the solvent is n-hexane.

[0036] In the embodiment of the present application, the volume ratio of the alloy melt to the porous preform in the pressure infiltration process is 1:2-3.

[0037] In the embodiment of the present application, the volume ratio of the polysilicocarbane solution to the porous preform in the vacuum infiltration process is 1:2-3.

[0038] In the foregoing step, the porous preform is subjected to multiple pressure infiltration-vacuum infiltration processes by using the alloy melt of Al-7Si alloy and the polysilicocarbane solution, the alloy melt of Al-7Si alloy and the polysilicocarbane solution are introduced into the porous preform, and a melt-infiltrated body is obtained.

[0039] The method for hot isostatic pressing sintering is that the melt-infiltrated body is placed in a hot isostatic pressing sintering furnace, is heated to 1400-1460 ℃ under the protection of a nitrogen atmosphere at a pressure of 100-200 MPa, and is subjected to hot isostatic pressing sintering for 2-6 h, so that an anti-multiple-impact ceramic composite material is prepared.

[0040] In the foregoing step, the polysilicocarbane in the melt-infiltrated body is converted into silicon carbide ceramic, the metal alloy is chemically bonded with the ceramic material under the action of high temperature, and a composite structure of metal-ceramic-metal-ceramic spring is formed, which effectively improves the interfacial shear strength between the metal and the ceramic in the ceramic composite material, and simultaneously improves the hardness, the fracture toughness and the density of the ceramic composite material; meanwhile, the buffering and energy-absorbing effect of the ceramic spring reinforcement in the ceramic composite material further improves the anti-multiple-impact performance of the ceramic composite material; and the foregoing measures comprehensively prevent the ceramic composite material from being damaged and losing the bulletproof capability due to destructive cracking after suffering multiple impacts.

[0041] The embodiment of the present application also provides an anti-multiple-impact ceramic composite material prepared by using the foregoing method.

[0042] The present application is further described below in combination with some specific embodiments.

[0043] Embodiment 1 The present embodiment provides a preparation method of an anti-multiple-impact ceramic composite material, in particular to: (1) Preparation of raw materials a. Preparation of ceramic slurry: 88 parts of β-silicon nitride powder, 9 parts of boron carbide powder, 2 parts of oleyl alcohol were mixed and ground uniformly to prepare a first powder; 45 parts of the first powder, 1.7 parts of No. 58 paraffin wax, 2.5 parts of No. 70 paraffin wax were mixed, heated to 105℃ and mixed uniformly to prepare a first premix, and kept warm for use; 45 parts of the first powder, 4 parts of polyethylene oxide, 7 parts of polypropylene, 2.4 parts of thermoplastic butadiene rubber were added to 42 parts of the first premix, and heated to 220℃ and mixed uniformly, then cooled to room temperature to prepare the ceramic slurry.

[0044] b. Preparation of metal slurry: 88 parts of niobium-zirconium alloy, 9 parts of β-silicon carbide powder, 4.5 parts of aluminum oxide powder were mixed and ground uniformly to prepare a second powder; 45 parts of the second powder, 1.7 parts of No. 58 paraffin wax, 2.5 parts of No. 70 paraffin wax were mixed, heated to 105℃ and mixed uniformly to prepare a second premix, and kept warm for use; 45 parts of the second powder, 4 parts of polyethylene oxide, 7 parts of polypropylene, 2.4 parts of thermoplastic butadiene rubber were added to 42 parts of the second premix, and heated to 220℃ and mixed uniformly, then cooled to room temperature to prepare the metal slurry.

[0045] (2) 3D printing forming The ceramic slurry and the metal slurry are 3D printed by a fused deposition 3D printing device with double nozzles, the ceramic slurry is 3D printed to form a plurality of ceramic spring reinforcements 1, the metal slurry is 3D printed to form a niobium-zirconium alloy matrix 2, each ceramic spring reinforcement 1 is embedded in the niobium-zirconium alloy matrix 2 to obtain a composite blank block with a plurality of ceramic spring reinforcements 1 embedded in the niobium-zirconium alloy matrix 2. Specifically, in the direction of the composite blank block, a plurality of ceramic spring reinforcements 1 are uniformly or non-uniformly embedded in the composite blank block; and each ceramic spring reinforcement 1 is coaxial with the direction of the composite blank block. At the same time, in any direction of the cross section of the composite blank block, at least one row of ceramic spring reinforcements 1 are uniformly or non-uniformly embedded in the composite blank block.

[0046] Among them, the weight percentage of the ceramic spring reinforcement 1 in the composite blank block is 40%.

[0047] (3) Degassing treatment The composite blank block obtained by 3D printing forming is subjected to degassing treatment, which is heated from room temperature to 630℃ at a heating rate of 3℃ / min, and kept for 90min for high-temperature degreasing and degassing treatment to obtain a porous preform.

[0048] (4) Infiltration impregnation Al-7Si alloy is melted, and the melting temperature is controlled at 735 ℃ to obtain an alloy melt; under the temperature condition of 735 ℃, the alloy melt enters into the porous preform obtained in step (3) through pressure infiltration along the channels after the glue is removed; wherein the pressure of the pressure infiltration is controlled at 80 MPa, and the pressure maintaining time is 20 min; after the pressure infiltration is completed, the polysilicocarbododecane solution (concentration 65 wt%, solvent n-hexane) is impregnated into the porous preform through vacuum impregnation; wherein the vacuum degree of the vacuum impregnation is controlled at 0.099 MPa, and the vacuum impregnation time is 18 h; the foregoing pressure infiltration-vacuum impregnation-pressure infiltration-vacuum impregnation process is repeated until the porous preform no longer increases in weight, and a melt-impregnated body is obtained.

[0049] In the pressure infiltration, the volume ratio of the alloy melt to the porous preform is 1:2.2.

[0050] In the vacuum impregnation, the volume ratio of the polysilicocarbododecane solution to the porous preform is 1:2.2.

[0051] (5) Hot isostatic sintering The melt-impregnated body obtained in step (4) is placed in a hot isostatic sintering furnace, and under the protection of a nitrogen atmosphere, the temperature is raised to 1450 ℃ under a pressure of 160 MPa, and hot isostatic sintering is performed for 5 h to obtain a ceramic composite material resistant to multiple impacts.

[0052] The embodiment also provides the ceramic composite material resistant to multiple impacts prepared by the foregoing method. The hardness of the ceramic composite material resistant to multiple impacts is 224 HB, the density is 99.5%, the fracture toughness is 11.3 MPa·m 1 / 2 ; the interfacial shear strength between the metal and the ceramic in the ceramic composite material is 335 MPa; and the ceramic composite material resistant to multiple impacts does not have destructive cracking and can still maintain the bulletproof ability after being subjected to 5 impacts.

[0053] Embodiment 2 The embodiment provides a preparation method of a ceramic composite material resistant to multiple impacts, and specifically comprises the following steps: (1) Preparation of raw materials a. Preparation of ceramic slurry: 85 parts of β-silicon nitride powder, 8 parts of boron carbide powder and 1 part of oleyl alcohol are uniformly ground after being mixed to prepare a first powder; 40 parts of the first powder, 1 part of No. 58 paraffin and 2 parts of No. 70 paraffin are mixed, heated to 100 ℃ and uniformly mixed to prepare a first premix, which is kept warm for use; 40 parts of the first premix, 3 parts of polyethylene oxide, 3 parts of polypropylene and 1.8 parts of thermoplastic butadiene rubber are added to 40 parts of the first premix, and then uniformly mixed after being continuously heated to 200 ℃ and cooled to room temperature to prepare a ceramic slurry.

[0054] b. Preparation of metal slurry: 85 parts of niobium-zirconium alloy, 8 parts of β-silicon carbide powder, 4 parts of alumina powder were mixed and ground uniformly to prepare a second powder; 40 parts of the second powder, 1 part of No. 58 paraffin, 2 parts of No. 70 paraffin were mixed and heated to 100°C to mix uniformly to prepare a second premix, and kept warm for use; 40 parts of the second premix, 3 parts of polyethylene oxide, 3 parts of polypropylene, and 1.8 parts of thermoplastic butadiene rubber were added and heated to 200°C to mix uniformly, and then cooled to room temperature to prepare a metal slurry.

[0055] (2) 3D printing forming The ceramic slurry and the metal slurry are 3D printed by a fused deposition 3D printing device with double nozzles, the ceramic slurry is 3D printed to form a plurality of ceramic spring reinforcements 1, the metal slurry is 3D printed to form a niobium-zirconium alloy matrix 2, each ceramic spring reinforcement 1 is embedded in the niobium-zirconium alloy matrix 2 to obtain a composite blank block with a plurality of ceramic spring reinforcements 1 embedded in the niobium-zirconium alloy matrix 2. Specifically, in the direction of the composite blank block, a plurality of ceramic spring reinforcements 1 are uniformly or non-uniformly embedded in the composite blank block; and each ceramic spring reinforcement 1 is coaxial with the direction of the composite blank block. At the same time, in any direction of the cross section of the composite blank block, at least one row of ceramic spring reinforcements 1 is uniformly or non-uniformly embedded in the composite blank block.

[0056] Among them, the weight percentage of the ceramic spring reinforcement 1 in the composite blank block is 42%.

[0057] (3) Degassing treatment The composite blank block obtained by 3D printing forming is subjected to degassing treatment, specifically, starting from room temperature, heating at a rate of 2°C / min to 600°C, and keeping for 120 min for high-temperature degreasing and degassing treatment to obtain a porous preform.

[0058] (4) Melt infiltration An Al-7Si alloy is melted to obtain an alloy melt by controlling the melting temperature to be 720°C; under the temperature condition of 720°C, the alloy melt enters into the porous preform obtained in step (3) along the channels after degassing by pressure infiltration; wherein the pressure of the pressure infiltration is controlled to be 60 MPa, and the pressure holding time is 30 min; after the pressure infiltration is completed, a polysilicon carbon solution (concentration 65 wt%, solvent n-hexane) is impregnated into the porous preform by vacuum impregnation; wherein the vacuum degree of the vacuum impregnation is controlled to be 0.08 MPa, and the vacuum impregnation time is 24 h; the foregoing pressure infiltration-vacuum impregnation-pressure infiltration-vacuum impregnation process is repeated until the weight of the porous preform no longer increases, and a melt infiltration body is obtained.

[0059] The volume ratio of the alloy melt used in the pressure infiltration to the porous preform is 1:2.

[0060] The volume ratio of the polysilicocarbano solution used in the vacuum impregnation to the porous preform is 1:2.

[0061] (5) Hot isostatic sintering The infiltrated impregnated body obtained in step (4) is placed in a hot isostatic sintering furnace, and is heated to 1400℃ under the protection of a nitrogen atmosphere at a pressure of 100 MPa, and is subjected to hot isostatic sintering for 6 h, thereby obtaining a ceramic composite material resistant to multiple impacts.

[0062] The embodiment also provides the ceramic composite material resistant to multiple impacts obtained by the method. The hardness of the ceramic composite material resistant to multiple impacts is 215 HB, the density is 99.3%, the fracture toughness is 10.9 MPa·m 1 / 2 ; the interfacial shear strength between the metal and the ceramic in the ceramic composite material is 327 MPa; and the ceramic composite material resistant to multiple impacts does not have destructive cracking and still has the ability to resist bullets after being subjected to 5 impacts.

[0063] Embodiment 3 The embodiment provides a method for preparing a ceramic composite material resistant to multiple impacts, and specifically comprises the following steps. (1) Preparation of raw materials a. Preparation of ceramic slurry: 90 parts of β-silicon nitride powder, 10 parts of boron carbide powder and 3 parts of oleyl alcohol are mixed and uniformly ground to obtain a first powder; 50 parts of the first powder, 2 parts of No. 58 paraffin and 3 parts of No. 70 paraffin are mixed, heated to 110℃ and uniformly mixed to obtain a first premix, which is kept warm for use; 50 parts of the first premix, 5 parts of polyethylene oxide, 8 parts of polypropylene and 3 parts of thermoplastic butadiene rubber are added, and the mixture is continuously heated to 230℃ and uniformly mixed, and then cooled to room temperature to obtain the ceramic slurry.

[0064] b. Preparation of metal slurry: 90 parts of niobium-zirconium alloy, 10 parts of β-silicon carbide powder and 5 parts of aluminum oxide powder are mixed and uniformly ground to obtain a second powder; 50 parts of the second powder, 2 parts of No. 58 paraffin and 3 parts of No. 70 paraffin are mixed, heated to 110℃ and uniformly mixed to obtain a second premix, which is kept warm for use; 50 parts of the second premix, 5 parts of polyethylene oxide, 8 parts of polypropylene and 3 parts of thermoplastic butadiene rubber are added, and the mixture is continuously heated to 200-230℃ and uniformly mixed, and then cooled to room temperature to obtain the metal slurry.

[0065] (2) 3D printing The ceramic slurry and the metal slurry are 3D printed by a fused deposition 3D printing device with double nozzles, the ceramic slurry is 3D printed into a plurality of ceramic spring reinforcements 1, the metal slurry is 3D printed into a niobium-zirconium alloy base 2, each ceramic spring reinforcement 1 is embedded in the niobium-zirconium alloy base 2, and a composite blank block with a plurality of ceramic spring reinforcements 1 embedded in the niobium-zirconium alloy base 2 is prepared. Specifically, in the direction of the composite blank block, a plurality of ceramic spring reinforcements 1 are uniformly or non-uniformly embedded in the composite blank block; and each ceramic spring reinforcement 1 is coaxial with the direction of the composite blank block. At the same time, in any direction of the cross section of the composite blank block, at least one row of ceramic spring reinforcements 1 is uniformly or non-uniformly embedded in the composite blank block.

[0066] The weight percentage of the ceramic spring reinforcement 1 in the composite blank block is 35%.

[0067] (3) Degreasing treatment The composite blank block prepared by 3D printing is subjected to degreasing treatment, specifically, starting from room temperature, the temperature is raised at a rate of 5℃ / min to 650℃, and high-temperature degreasing treatment is carried out for 120min, and a porous preform is obtained.

[0068] (4) Infiltration and impregnation The Al-7Si alloy is melted, and the melting temperature is controlled at 750℃ to obtain an alloy melt; under the temperature condition of 750℃, the alloy melt enters into the porous preform obtained in step (3) along the channels after degreasing by pressure infiltration; wherein the pressure of pressure infiltration is controlled at 100MPa, and the pressure holding time is 15min; after pressure infiltration, polysilicocarbalkane solution (concentration 65wt%, solvent n-hexane) is impregnated into the porous preform by vacuum impregnation; wherein the vacuum degree of vacuum impregnation is controlled at 0.09MPa, and the vacuum impregnation time is 20h; the foregoing pressure infiltration-vacuum impregnation-pressure infiltration-vacuum impregnation process is repeated until the weight of the porous preform no longer increases, and an infiltration and impregnation body is obtained.

[0069] The volume ratio of the alloy melt to the porous preform used in the pressure infiltration is 1:3.

[0070] The volume ratio of the polysilicocarbalkane solution to the porous preform used in the vacuum impregnation is 1:3.

[0071] (5) Hot isostatic pressing sintering The infiltration and impregnation body obtained in step (4) is placed in a hot isostatic pressing sintering furnace, and is subjected to hot isostatic pressing sintering at 180MPa under nitrogen atmosphere protection, and is heated to 1460℃, and is kept for 3h, to prepare a ceramic composite material resistant to multiple impacts.

[0072] The anti-multiple-impact ceramic composite material prepared by the method has a hardness of 209 HB, a density of 99.2%, a fracture toughness of 10.5 MPa·m 1 / 2 , an interface shear strength between the metal and the ceramic in the ceramic composite material of 323 MPa, and no destructive cracking occurs after 5 impacts, and the anti-multiple-impact ceramic composite material still has the bulletproof ability.

[0073] Comparative Example 1 For intuitive comparison, the technical scheme of Example 1 is adopted in Comparative Example 1, except that the infiltration and impregnation step is omitted, and the porous preform obtained by the glue removal treatment is directly subjected to hot isostatic pressing sintering.

[0074] It is detected that the ceramic composite material prepared in Comparative Example 1 has a hardness of 104 HB, a density of 87.8%, a fracture toughness of 7.0 MPa·m 1 / 2 , an interface shear strength between the metal and the ceramic in the ceramic composite material of 151 MPa, and destructive cracking occurs after 3 impacts, and the ceramic composite material cannot maintain the bulletproof ability.

[0075] It can be seen that the anti-multiple-impact ceramic composite material prepared by the method has the following advantages. The ceramic slurry containing β-silicon nitride powder and boron carbide powder is combined with the metal slurry containing niobium-zirconium alloy, β-silicon carbide powder and aluminum oxide powder to perform 3D printing to inlay the composite material green body block with the ceramic spring reinforcing body in the niobium-zirconium alloy matrix, and then perform glue removal treatment to obtain a porous preform with multiple channels, which provides a densification path for the subsequent infiltration and impregnation of the alloy melt and polysilicon alkane solution, and is beneficial to the densification of the ceramic composite material. Then, the porous preform is subjected to multiple pressure infiltration-vacuum impregnation processes of the alloy melt and polysilicon alkane solution of Al-7Si alloy, the alloy melt and polysilicon alkane solution of Al-7Si alloy are introduced into the porous preform, and the infiltration and impregnation body is obtained. Then, in the process of hot isostatic pressing sintering, the polysilicon alkane in the infiltration and impregnation body is converted into silicon carbide ceramic, and the metal alloy is chemically bonded with the ceramic material under the action of high temperature to form a composite structure of metal-ceramic-metal-ceramic spring, which effectively improves the interface shear strength between the metal and the ceramic in the ceramic composite material, and simultaneously improves the hardness, fracture toughness and density thereof. At the same time, the buffering and energy absorption effect of the ceramic spring reinforcing body in the ceramic composite material further improves the anti-multiple-impact performance of the ceramic composite material. The above-mentioned methods are combined to effectively prevent the ceramic composite material from losing the bulletproof ability due to destructive cracking after suffering multiple impacts.

[0076] Unless otherwise stated, all percentages used in the present application are in mass percent.

[0077] Finally, it should be noted that the above only represents the preferred embodiments of the present application, and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that modifications can be made to the technical solutions described in the foregoing embodiments, or some of the technical features thereof can be replaced by equivalent features. Any modifications, equivalent replacements, improvements, and the like made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method for producing a ceramic composite material resistant to multiple impacts, characterized in that, The method comprises the following steps: 3D printing forming, degassing treatment, infiltration impregnation, and hot isostatic sintering. The 3D printing forming method is that ceramic slurry and metal slurry are simultaneously 3D printed, the ceramic slurry is 3D printed into a plurality of ceramic spring reinforcements (1), and the metal slurry is 3D printed into a niobium-zirconium alloy matrix (2); each ceramic spring reinforcement (1) is embedded in the niobium-zirconium alloy matrix (2) to obtain a composite blank block. The ceramic slurry comprises β-silicon nitride powder and boron carbide powder. The metal slurry comprises niobium-zirconium alloy, β-silicon carbide powder, and alumina powder. After the degassing treatment of the composite blank block, a porous preform is obtained. The infiltration impregnation method is that the porous preform is contacted with an alloy melt of Al-7Si alloy for pressure infiltration, and then contacted with a polysilicocarbosane solution for vacuum impregnation; the pressure infiltration-vacuum impregnation is repeated until the porous preform reaches a constant weight, to obtain an infiltration impregnated body. The infiltration impregnated body is sintered by hot isostatic pressing to obtain a ceramic composite material resistant to multiple impacts.

2. The method for preparing the ceramic composite material resistant to repeated impacts according to claim 1, characterized in that, The niobium-zirconium alloy matrix (2) of the composite blank block is embedded with a plurality of ceramic spring reinforcements (1) in a uniform or non-uniform distribution; each ceramic spring reinforcement (1) is coaxial with the impact direction of the composite blank block. The weight percentage of the ceramic spring reinforcements (1) in the composite blank block is 30-50%.

3. The method for preparing the ceramic composite material resistant to repeated impacts according to claim 1, characterized in that, The weight ratio of the β-silicon nitride powder to the boron carbide powder in the ceramic slurry is 85-90:8-10. The weight ratio of the niobium-zirconium alloy to the β-silicon carbide powder to the alumina powder in the metal slurry is 85-90:8-10:4-5.

4. The method for preparing the ceramic composite material resistant to repeated impacts according to claim 1, characterized in that, The degassing treatment method is that the temperature of the composite blank block is raised from room temperature to 600-650°C at a temperature raising rate of 2-5°C / min, and then the temperature is kept constant for degassing, to obtain the porous preform.

5. The method for preparing the ceramic composite material resistant to repeated impacts according to claim 1, characterized in that, The pressure infiltration temperature is 720-750°C, the pressure is 60-100 MPa, and the pressure infiltration time is 15-30 min. The vacuum degree of the vacuum impregnation is 0.080-0.099 MPa, and the vacuum impregnation time is 12-24 h.

6. The method for preparing the ceramic composite material resistant to repeated impacts according to claim 1, characterized in that, The volume ratio of the alloy melt to the porous preform in the pressure infiltration is 1:2-3. The volume ratio of the polysilicocarbosane solution to the porous preform in the vacuum impregnation is 1:2-3. The concentration of the polysilicocarbosane solution is 60-70 wt%.

7. The method for preparing the ceramic composite material resistant to repeated impacts according to claim 1, characterized in that, The hot isostatic sintering method is that the infiltration impregnated body is heated to 1400-1460°C under the protection of a nitrogen atmosphere and a pressure of 100-200 MPa, and then sintered for 2-6 h, to obtain the ceramic composite material resistant to multiple impacts.

8. The method for preparing the ceramic composite material resistant to repeated impacts according to claim 1, characterized in that, The preparation method of the ceramic slurry is as follows: 85-90 parts of β-silicon nitride powder, 8-10 parts of boron carbide powder and 1-3 parts of oleyl alcohol are uniformly mixed to obtain a first powder; 40-50 parts of the first powder, 1-2 parts of No. 58 paraffin and 2-3 parts of No. 70 paraffin are uniformly heated and mixed to obtain a first premix; 40-50 parts of the first powder, 3-5 parts of polyethylene oxide, 3-8 parts of polypropylene and 0.5-3 parts of thermoplastic butadiene rubber are added into 30-50 parts of the first premix, which are uniformly heated and mixed to obtain the ceramic slurry.

9. The method for preparing the ceramic composite material resistant to repeated impacts according to claim 1, characterized in that, The preparation method of the metal slurry is as follows: 85-90 parts of niobium-zirconium alloy, 8-10 parts of β-silicon carbide powder and 4-5 parts of aluminum oxide powder are uniformly mixed to obtain a second powder; 40-50 parts of the second powder, 1-2 parts of No. 58 paraffin and 2-3 parts of No. 70 paraffin are uniformly heated and mixed to obtain a second premix; 40-50 parts of the second powder, 3-5 parts of polyethylene oxide, 3-8 parts of polypropylene and 0.5-3 parts of thermoplastic butadiene rubber are added into 30-50 parts of the second premix, which are uniformly heated and mixed to obtain the metal slurry.

10. A ceramic composite material resistant to multiple impacts prepared by the preparation method of any one of claims 1-9.

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