Preparation method of multilayer multiphase imitation ceramic material

Abstract

The invention provides a preparation method of a multi-layer and multi-phase imitation ceramic material, and relates to the field of bulletproof materials, and the preparation method comprises the following steps: S1, designing a multi-layer and multi-phase imitation ceramic layer: designing a multi-layer ceramic layer formed by alternately laying a hard layer material and a soft layer material; s2, designing a cavity matrix structure: designing a cavity of a lattice structure in the multilayer ceramic layer; s3, preparing a ceramic panel base body: obtaining the ceramic panel base body by adopting a photocuring printing technology; and S4, metal phase infiltration is conducted, specifically, the ceramic panel base body is infiltrated with a molten metal material through infiltration. According to the method, through the ceramic layer structure formed by alternately stacking the hard layers and the soft layers and the metal material infiltrated in the dot matrix mode, the supporting efficiency, fracture toughness and energy absorption rate of ceramics are effectively improved, and the problem that an existing bulletproof plate is insufficient in multi-shot striking resistance is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of bulletproof materials, and particularly relates to a preparation method of a multilayer and multiphase biomimetic ceramic material. BACKGROUND

[0002] The bulletproof plate adopts a double-layer structure of a ceramic panel and a composite material back plate, wherein the ceramic panel mainly adopts any one of B4C, Al2O3 and SiC, and the composite material back plate mainly adopts any one of ultrahigh molecular weight polyethylene, aramid fiber and carbon fiber. Since the ceramic material has the advantages of low density, high hardness, high compressive strength and the like, the existing bulletproof plate mainly takes the high hardness of the ceramic material (namely, B4C, Al2O3 and SiC) as the bulletproof core, but the brittle nature of the ceramic material causes it to easily lose structural continuity after the first impact: the first impact forms a "inverted pyramid" damage cone on the surface of the ceramic, accompanied by a large number of radial and hoop cracks, due to the high brittleness of the high-hardness ceramic (for example, B4C), the cracks rapidly expand along the grain boundaries or defects, causing the ceramic layer to break and lose the protection effect during the continuous multiple impact process (such as the second impact); while the ceramic with relatively high toughness (such as Al2O3) can slow down the crack propagation rate to a certain extent during the first impact process, but its hardness is relatively low, and the broken particles after the impact are easily "plowed" by the bullet, resulting in a decrease in the kinetic energy attenuation efficiency of the bullet during the second bulletproof process. At the same time, the existing ceramic panel is prone to local stress concentration during non-frontal impact, and cannot effectively disperse stress, thereby causing the ceramic panel to rapidly crack and lose the protection effect. SUMMARY

[0003] In view of the problems in the prior art, the present application aims to provide a preparation method of a multilayer and multiphase biomimetic ceramic material, which prepares a multilayer biomimetic ceramic material with a point array structure space by a ceramic layer structure design of alternating hard layer and soft layer and a metal material of point array sintering, improves the support performance of the ceramic, improves the fracture toughness and energy absorption rate of the ceramic, and effectively solves the problem of insufficient multiple impact resistance of the existing bulletproof plate.

[0004] The purpose of the present application is achieved by the following technical scheme: The present application provides a preparation method of a multilayer and multiphase biomimetic ceramic material, which comprises the following steps: Step S1, design of a multilayer and multiphase biomimetic ceramic layer: first, any two ceramic materials are selected from B4C, Al2O3, SiC and TiB2, and the two ceramic materials are divided into hard layer material and soft layer material (namely, the ceramic material with high hardness is used as the hard layer material, and the ceramic material with low hardness is used as the soft layer material) according to the hardness of the materials, the hard layer material and the soft layer material are alternately laid and stacked to form a multilayer ceramic layer; Step S2, cavity matrix structure design: a metal lattice model composed of multiple cell structures is established by an array method, and the metal lattice model is matched with a multi-layer ceramic layer structure to form a multi-layer ceramic model with a lattice structure cavity inside; Step S3, ceramic panel substrate preparation: according to the multi-layer ceramic layer design in step S1, hard layer ceramic slurry and soft layer ceramic slurry are respectively configured, and the light curing printing technology is adopted to perform layer-by-layer printing of the hard layer and the soft layer according to the multi-layer ceramic model in step S2 (according to the reserved lattice structure cavity in the multi-layer ceramic model); after printing, cleaning, degreasing and sintering treatment are sequentially performed to obtain a ceramic panel substrate; Step S4, metal phase infiltration: by infiltrating molten metal material into the ceramic panel substrate, a biomimetic ceramic material with embedded metal lattice structure is obtained.

[0005] Based on the further optimization of the above scheme, in the multi-layer ceramic layer, the thickness of the hard layer is 1-5 mm, the thickness of the soft layer is 0.5-1 mm, and the thickness ratio of the hard layer to the soft layer is 2-10:1.

[0006] Based on the further optimization of the above scheme, the cell structure adopts any one of a tetrahedral structure, a pyramid structure and an X-shaped structure (selected according to different defense projectiles); the thickness t of the plate core of the cell structure is 1-3 mm, the width d of the plate core is 1-3 mm, the length a of the single arm is 20-30 mm, the arm spread width b is 10-20 mm, the height h is 4-8 mm, and the single arm inclination angle α is 30°-60°.

[0007] Based on the further optimization of the above scheme, the hard layer slurry includes hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amounts of them are: 50-60wt%, 30-40wt%, 2-4wt%, 1.8-2.6wt%, 0.6-1wt%, and 3-5wt%.

[0008] Based on the further optimization of the above scheme, the hard ceramic mixed powder includes B4C ceramic powder (purity ≥ 99%, particle size 1-2 μm, hardness about 3180 kgf / mm 2 ), Ti3SiC2 powder (particle size 3-5 μm), nano-SiC (particle size 40-60 nm) and nano-carbon black (particle size 20-40 nm); wherein the amount of Ti3SiC2 powder is 6-8wt% of the hard ceramic mixed powder, the amount of nano-SiC is 0.4-0.6wt% of the hard ceramic mixed powder, the amount of nano-carbon black is 0.15-0.25wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder.

[0009] Based on the further optimization of the above scheme, the soft layer slurry comprises soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each component is 40-50wt%, 40-50wt%, 2.6-4.6wt%, 1.4-2.2wt%, 0.9-1.3wt%, and 2.5-4.5wt%, respectively.

[0010] Based on the further optimization of the above scheme, the soft ceramic mixed powder comprises Al2O3 ceramic powder (particle size 1-2μm, hardness about 2000kgf / mm 2 ), glass powder (particle size 4-6μm), CrB powder (particle size 1-2μm), nano-AlN (particle size 80-120nm) and nano-ZrO2 (particle size 40-60nm); wherein the amount of glass powder is 11-13wt% of the soft ceramic mixed powder, the amount of CrB powder is 2.5-3.5wt% of the soft ceramic mixed powder, the amount of nano-AlN is 1.8-2.2wt% of the soft ceramic mixed powder, the amount of nano-ZrO2 is 1.3-1.7wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder.

[0011] Based on the further optimization of the above scheme, the glass powder is prepared from SiO2, Al2O3, CaO and B2O3, specifically: SiO2, Al2O3, CaO and B2O3 are proportioned according to the mass ratio of 9-11:2.5-3.5:3.5-4.5:2.5-3.5, and then melted at 1150-1250℃ for 1.8-2.2h, followed by quenching and ball milling.

[0012] Based on the further optimization of the above scheme, the photoinitiator is a compound of photoinitiator 819 and photoinitiator TPO, and the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:2 or 3 (the mass ratio of photoinitiator 819 to photoinitiator TPO in the hard layer slurry is 1:2, and the mass ratio of photoinitiator 819 to photoinitiator TPO in the soft layer slurry is 1:3); the dispersant is a compound of BYK-9076 and EL-6976, and the mass ratio of BYK-9076 to EL-6976 is 2 or 3:1 (the mass ratio of BYK-9076 to EL-6976 in the hard layer slurry is 2:1, and the mass ratio of BYK-9076 to EL-6976 in the soft layer slurry is 3:1); the silane coupling agent is any one of KH560 and KH550.

[0013] Based on the further optimization of the above scheme, the light curing printing imports the model file that has been sliced on the DLP printer, and synchronously sets the printing parameters: light output power 200%-250%, light output time 7-10s.

[0014] Based on further optimization of the above scheme, the cleaning after printing in step S3 is specifically: ultrasonic cleaning with isopropyl alcohol with a concentration of 99% or above for 12-18 min to remove un-solidified resin and residual slurry.

[0015] Based on further optimization of the above scheme, the debinding in step S3 is specifically: in an air atmosphere, oxygen is introduced, the oxygen flow is 0.4-0.6 L / min; first, the temperature is raised to 180-220°C at a rate of 4.5-5.5°C / min, and the temperature is kept for 0.8-1.2 h; then, the temperature is raised to 380-420°C at a rate of 1.5-2.5°C / min, and the temperature is kept for 2.8-3.2 h; finally, the temperature is raised to 580-620°C at a rate of 0.5-1.5°C / min, and the temperature is kept for 1-2 h.

[0016] Based on further optimization of the above scheme, the sintering in step S3 is specifically: in an argon atmosphere, the argon flow is 7.5-8.5 L / min, first, the temperature is raised to 1150-1250°C at a rate of 4.5-5.5°C / min, and the temperature is kept for 1.5-2.5 h; then, the temperature is raised to 1530-1570°C at a rate of 1-2°C / min, and the temperature is kept for 1.5-2.5 h; finally, the furnace is cooled to 620-680°C.

[0017] Based on further optimization of the above scheme, the molten metal material in step S4 is any one of Al-based alloy or Ti-based alloy, specifically: Al-5Mg-2Si-1Cu (wt%) or Ti-6Al-2Si-1Nb (wt%).

[0018] Based on further optimization of the above scheme, the metal phase infiltration is specifically: First, at room temperature, the sintered ceramic plate is immersed in a mixed solution of 10% concentration HF and 5% concentration nitric acid for 18-22 min; then, it is washed with deionized water until it is neutral, and it is dried at 130-170°C for 1.8-2.2 h; Then, a carbon layer with a thickness of 50-100 nm is deposited on one side of the ceramic panel substrate with a dot matrix cavity using chemical vapor deposition; After that, in an inert atmosphere, Al-5Mg-2Si-1Cu (wt%) is heated to 700-750°C until the alloy is completely melted; the ceramic panel substrate obtained in step S3 is kept at 650-700°C for 30-60 min, and then the ceramic panel substrate after keeping is immersed in the molten alloy, a pressure of 5-8 MPa is applied for 1.5-3 h to fill the cavity matrix with molten metal; Finally, the temperature is lowered to room temperature at a rate of 5-8°C / min to obtain a biomimetic ceramic material.

[0019] The following are the technical effects possessed by the present scheme: The present application divides ceramic materials into hard layer materials and soft layer materials according to the hardness of ceramic materials, and forms a multilayer biomimetic ceramic structure by alternately laying the hard layer materials and the soft layer materials. The soft-hard superimposed ceramic structure effectively prolongs the crack propagation path, improves the fracture toughness of the ceramic structure, and improves the energy absorption effect. Meanwhile, the present application uses 3D printing technology to reserve a cavity of a dot matrix structure on the multilayer biomimetic ceramic structure, and fills a specific metal material in the cavity. The metal material forms a support for the ceramic layer structure, thereby improving the support performance of the ceramic structure and further improving the energy absorption rate of the ceramic material and avoiding rapid crack propagation during multiple impact processes.

[0020] The present application uses B4C ceramic powder, Ti3SiC2 powder, nano-SiC and nano-carbon black as ceramic powder of hard layer materials, and uses Al2O3 ceramic powder, glass powder, CrB powder, nano-AlN and nano-ZrO2 as ceramic powder of soft layer materials. The in-situ generated whiskers and particles effectively suppress crack propagation and reduce the risk of brittle fracture of the ceramic structure after single impact. The impact stress is effectively buffered, and the secondary damage of the hard layer caused by stress concentration is reduced. Meanwhile, the combination of soft layer materials and hard layer materials effectively reduces the risk of interface cracking caused by cold and hot cycles or impact thermal stress, improves the interface bonding capacity between ceramic layers, effectively suppresses the delamination failure of the ceramic layer structure during impact, and ensures the integrity of the structure. In addition, the combination of ceramic layer structure and metal filling material not only ensures the gapless combination of metal material and ceramic interface, guarantees the complete filling of metal material, avoids stress concentration during impact, fully plays the supporting role of metal material, effectively suppresses the interface reaction between metal material and ceramic material, avoids the generation of a large number of interface brittle phases, further improves the mechanical properties of the ceramic material as a whole, and avoids the rapid generation and expansion of cracks during impact. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a schematic diagram of the cell structure in the embodiment of the present application; wherein, Figure 1 (a) is a schematic diagram of a tetrahedral structure, Figure 1 (b) is a schematic diagram of a pyramid structure, Figure 1 (c) is a schematic diagram of an X-shaped structure.

[0022] Figure 2 is a schematic diagram of the preparation process of the ceramic panel substrate in the embodiment of the present application. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly described below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0024] Example 1: A method for preparing a multi-layer multi-phase biomimetic ceramic material, comprising: Step S1, multi-layer multi-phase bionic ceramic layer design: First, select B4C (hardness about 3180 kgf / mm 2 ), Al2O3 (hardness about 2000 kgf / mm 2 ) are used as the main ceramic materials for the hard layer material and the soft layer material respectively. The hard layer material and the soft layer material are alternately stacked to form a multi-layer ceramic layer, wherein: the hard layer thickness is 1 mm, and the soft layer thickness is 0.5 mm (7 hard layer layers, 6 soft layer layers, and a total thickness of 10 mm).

[0025] Step S2, cavity matrix structure design: a metal lattice model composed of multiple cell structures is established by an array method, and the metal lattice model is matched with the multilayer ceramic layer structure to form a multilayer ceramic model with a lattice structure cavity inside (i.e., the array distribution of the cavities on the multilayer ceramic model matches the cell structure, such as Figure 2 As shown in the model design of Figure 1 As shown, the cellular structure adopts any one of the tetrahedral structure, pyramid structure and X-shaped structure (selected according to the different types of bullets to be defended); the core thickness t of the cellular structure is 1 mm, the core width d is 1 mm, the single arm length a is 20 mm, the arm span width b is 10 mm, the height h is 4 mm, and the single arm inclination angle α is 30°.

[0026] Step S3, preparation of ceramic panel substrate: According to the multi-layer ceramic layer design in step S1, hard layer ceramic slurry and soft layer ceramic slurry are respectively prepared: the hard layer slurry includes hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickener N-228, and the amounts thereof are: 50wt%, 40wt%, 3.8wt%, 2wt%, 0.9wt%, and 3.5wt%. The hard ceramic mixed powder includes B4C ceramic powder (purity ≥99%, particle size 1-2μm, hardness of about 3180kgf / mm 2), Ti3SiC2 powder (particle size 3-5μm), nano SiC (particle size 40-60nm) and nano carbon black (particle size 20-40nm); wherein, the amount of Ti3SiC2 powder is 6wt% of the hard ceramic mixed powder, the amount of nano SiC is 0.4wt% of the hard ceramic mixed powder, the amount of nano carbon black is 0.15wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder; the soft layer slurry includes soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickener N-228, and the amount thereof is: 40wt%, 50wt%, 4.2wt%, 1.6wt%, 1.2wt%, 3wt%, and the soft ceramic mixed powder includes Al2O3 ceramic powder (particle size 1-2μm, hardness of about 2000kgf / mm 2 ), glass powder (particle size 4-6μm), CrB powder (particle size 1-2μm), nano AlN (particle size 80-120nm) and nano ZrO2 (particle size 40-60nm); wherein, the amount of glass powder is 11wt% of the soft ceramic mixed powder, the amount of CrB powder is 2.5wt% of the soft ceramic mixed powder, the amount of nano AlN is 1.8wt% of the soft ceramic mixed powder, the amount of nano ZrO2 is 1.3wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder. The glass powder is prepared by SiO2, Al2O3, CaO, and B2O3. Specifically, SiO2, Al2O3, CaO, and B2O3 are prepared in a mass ratio of 9:2.5:3.5:2.5, and are melted at 1150°C for 2.2h, and then quenched and ball milled.

[0027] The photoinitiator is a compound of photoinitiator 819 and photoinitiator TPO, and the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:2 or 3 (in the hard layer slurry, the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:2; in the soft layer slurry, the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:3); the dispersant is a compound of BYK-9076 and EL-6976, and the mass ratio of BYK-9076 to EL-6976 is 2 or 3:1 (in the hard layer slurry, the mass ratio of BYK-9076 to EL-6976 is 2:1; in the soft layer slurry, the mass ratio of BYK-9076 to EL-6976 is 3:1); and the silane coupling agent is KH550.

[0028] The preparation method of the hard layer slurry and the soft layer slurry is as follows: the corresponding raw materials of the slurry are stirred respectively according to the above-mentioned formulation, and then placed in a homogenizer for averaging treatment to obtain the corresponding ceramic layer slurry.

[0029] According to the multilayer ceramic model in step S2, the hard layer and the soft layer are printed layer by layer (according to the lattice structure cavity reserved in the multilayer ceramic model) by using the light curing printing technology, that is, the sliced model file is imported on the DLP printer, and the printing parameters are set synchronously: light output power 200%, light output time 10s, the configured ceramic slurry is spread on the forming table according to the designed model, and light curing is performed, and the process is repeated layer by layer until the printing is completed.

[0030] After printing is completed, the printed sample is gently scooped off from the forming table, and then cleaning, debinding and sintering treatment are sequentially performed to obtain a ceramic panel substrate; cleaning: isopropyl alcohol with a concentration of 99% or above is used for ultrasonic cleaning for 12 minutes to remove unhardened resin and residual slurry. Debinding: in an air atmosphere, oxygen is introduced, and the oxygen flow is 0.4L / min; first, the temperature is raised to 180°C at a rate of 4.5°C / min, and the temperature is kept for 1.2h; then, the temperature is raised to 380°C at a rate of 1.5°C / min, and the temperature is kept for 3.2h; finally, the temperature is raised to 580°C at a rate of 0.5°C / min, and the temperature is kept for 2h. Sintering: in an argon atmosphere, the argon flow is 7.5L / min, first, the temperature is raised to 1150°C at a rate of 4.5°C / min, and the temperature is kept for 2.5h; then, the temperature is raised to 1530°C at a rate of 1°C / min, and the temperature is kept for 2.5h; finally, the furnace is cooled to 620°C.

[0031] Step S4, metal phase infiltration: by infiltrating molten metal material into the ceramic panel substrate, a biomimetic ceramic material with embedded metal lattice structure is obtained; the molten metal material is Al-5Mg-2Si-1Cu (wt%, that is, 5wt% of Mg, 2wt% of Si and 1wt% of Cu are added to the aluminum matrix to form a molten metal alloy material).

[0032] The metal phase infiltration is specifically as follows: First, the sintered ceramic plate is soaked in a mixed solution of 10% concentration HF and 5% concentration nitric acid at room temperature for 18 minutes, then washed with deionized water until neutral, and dried at 130°C for 2.2h; then, a carbon layer with a thickness of 50-100nm is deposited on one side of the ceramic panel substrate with a lattice cavity by using chemical vapor deposition method; then, the Al-5Mg-2Si-1Cu (wt%) is heated to 700°C in an inert atmosphere until the alloy is completely melted; the ceramic panel substrate obtained in step S3 is kept at 650°C for 60min, and then the ceramic panel substrate after keeping is immersed in the molten alloy, a pressure of 5MPa is applied for 3h to fill the cavity matrix with molten metal; finally, the temperature is lowered to room temperature at a rate of 5°C / min to obtain a biomimetic ceramic material.

[0033] Example 2: A preparation method of a multilayer and multiphase biomimetic ceramic material, comprising: Step S1, design of a multilayer and multiphase biomimetic ceramic layer: first, B4C (hardness about 3180 kgf / mm 2 ) and Al2O3 (hardness about 2000 kgf / mm 2 ) are selected as the main ceramic materials of the hard layer material and the soft layer material, respectively, the hard layer material and the soft layer material are alternately laid to form a multilayer ceramic layer, wherein: the thickness of the hard layer is 3 mm, the thickness of the soft layer is 0.75 mm (3 layers of hard layer and 2 layers of soft layer, total thickness 10.5 mm).

[0034] Step S2, design of a cavity matrix structure: a metal lattice model composed of multiple cell structures is established by an array method, and the metal lattice model is matched with the multilayer ceramic layer structure to form a multilayer ceramic model with a point array structure cavity inside (i.e., the model designed as shown in Figure 2 ); as shown in Figure 1 , the cell structure adopts any one of a tetrahedral structure, a pyramid structure and an X-shaped structure (selected according to different types of defense bullets); the thickness t of the plate core of the cell structure is 2 mm, the width d of the plate core is 2 mm, the length a of the single arm is 25 mm, the width b of the arm spread is 15 mm, the height h is 6 mm, and the single arm inclination angle α is 45°.

[0035] Step S3, preparation of a ceramic panel substrate: the hard layer ceramic slurry and the soft layer ceramic slurry are respectively configured according to the multilayer ceramic layer design in step S1: the hard layer slurry includes hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each is: 55wt%, 35wt%, 3wt%, 2.2wt%, 0.8wt%, 4wt%, the hard ceramic mixed powder includes B4C ceramic powder (purity ≥ 99%, particle size 1-2 μm, hardness about 3180 kgf / mm 2), Ti3SiC2 powder (particle size 3-5μm), nano SiC (particle size 40-60nm) and nano carbon black (particle size 20-40nm); wherein, the amount of Ti3SiC2 powder is 7wt% of the hard ceramic mixed powder, the amount of nano SiC is 0.5wt% of the hard ceramic mixed powder, the amount of nano carbon black is 0.2wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder; the soft layer slurry includes soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickener N-228, and the amount thereof is: 45wt%, 45wt%, 3.6wt%, 1.8wt%, 1.1wt%, 3.5wt%, and the soft ceramic mixed powder includes Al2O3 ceramic powder (particle size 1-2μm, hardness of about 2000kgf / mm 2 ), glass powder (particle size 4-6μm), CrB powder (particle size 1-2μm), nano AlN (particle size 80-120nm) and nano ZrO2 (particle size 40-60nm); wherein, the amount of glass powder is 12wt% of the soft ceramic mixed powder, the amount of CrB powder is 3wt% of the soft ceramic mixed powder, the amount of nano AlN is 2wt% of the soft ceramic mixed powder, the amount of nano ZrO2 is 1.5wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder. The glass powder is prepared by SiO2, Al2O3, CaO, and B2O3. Specifically, SiO2, Al2O3, CaO, and B2O3 are prepared in a mass ratio of 10:3:4:3, and are melted at 1200°C for 2h, and then quenched and ball-milled.

[0036] The photoinitiator is a compound of photoinitiator 819 and photoinitiator TPO, and the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:2 or 3 (in the hard layer slurry, the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:2; in the soft layer slurry, the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:3); the dispersant is a compound of BYK-9076 and EL-6976, and the mass ratio of BYK-9076 to EL-6976 is 2 or 3:1 (in the hard layer slurry, the mass ratio of BYK-9076 to EL-6976 is 2:1; in the soft layer slurry, the mass ratio of BYK-9076 to EL-6976 is 3:1); the silane coupling agent is KH560.

[0037] The preparation method of the hard layer slurry and the soft layer slurry is as follows: the corresponding raw materials of the slurry are stirred respectively according to the above-mentioned formulation, and then placed in a homogenizer for averaging treatment to obtain the corresponding ceramic layer slurry.

[0038] According to the multilayer ceramic model in step S2, the hard layer and the soft layer are printed layer by layer (according to the lattice structure cavity reserved in the multilayer ceramic model), that is, the sliced model file is imported on the DLP printer, and the printing parameters are set synchronously: light output power 225%, light output time 8.5s, the configured ceramic slurry is spread on the forming table according to the design model, and light curing is performed, and the process is repeated layer by layer until printing is completed.

[0039] After printing is completed, the printed sample is gently scooped off from the forming table, and then cleaning, debinding and sintering treatment are sequentially performed to obtain a ceramic panel substrate; cleaning: isopropyl alcohol with a concentration of 99% or above is used for ultrasonic cleaning for 15 minutes to remove unhardened resin and residual slurry. Debinding: in an air atmosphere, oxygen is introduced, the oxygen flow is 0.5L / min; first, the temperature is raised to 200°C at a rate of 5°C / min, and the temperature is kept for 1h; then, the temperature is raised to 400°C at a rate of 2°C / min, and the temperature is kept for 3h; finally, the temperature is raised to 600°C at a rate of 1°C / min, and the temperature is kept for 1.5h. Sintering: in an argon atmosphere, the argon flow is 8L / min, first, the temperature is raised to 1200°C at a rate of 5°C / min, and the temperature is kept for 2h; then, the temperature is raised to 1550°C at a rate of 1.5°C / min, and the temperature is kept for 2h; finally, the furnace is cooled to 650°C.

[0040] Step S4, metal phase infiltration: by infiltrating a molten metal material into the ceramic panel substrate, a biomimetic ceramic material with an embedded metal lattice structure is obtained; the molten metal material uses Al-5Mg-2Si-1Cu (wt%, that is, 5wt% Mg, 2wt% Si and 1wt% Cu are added to the aluminum matrix to form a molten metal alloy material).

[0041] The metal phase infiltration is specifically as follows: First, at room temperature, the sintered ceramic plate is soaked in a mixed solution of 10% concentration HF and 5% concentration nitric acid for 20 minutes, then washed with deionized water until neutral, and dried at 150°C for 2 hours; then, a carbon layer with a thickness of 50-100nm is deposited on one side of the ceramic panel substrate with a lattice cavity using chemical vapor deposition; then, under an inert atmosphere, Al-5Mg-2Si-1Cu (wt%) is heated to 725°C until the alloy is completely melted; the ceramic panel substrate obtained in step S3 is kept at 675°C for 45 minutes, and then the ceramic panel substrate after keeping is immersed in the molten alloy, a pressure of 6.5MPa is applied for 2.2h to fill the cavity matrix with molten metal; finally, the temperature is lowered to room temperature at a rate of 6.5°C / min to obtain a biomimetic ceramic material.

[0042] Example 3: A method for preparing a multilayer and multiphase biomimetic ceramic material, comprising: Step S1, multi-layered multi-phase biomimetic ceramic layer design: first, B4C (hardness about 3180 kgf / mm 2 , Al2O3 (hardness about 2000 kgf / mm 2 ) are selected as the main ceramic materials of hard layer material and soft layer material respectively, and the hard layer material and the soft layer material are alternately laid to form a multi-layer ceramic layer, wherein the thickness of the hard layer is 5 mm and the thickness of the soft layer is 1 mm (2 layers of hard layer and 1 layer of soft layer, total thickness 11 mm).

[0043] Step S2, cavity matrix structure design: a metal lattice model composed of multiple cell structures is established by array method, and the metal lattice model is matched with the multi-layer ceramic layer structure to form a multi-layer ceramic model with a point array structure cavity inside (i.e. a multi-layer ceramic model with an array distributed cavity matching the cell structure, as shown in the model design of Figure 2 ); as shown in Figure 1 , the cell structure adopts any one of tetrahedral structure, pyramid structure and X-shaped structure (selected according to different types of defense bullets); the thickness t of the plate core of the cell structure is 3 mm, the width d of the plate core is 3 mm, the length a of the single arm is 30 mm, the width b of the arm spread is 20 mm, the height h is 8 mm, and the single arm inclination angle a is 60°.

[0044] Step S3, ceramic panel substrate preparation: according to the multi-layer ceramic layer design in step S1, the hard layer ceramic slurry and the soft layer ceramic slurry are configured respectively: the hard layer slurry includes hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each is: 60wt%, 30wt%, 2.4wt%, 2.4wt%, 0.7wt%, 4.5wt%, the hard ceramic mixed powder includes B4C ceramic powder (purity ≥ 99%, particle size 1-2 μm, hardness about 3180 kgf / mm 2 ), Ti3SiC2 powder (particle size 3-5 μm), nano-SiC (particle size 40-60 nm) and nano-carbon black (particle size 20-40 nm); wherein the amount of Ti3SiC2 powder is 8wt% of the hard ceramic mixed powder, the amount of nano-SiC is 0.6wt% of the hard ceramic mixed powder, the amount of nano-carbon black is 0.25wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder; the soft layer slurry includes soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each is: 50wt%, 40wt%, 3wt%, 2wt%, 1wt%, 4wt%, the soft ceramic mixed powder includes Al2O3 ceramic powder (particle size 1-2 μm, hardness about 2000 kgf / mm 2glass powder (particle size 4-6 μm), CrB powder (particle size 1-2 μm), nano-AlN (particle size 80-120 nm) and nano-ZrO2 (particle size 40-60 nm); wherein the glass powder accounts for 13 wt% of the soft ceramic mixed powder, the CrB powder accounts for 3.5 wt% of the soft ceramic mixed powder, the nano-AlN accounts for 2.2 wt% of the soft ceramic mixed powder, the nano-ZrO2 accounts for 1.7 wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder; the glass powder is prepared from SiO2, Al2O3, CaO and B2O3, specifically: SiO2, Al2O3, CaO and B2O3 are proportioned according to a mass ratio of 11:3.5:4.5:3.5, and then melted at 1250°C for 1.8 h, followed by quenching and ball milling.

[0045] The photoinitiator is a compound of photoinitiator 819 and photoinitiator TPO, and the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:2 or 3 (the mass ratio of photoinitiator 819 to photoinitiator TPO in the hard layer slurry is 1:2, and the mass ratio of photoinitiator 819 to photoinitiator TPO in the soft layer slurry is 1:3); the dispersant is a compound of BYK-9076 and EL-6976, and the mass ratio of BYK-9076 to EL-6976 is 2 or 3:1 (the mass ratio of BYK-9076 to EL-6976 in the hard layer slurry is 2:1, and the mass ratio of BYK-9076 to EL-6976 in the soft layer slurry is 3:1); the silane coupling agent is KH560.

[0046] The preparation method of the hard layer slurry and the soft layer slurry is as follows: the corresponding raw materials of the slurry are respectively stirred according to the above proportioning, and then subjected to homogenization treatment in a homogenizer to obtain the corresponding ceramic layer slurry.

[0047] The light curing printing technology is used to perform layer-by-layer printing of the hard layer and the soft layer according to the multi-layer ceramic model in step S2 (according to the reserved lattice structure cavity of the multi-layer ceramic model), that is, the sliced model file is imported into the DLP printer, and the printing parameters are set synchronously: light output power 250%, light output time 7 s, the configured ceramic slurry is spread on the forming table according to the design model, and light curing is performed, which is repeated layer by layer until the printing is completed.

[0048] After printing, the printed sample is gently scooped off the forming table, and sequentially cleaned, degreased and sintered to obtain the ceramic panel substrate; cleaning: using isopropyl alcohol with a concentration of 99% or above for ultrasonic cleaning for 18 min to remove un-solidified resin and residual slurry. Degreasing: in an air atmosphere, oxygen is introduced, the oxygen flow is 0.6 L / min; first, the temperature is raised to 220 DEG C at a rate of 5.5 DEG C / min, and the temperature is kept for 0.8 h; then, the temperature is raised to 420 DEG C at a rate of 2.5 DEG C / min, and the temperature is kept for 2.8 h; finally, the temperature is raised to 620 DEG C at a rate of 1.5 DEG C / min, and the temperature is kept for 1 h. Sintering: in an argon atmosphere, the argon flow is 8.5 L / min, first, the temperature is raised to 1250 DEG C at a rate of 5.5 DEG C / min, and the temperature is kept for 1.5 h; then, the temperature is raised to 1570 DEG C at a rate of 2 DEG C / min, and the temperature is kept for 1.5 h; finally, the furnace is cooled to 680 DEG C.

[0049] Step S4, metal phase infiltration: by infiltrating the molten metal material into the ceramic panel substrate to obtain a biomimetic ceramic material with an embedded metal lattice structure; the molten metal material uses Al-5Mg-2Si-1Cu (wt%, that is, 5wt% Mg, 2wt% Si and 1wt% Cu are added to the aluminum matrix to form a molten metal alloy material).

[0050] The metal phase infiltration is specifically: First, at room temperature, the sintered ceramic plate is soaked in a mixed solution of 10% concentration HF and 5% concentration nitric acid for 22 min, then washed with deionized water until neutral, and dried at 170 DEG C for 1.8 h; then, a carbon layer with a thickness of 50-100 nm is deposited on one side of the ceramic panel substrate with a lattice cavity using chemical vapor deposition; then, Al-5Mg-2Si-1Cu (wt%) is heated to 750 DEG C in an inert atmosphere until the alloy is completely melted; the ceramic panel substrate obtained in step S3 is kept at 700 DEG C for 30 min, and then the ceramic panel substrate after heat preservation is immersed in the molten alloy, and a pressure of 8 MPa is applied for 1.5 h to fill the cavity matrix with molten metal; finally, the temperature is lowered to room temperature at a rate of 8 DEG C / min to obtain a biomimetic ceramic material.

[0051] Example 4: As another preferred embodiment of the present application, on the basis of any one of examples 1-3, the chemical vapor deposition method is used to deposit a carbon layer with a thickness of 50-100 nm on one side of the ceramic panel substrate with a lattice cavity, which is specifically: The ceramic panel substrate is first placed in a deposition chamber at 200-300 DEG C for 30-40 min; argon is first introduced at a rate of 25-30 mL / min to discharge the residual air in the chamber, and then hydrogen is introduced at a flow rate of 4-8 mL / min, and stabilized for 3-5 min; then, the pressure in the deposition chamber is adjusted to 50-60 Pa, and the radio frequency power is started, and the power is slowly increased to 100 W; then, carbon source gas methane is introduced at a rate of 8-10 mL / min, and the pressure is maintained at 50-60 Pa, and carbon layer deposition is performed, and the deposition time is determined according to the specific thickness and deposition rate.

[0052] Comparative Example 1 A method for preparing a multilayer ceramic material, comprising: Step S1, multilayer and multiphase biomimetic ceramic layer design: consistent with step S1 in Example 2.

[0053] Step S2, cavity matrix structure design: consistent with step S2 in Example 2.

[0054] Step S3, ceramic panel substrate preparation: according to the multilayer ceramic layer design in step S1, hard layer ceramic slurry and soft layer ceramic slurry are respectively configured: the hard layer slurry includes hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amounts of them are: 55wt%, 35wt%, 3wt%, 2.2wt%, 0.8wt%, 4wt%, the hard ceramic mixed powder includes B4C ceramic powder (purity ≥ 99%, particle size 1-2 μm, hardness about 3180 kgf / mm 2 ), nano-SiC (particle size 40-60 nm) and nano-carbon black (particle size 20-40 nm); wherein the amount of nano-SiC is 0.5wt% of the hard ceramic mixed powder, the amount of nano-carbon black is 0.2wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder; the soft layer slurry includes soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amounts of them are: 45wt%, 45wt%, 3.6wt%, 1.8wt%, 1.1wt%, 3.5wt%, the soft ceramic mixed powder includes Al2O3 ceramic powder (particle size 1-2 μm, hardness about 2000 kgf / mm 2Glass powder (particle size 4-6 μm), CrB powder (particle size 1-2 μm), nano-AlN (particle size 80-120 nm) and nano-ZrO2 (particle size 40-60 nm); wherein the amount of glass powder is 12 wt% of the soft ceramic mixed powder, the amount of CrB powder is 3 wt% of the soft ceramic mixed powder, the amount of nano-AlN is 2 wt% of the soft ceramic mixed powder, the amount of nano-ZrO2 is 1.5 wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder; the glass powder is prepared from SiO2, Al2O3, CaO and B2O3, specifically: SiO2, Al2O3, CaO and B2O3 are proportioned according to a mass ratio of 10:3:4:3, and then melted at 1200°C for 2 h, followed by quenching and ball milling.

[0055] The photoinitiator is a compound of photoinitiator 819 and photoinitiator TPO, the mass ratio of photoinitiator 819 to photoinitiator TPO being 1:2 or 3 (the mass ratio of photoinitiator 819 to photoinitiator TPO in the hard layer slurry is 1:2, and the mass ratio of photoinitiator 819 to photoinitiator TPO in the soft layer slurry is 1:3); the dispersant is a compound of BYK-9076 and EL-6976, the mass ratio of BYK-9076 to EL-6976 being 2 or 3:1 (the mass ratio of BYK-9076 to EL-6976 in the hard layer slurry is 2:1, and the mass ratio of BYK-9076 to EL-6976 in the soft layer slurry is 3:1); the silane coupling agent is KH560.

[0056] The preparation of the hard layer slurry and the soft layer slurry, the photocuring printing, the cleaning, the degreasing, the sintering and other treatments after printing are consistent with step S3 in Example 2.

[0057] Step S4, metal phase infiltration: consistent with step S4 in Example 2.

[0058] Comparative Example 2 A method for preparing a multilayer ceramic material, comprising: Step S1, design of a multilayer and multiphase biomimetic ceramic layer: consistent with step S1 in Example 2.

[0059] Step S2, design of a cavity matrix structure: consistent with step S2 in Example 2.

[0060] Step S3, ceramic panel base preparation: configure hard layer ceramic slurry and soft layer ceramic slurry according to the multi-layer ceramic layer design in step S1: the hard layer slurry includes hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each component is 55wt%, 35wt%, 3wt%, 2.2wt%, 0.8wt% and 4wt% respectively; the hard ceramic mixed powder includes B4C ceramic powder (purity ≥ 99%, particle size 1-2 μm, hardness about 3180 kgf / mm 2 ), Ti3SiC2 powder (particle size 3-5 μm), nano-SiC (particle size 40-60 nm) and nano-carbon black (particle size 20-40 nm); the amount of Ti3SiC2 powder is 7wt% of the hard ceramic mixed powder, the amount of nano-SiC is 0.5wt% of the hard ceramic mixed powder, the amount of nano-carbon black is 0.2wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder; the soft layer slurry includes soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each component is 45wt%, 45wt%, 3.6wt%, 1.8wt%, 1.1wt% and 3.5wt% respectively; the soft ceramic mixed powder includes Al2O3 ceramic powder (particle size 1-2 μm, hardness about 2000 kgf / mm 2 ), CrB powder (particle size 1-2 μm), nano-AlN (particle size 80-120 nm) and nano-ZrO2 (particle size 40-60 nm); the amount of CrB powder is 3wt% of the soft ceramic mixed powder, the amount of nano-AlN is 2wt% of the soft ceramic mixed powder, the amount of nano-ZrO2 is 1.5wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder.

[0061] The photoinitiator is a combination of photoinitiator 819 and photoinitiator TPO, and the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:2 or 3 (the mass ratio of photoinitiator 819 to photoinitiator TPO in the hard layer slurry is 1:2, and the mass ratio of photoinitiator 819 to photoinitiator TPO in the soft layer slurry is 1:3); the dispersant is a combination of BYK-9076 and EL-6976, and the mass ratio of BYK-9076 to EL-6976 is 2 or 3:1 (the mass ratio of BYK-9076 to EL-6976 in the hard layer slurry is 2:1, and the mass ratio of BYK-9076 to EL-6976 in the soft layer slurry is 3:1); the silane coupling agent is KH560.

[0062] The preparation of hard layer slurry and soft layer slurry, photocuring printing, cleaning, degreasing, sintering and other treatments after printing are consistent with step S3 in example 2.

[0063] Step S4, metal phase infiltration: consistent with step S4 in Example 2.

[0064] Comparative Example 3: A method for preparing a multilayer ceramic material, comprising: Step S1, design of multilayer and multiphase biomimetic ceramic layer: consistent with step S1 in Example 2.

[0065] Step S2, design of cavity matrix structure: consistent with step S2 in Example 2.

[0066] Step S3, preparation of ceramic panel substrate: according to the design of multilayer ceramic layer in step S1, hard layer ceramic slurry and soft layer ceramic slurry are respectively configured: the hard layer slurry comprises hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each component is 55wt%, 35wt%, 3wt%, 2.2wt%, 0.8wt% and 4wt%, respectively; the hard ceramic mixed powder comprises B4C ceramic powder (purity ≥ 99%, particle size 1-2 μm, hardness about 3180 kgf / mm 2 ), Ti3SiC2 powder (particle size 3-5 μm), nano-SiC (particle size 40-60 nm) and nano-carbon black (particle size 20-40 nm); wherein the amount of Ti3SiC2 powder is 7wt% of the hard ceramic mixed powder, the amount of nano-SiC is 0.5wt% of the hard ceramic mixed powder, the amount of nano-carbon black is 0.2wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder; the soft layer slurry comprises soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each component is 45wt%, 45wt%, 3.6wt%, 1.8wt%, 1.1wt% and 3.5wt%, respectively; the soft ceramic mixed powder comprises Al2O3 ceramic powder (particle size 1-2 μm, hardness about 2000 kgf / mm 2 ), glass powder (particle size 4-6 μm), nano-AlN (particle size 80-120 nm) and nano-ZrO2 (particle size 40-60 nm); wherein the amount of glass powder is 12wt% of the soft ceramic mixed powder, the amount of nano-AlN is 2wt% of the soft ceramic mixed powder, the amount of nano-ZrO2 is 1.5wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder; the glass powder is prepared by SiO2, Al2O3, CaO and B2O3, specifically: SiO2, Al2O3, CaO and B2O3 are weighed according to the mass ratio of 10:3:4:3, and then melted at 1200℃ for 2h, followed by quenching and ball milling.

[0067] The photoinitiator is a compound of photoinitiator 819 and photoinitiator TPO, the mass ratio of photoinitiator 819 and photoinitiator TPO is 1:2 or 3 (the mass ratio of photoinitiator 819 and photoinitiator TPO in the hard layer slurry is 1:2; the mass ratio of photoinitiator 819 and photoinitiator TPO in the soft layer slurry is 1:3); the dispersant is a compound of BYK-9076 and EL-6976, the mass ratio of BYK-9076 and EL-6976 is 2 or 3:1 (the mass ratio of BYK-9076 and EL-6976 in the hard layer slurry is 2:1; the mass ratio of BYK-9076 and EL-6976 in the soft layer slurry is 3:1); the silane coupling agent is KH560.

[0068] The preparation of the hard layer slurry and the soft layer slurry, the photocuring printing, the cleaning, the degreasing, the sintering and other treatments after printing are consistent with step S3 in Example 2.

[0069] Step S4, metal phase infiltration: consistent with step S4 in Example 2.

[0070] Comparative Example 4: A method for preparing a multilayer ceramic material, comprising: Step S1, design of multilayer and multiphase biomimetic ceramic layer: consistent with step S1 in Example 2.

[0071] Step S2, design of cavity matrix structure: consistent with step S2 in Example 2.

[0072] Step S3, preparation of ceramic panel substrate: according to the multilayer ceramic layer design in step S1, hard layer ceramic slurry and soft layer ceramic slurry are respectively configured: the hard layer slurry includes hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amount of each component is 55wt%, 35wt%, 3wt%, 2.2wt%, 0.8wt% and 4wt%, respectively; the hard ceramic mixed powder includes B4C ceramic powder (purity ≥ 99%, particle size 1-2 μm, hardness about 3180 kgf / mm 2Ti3SiC2 powder (particle size 3-5 μm), nano-SiC (particle size 40-60 nm) and nano-carbon black (particle size 20-40 nm); wherein the amount of Ti3SiC2 powder is 7 wt% of the hard ceramic mixed powder, the amount of nano-SiC is 0.5 wt% of the hard ceramic mixed powder, the amount of nano-carbon black is 0.2 wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder; the soft layer slurry includes soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickening agent N-228, and the amounts of them are 45 wt%, 45 wt%, 3.6 wt%, 1.8 wt%, 1.1 wt% and 3.5 wt% respectively; the soft ceramic mixed powder includes Al2O3 ceramic powder (particle size 1-2 μm, hardness about 2000 kgf / mm 2 ), glass powder (particle size 4-6 μm), CrB powder (particle size 1-2 μm) and nano-AlN (particle size 80-120 nm); wherein the amount of glass powder is 12 wt% of the soft ceramic mixed powder, the amount of CrB powder is 3 wt% of the soft ceramic mixed powder, the amount of nano-AlN is 2 wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder; the glass powder is prepared from SiO2, Al2O3, CaO and B2O3, specifically: SiO2, Al2O3, CaO and B2O3 are proportioned according to the mass ratio of 10:3:4:3, and then melted at 1200℃ for 2h, followed by quenching and ball milling.

[0073] The photoinitiator is a compound of photoinitiator 819 and photoinitiator TPO, and the mass ratio of photoinitiator 819 to photoinitiator TPO is 1:2 or 3 (the mass ratio of photoinitiator 819 to photoinitiator TPO in the hard layer slurry is 1:2, and the mass ratio of photoinitiator 819 to photoinitiator TPO in the soft layer slurry is 1:3); the dispersant is a compound of BYK-9076 and EL-6976, and the mass ratio of BYK-9076 to EL-6976 is 2 or 3:1 (the mass ratio of BYK-9076 to EL-6976 in the hard layer slurry is 2:1, and the mass ratio of BYK-9076 to EL-6976 in the soft layer slurry is 3:1); the silane coupling agent is KH560.

[0074] The preparation of the hard layer slurry and the soft layer slurry, the light curing printing, the cleaning, the degreasing, the sintering and other treatments after the printing are consistent with step S3 in Example 2.

[0075] Step S4, metal phase infiltration: consistent with step S4 in Example 2.

[0076] Comparative Example 5: A method for preparing a multilayer ceramic material, comprising: Step S1, multi-layer multi-phase biomimetic ceramic layer design: consistent with step S1 in embodiment 2.

[0077] Step S2, cavity matrix structure design: consistent with step S2 in embodiment 2.

[0078] Step S3, ceramic panel substrate preparation: consistent with step S3 in embodiment 2.

[0079] Step S4, metal phase infiltration: by infiltrating a molten metal material into the ceramic panel substrate, a biomimetic ceramic material with an embedded metal dot array structure is obtained; the molten metal material uses Al.

[0080] The metal phase infiltration is specifically: First, at room temperature, the sintered ceramic plate is soaked in a mixed solution of 10% HF and 5% nitric acid for 20 min, then washed with deionized water to neutral, and dried at 150°C for 2h; then, a carbon layer with a thickness of 50-100 nm is deposited on one side of the ceramic panel substrate with a dot array cavity by chemical vapor deposition; then, Al is heated to 680°C under inert atmosphere until the alloy is completely melted; the ceramic panel substrate obtained in step S3 is kept at 650°C for 45 min, and then the heat-treated ceramic panel substrate is immersed in the molten alloy, a pressure of 6.5 MPa is applied for 2.2 h to fill the cavity matrix with molten metal; finally, the temperature is lowered to room temperature at a rate of 6.5°C / min, and a biomimetic ceramic material is obtained.

[0081] Comparative example 6: A method for preparing a multi-layer ceramic material, comprising: Step S1, multi-layer multi-phase biomimetic ceramic layer design: consistent with step S1 in embodiment 2.

[0082] Step S2, cavity matrix structure design: consistent with step S2 in embodiment 2.

[0083] Step S3, ceramic panel substrate preparation: consistent with step S3 in embodiment 2.

[0084] Step S4, metal phase infiltration: by infiltrating a molten metal material into the ceramic panel substrate, a biomimetic ceramic material with an embedded metal dot array structure is obtained; the molten metal material uses Al-5Mg-2Si-1Cu (wt%, i.e. 5wt% Mg, 2wt% Si, 1wt% Cu are added to the aluminum matrix to form a molten metal alloy material).

[0085] The metal phase infiltration is specifically: First, the sintered ceramic plate is soaked in a mixed solution of 10% HF and 5% nitric acid at room temperature for 20 min, then washed with deionized water until neutral, and dried at 150°C for 2 h; then, Al-5Mg-2Si-1Cu (wt%) is heated to 725°C under an inert atmosphere until the alloy is completely melted; the ceramic panel substrate obtained in step S3 is kept at 675°C for 45 min, and then the ceramic panel substrate after keeping is immersed in the molten alloy, a pressure of 6.5 MPa is applied for 2.2 h to fill the cavity matrix with molten metal; finally, the temperature is lowered to room temperature at a rate of 6.5°C / min, and a biomimetic ceramic material is obtained.

[0086] The ceramic materials in Examples 1-3 and Comparative Examples 1-6 are controlled in the same areal density range, and the biomimetic ceramic panels prepared in Examples 1-3 and Comparative Examples 1-6 are laminated with an ultra-high molecular weight polyethylene backboard (the backboard is prepared by using existing products or prior art in the art) by a hot-pressing composite process to prepare a bulletproof plate with an areal density of (32±0.2) kg / m 3 , a size of 300 mm*300 mm, and the test results are as follows:

[0087] As can be seen from the test results in the above table, the multilayer ceramic structure prepared by using the specific hard layer slurry and soft layer slurry of the present application, combined with the dot matrix support skeleton formed by melting a specific alloy, has high interfacial bonding strength and strong energy absorption and dissipation capacity, thereby effectively reducing the cracking of the ceramic and delaying the propagation of the cracks during a single impact process, thereby significantly improving the number of anti-bullet plates against bullets.

Claims

1. A method for preparing a multi-layer multi-phase biomimetic ceramic material, characterized by: include: Step S1, multi-layer multi-phase bionic ceramic layer design: First, select any two ceramic materials from B4C, Al2O3, SiC, and TiB2, and divide the two ceramic materials into hard layer materials and soft layer materials according to the hardness of the materials, and alternately stack the hard layer materials and the soft layer materials to form a multi-layer ceramic layer; Step S2, cavity matrix structure design: establishing a metal lattice model composed of multiple cell structures through an array method, and matching the metal lattice model with a multilayer ceramic layer structure to form a multilayer ceramic model with a lattice structure cavity inside; Step S3, preparing the ceramic panel substrate: preparing the hard layer ceramic slurry and the soft layer ceramic slurry according to the multi-layer ceramic layer design in step S1, and using the light-curing printing technology, printing the hard layer and the soft layer layer by layer according to the multi-layer ceramic model in step S2; After printing is completed, cleaning, degreasing and sintering are carried out in sequence to obtain the ceramic panel substrate; Step S4, metal phase infiltration: infiltrating molten metal material into the ceramic panel matrix by infiltration to obtain a bionic ceramic material with an embedded metal lattice structure.

2. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to claim 1, characterized in that: In the multi-layer ceramic layer, the hard layer has a thickness of 1 to 5 mm, the soft layer has a thickness of 0.5 to 1 mm, and the ratio of the thickness of the hard layer to the soft layer is 2 to 10:

1.

3. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to claim 1 or 2, characterized in that: The cell structure adopts any one of a tetrahedral structure, a pyramid structure and an X-shaped structure; the core thickness t of the cell structure is 1 to 3 mm, the core width d is 1 to 3 mm, the single arm length a is 20 to 30 mm, the arm span width b is 10 to 20 mm, the height h is 4 to 8 mm, and the single arm inclination angle α is 30° to 60°.

4. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to any one of claims 1 to 3, characterized in that: The hard layer slurry includes hard ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickener N-228, and the amounts thereof are: 50-60wt%, 30-40wt%, 2-4wt%, 1.8-2.6wt%, 0.6-1wt% and 3-5wt%.

5. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to claim 4, characterized in that: The hard ceramic mixed powder includes B4C ceramic powder, Ti3SiC2 powder, nano-SiC and nano-carbon black; wherein, the amount of Ti3SiC2 powder is 6-8wt% of the hard ceramic mixed powder, the amount of nano-SiC is 0.4-0.6wt% of the hard ceramic mixed powder, the amount of nano-carbon black is 0.15-0.25wt% of the hard ceramic mixed powder, and the rest is B4C ceramic powder.

6. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to any one of claims 1 to 3, characterized in that: The soft layer slurry includes soft ceramic mixed powder, OPPEA resin, photoinitiator, dispersant, silane coupling agent and thickener N-228, and the amounts thereof are: 40-50wt%, 40-50wt%, 2.6-4.6wt%, 1.4-2.2wt%, 0.9-1.3wt% and 2.5-4.5wt%.

7. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to claim 6, characterized in that: The soft ceramic mixed powder includes Al2O3 ceramic powder, glass powder, CrB powder, nano-AlN and nano-ZrO2; among them, the amount of glass powder is 11-13wt% of the soft ceramic mixed powder, the amount of CrB powder is 2.5-3.5wt% of the soft ceramic mixed powder, the amount of nano-AlN is 1.8-2.2wt% of the soft ceramic mixed powder, the amount of nano-ZrO2 is 1.3-1.7wt% of the soft ceramic mixed powder, and the rest is Al2O3 ceramic powder.

8. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to claim 7, characterized in that: The glass powder is prepared by SiO2, Al2O3, CaO, and B2O3, specifically: SiO2, Al2O3, CaO, and B2O3 are mixed in a mass ratio of 9-11:2.5-3.5:3.5-4.5:2.5-3.5, and melted at 1150-1250°C for 1.8-2.2h, and then quenched and ball-milled.

9. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to claim 1, characterized in that: In step S4, the molten metal material is any one of an Al-based alloy or a Ti-based alloy, specifically Al-5Mg-2Si-1Cu or Ti-6Al-2Si-1Nb.

10. The method for preparing a multi-layer multi-phase biomimetic ceramic material according to claim 9, characterized in that: The metal phase infiltration is specifically: First, the sintered ceramic plate is immersed in a mixture of 10% HF and 5% nitric acid at room temperature for 18 to 22 minutes; then rinsed with deionized water until neutral, and dried at 130 to 170°C for 1.8 to 2.2 hours; Then, a carbon layer with a thickness of 50 to 100 nm is deposited on the side of the ceramic panel substrate with the lattice cavity by chemical vapor deposition; Then, under an inert atmosphere, the Al-5Mg-2Si-1Cu is heated to 700-750°C until the alloy is completely melted; the ceramic panel substrate obtained in step S3 is kept at 650-700°C for 30-60 minutes, and then the ceramic panel substrate after the holding is immersed in the molten alloy, and a pressure of 5-8 MPa is applied and maintained for 1.5-3 hours, so that the molten metal fills the cavity matrix; Finally, the temperature was lowered to room temperature at a cooling rate of 5 to 8°C / min to obtain a bionic ceramic material.

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