CN118164762A - Boron carbide/diamond composite bulletproof ceramic and preparation method thereof - Google Patents
Boron carbide/diamond composite bulletproof ceramic and preparation method thereof Download PDFInfo
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 159
- 239000010432 diamond Substances 0.000 title claims abstract description 159
- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 97
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 239000000919 ceramic Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 113
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005011 phenolic resin Substances 0.000 claims abstract description 15
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 15
- 239000011268 mixed slurry Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 58
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 229910052810 boron oxide Inorganic materials 0.000 claims description 17
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 17
- 238000003825 pressing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000011863 silicon-based powder Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 7
- 238000005475 siliconizing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- -1 oxygen isopropyl borate Chemical compound 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 9
- 229910010271 silicon carbide Inorganic materials 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000005488 sandblasting Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SURBAJYBTYLRMQ-UHFFFAOYSA-N dioxido(propan-2-yloxy)borane Chemical compound CC(C)OB([O-])[O-] SURBAJYBTYLRMQ-UHFFFAOYSA-N 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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Abstract
The invention discloses boron carbide/diamond composite bulletproof ceramic and a preparation method thereof, which belong to the technical field of bulletproof ceramic preparation, wherein the preparation method comprises the following steps: preparing composite diamond micro powder, preparing coated diamond, mixing, granulating, preparing a blank, preparing a silicon plate, sintering and performing aftertreatment; the mixed material is prepared by mixing large-particle-size boron carbide micro powder, medium-particle-size boron carbide micro powder, small-particle-size boron carbide micro powder, composite diamond micro powder, coated diamond, carbon powder, phenolic resin, glycerol and water according to mass parts, and uniformly stirring to obtain mixed slurry; the composite bulletproof ceramic prepared by the invention has high elastic modulus, hardness, strength and thermal conductivity, large toughness, high bulletproof performance and strong neutron absorption capability.
Description
Technical Field
The invention relates to the technical field of preparation of bulletproof ceramics, in particular to boron carbide/diamond composite bulletproof ceramics and a preparation method thereof.
Background
The bulletproof ceramic belongs to inorganic nonmetallic materials and is one of special ceramics. The bulletproof ceramic has extremely high hardness and strength, and after the bulletproof ceramic is impacted by the bullets, the bulletproof ceramic can be broken, so that most of energy of the bullets is consumed, and an inverted pyramid-shaped destruction cone is formed at the impact position. For the bulletproof ceramic, the higher the elastic modulus, hardness, strength and thermal conductivity, the higher the toughness, the lower the density, the higher the bulletproof performance, and the higher the absorption capacity of the bulletproof ceramic to kinetic energy.
Currently, the bulletproof ceramics used are alumina, silicon carbide, boron carbide, silicon nitride, titanium boride and the like, wherein the most common bulletproof ceramics are alumina, silicon carbide and boron carbide. With the upgrading and upgrading of weapon systems, the requirements on bulletproof equipment are also higher and higher, and the traditional single-phase ceramics cannot meet the current requirements due to the limited elastic modulus, hardness, toughness and strength, so that the bulletproof ceramics start to develop towards compounding.
Boron carbide is a strong covalent bond compound, has high melting point, high elastic modulus, high strength, high thermal conductivity, high anti-elasticity performance, low density, ultra-high hardness and good neutron absorption capacity, and can realize smaller prominence in shooting tests, so that boron carbide is the optimal choice of bulletproof ceramics, but the toughness of boron carbide is small, and the development of boron carbide in the field of bulletproof ceramics is affected.
Diamond is a mineral composed of carbon elements, is an allotrope of graphite, is also a common diamond body, is the hardest substance naturally occurring in nature, and in addition, has excellent thermal conductivity, electrical conductivity and chemical stability, and can be added into ceramics to improve the hardness and toughness of the ceramics, so that diamond is increasingly used in research of bulletproof ceramics.
The composite bulletproof ceramic prepared by compositing diamond and boron carbide has ultrahigh hardness, but the interface bonding strength between diamond and boron carbide is poor, and diamond with small particle size is easy to agglomerate when mixed with boron carbide, so that the elastic modulus, strength and toughness of the composite bulletproof ceramic are affected, and the bulletproof performance of the composite bulletproof ceramic is also affected.
In order to solve the problems, the most commonly used method at present is to carry out siliconizing on a blank body made of diamond and boron carbide, and react the silicon with part of diamond to produce silicon carbide, so that a composite of diamond and silicon carbide is formed, and the silicon carbide can improve the interface bonding strength with the boron carbide, so that the influence on the elastic modulus and toughness of the composite bulletproof ceramic due to the poor interface bonding strength is avoided. However, this method has the following problems: free silicon is generated in the reaction process of diamond and silicon, and the free silicon can influence the elastic modulus, strength, heat conductivity and toughness of the composite bulletproof ceramic; silicon carbide is generated in the siliconizing process, and the addition of the silicon carbide can reduce the neutron absorption capacity of the composite bulletproof ceramic.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the boron carbide/diamond composite bulletproof ceramic and the preparation method thereof, and the prepared composite bulletproof ceramic has the advantages of high elastic modulus, hardness, strength, thermal conductivity, high toughness, high bulletproof performance and strong neutron absorption capability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
The preparation method of the boron carbide/diamond composite bulletproof ceramic comprises the following steps: preparing composite diamond micro powder, preparing coated diamond, mixing, granulating, preparing a blank, preparing a silicon plate, sintering and performing aftertreatment;
Mixing dodecyl trimethyl ammonium bromide, absolute ethyl alcohol and water, stirring at a stirring speed of 300-500rpm for 10-20min at room temperature, adding ammonia water to adjust the pH value to 9-10, then adding tetraethoxysilane, aluminum oxide and boron oxide, stirring at a stirring speed of 300-500rpm for 12-15h at 70-80 ℃, adding small-particle-size diamond micro powder, and continuing stirring for 2-3h to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle, putting the hydrothermal synthesis reaction kettle into a baking oven, controlling the temperature of the baking oven to be 140-160 ℃, and taking out after 15-18 hours to obtain a hydrothermal reactant; transferring the hydrothermal reactant into a baking oven, controlling the temperature of the baking oven to be 110-130 ℃, taking out after 3-4 hours, and crushing to obtain composite diamond micro powder with the median particle diameter of 20-25 mu m;
In the preparation of the composite diamond micro powder, the mass ratio of the dodecyl trimethyl ammonium bromide, the absolute ethyl alcohol, the water, the ethyl orthosilicate, the aluminum oxide, the boron oxide and the small-particle-size diamond micro powder is 70-75:100-120:500-550:100-120:75-80:50-60:100-120;
The concentration of the ammonia water is 25wt%;
The particle size of the alumina is 1-2 mu m;
the particle size of the boron oxide is 1-2 mu m;
The grain diameter of the diamond micropowder with small grain diameter is 8-10 mu m;
Mixing boron powder, gamma-aminopropyl triethoxysilane, first part of absolute ethyl alcohol and water, stirring at a stirring speed of 100-300rpm for 5-6 hours at 40-50 ℃, centrifuging, controlling the rotation speed of the centrifuging to 5000-6000rpm for 8-10 minutes, then using absolute ethyl alcohol to wash precipitate for 3-4 times, transferring into an oven, controlling the temperature of the oven to 110-130 ℃ for 2-3 hours, and taking out to obtain modified boron powder; mixing large-particle diamond micro powder, distearoyl oxygen isopropyl borate and a second part of absolute ethyl alcohol, stirring at a stirring speed of 100-300rpm for 1.5-2 hours at 30-50 ℃, centrifuging, controlling the rotation speed of the centrifuging to 3000-4000rpm for 5-6 minutes, washing the precipitate with the absolute ethyl alcohol for 3-4 times, transferring into an oven, controlling the temperature of the oven to 110-130 ℃, and taking out after 2-3 hours to obtain modified diamond micro powder; mixing the modified boron powder with the modified diamond micro powder, performing ball milling, controlling the rotational speed of the ball milling to be 200-300rpm, and obtaining coated diamond after the ball-material ratio is 8-10:1 and 2-3 hours;
In the preparation of the coated diamond, the mass ratio of the boron powder to the gamma-aminopropyl triethoxysilane to the first part of absolute ethyl alcohol to the water to the large-particle diamond micro powder to the second part of absolute ethyl alcohol is 100-110:20-25:1000-1500:1000-1200:500-600:30-35:3000-4000;
The grain diameter of the boron powder is 1-2 mu m;
The grain diameter of the large-grain diameter diamond micro powder is 80-100 mu m;
The mixed material is prepared by mixing large-particle-size boron carbide micro powder, medium-particle-size boron carbide micro powder, small-particle-size boron carbide micro powder, composite diamond micro powder, coated diamond, carbon powder, phenolic resin, glycerol and water according to mass parts, and uniformly stirring to obtain mixed slurry;
in the mixed material, the mass ratio of the large-grain-size boron carbide micro powder to the medium-grain-size boron carbide micro powder to the small-grain-size boron carbide micro powder to the composite diamond micro powder to the coated diamond to the carbon powder to the phenolic resin to the glycerol to the water is 35-40:15-20:5-7:10-12:15-18:3-5:10-15:10-15:80-110;
the particle size of the large-particle size boron carbide micro powder is 50-60 mu m;
The particle size of the medium-particle-size boron carbide micro powder is 4-6 mu m;
the particle size of the small-particle size boron carbide micro powder is 300-500nm;
the particle size of the carbon powder is 7-10 mu m;
the granulation is carried out, the mixed slurry is sprayed and granulated, and then is sieved by a 60-100 mesh sieve, and the undersize is taken as ceramic powder;
The preparation of a green body, namely transferring ceramic powder into a die, pressing after leveling, and controlling the pressing pressure to be 25-35MPa to obtain the green body;
The preparation method comprises the steps of uniformly mixing silicon powder and phenolic resin according to parts by weight, pressing the mixture into a silicon plate, controlling the mass of the silicon plate to be 2.4-2.7 times of the mass of a blank, and controlling the shape of the silicon plate to be the same as the siliconizing surface of the blank;
In the preparation of the silicon plate, the mass ratio of the silicon powder to the phenolic resin is 100-110:12-15;
The grain diameter of the silicon powder is 60-80 mu m;
the sintering is carried out, a silicon plate is placed on a green body, the green body is sintered in a vacuum furnace, the vacuum degree of sintering is controlled to be 50-100Pa, the temperature is controlled to be 1600-1800 ℃, and after 29-31 hours, the green body is naturally cooled to room temperature, so that a sintered green body is obtained;
And (3) carrying out post-treatment, and carrying out sand blasting and detection on the sintered blank to obtain the boron carbide/diamond composite bulletproof ceramic.
The boron carbide/diamond composite bulletproof ceramic prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the boron carbide/diamond composite bulletproof ceramic, the elastic modulus of the prepared boron carbide/diamond composite bulletproof ceramic is 417-435GPa;
(2) According to the preparation method of the boron carbide/diamond composite bulletproof ceramic, the Vickers hardness of the prepared boron carbide/diamond composite bulletproof ceramic is 41-47GPa;
(3) According to the preparation method of the boron carbide/diamond composite bulletproof ceramic, the bending strength of the prepared boron carbide/diamond composite bulletproof ceramic is 408-445MPa;
(4) According to the preparation method of the boron carbide/diamond composite bulletproof ceramic, the thermal conductivity of the prepared boron carbide/diamond composite bulletproof ceramic is 103-117W/(m.K);
(5) According to the preparation method of the boron carbide/diamond composite bulletproof ceramic, the fracture toughness of the prepared boron carbide/diamond composite bulletproof ceramic is 5.26-5.57 MPa.m 1/2;
(6) According to the preparation method of the boron carbide/diamond composite bulletproof ceramic, the prepared boron carbide/diamond composite bulletproof ceramic can prevent 4 gun bullets, and the average number of the saliency after each gun bullet is 12-16mm.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A preparation method of boron carbide/diamond composite bulletproof ceramic specifically comprises the following steps:
1. Preparing composite diamond micro powder: mixing 70g of dodecyl trimethyl ammonium bromide, 100g of absolute ethyl alcohol and 500g of water, stirring at room temperature for 10min at a stirring speed of 300rpm, adding ammonia water to adjust the pH value to 9, then adding 100g of tetraethoxysilane, 75g of aluminum oxide and 50g of boron oxide, stirring at 70 ℃ for 12h at a stirring speed of 300rpm, adding 100g of small-particle-size diamond micro powder, and continuously stirring for 2h to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle, putting the hydrothermal synthesis reaction kettle into a baking oven, controlling the temperature of the baking oven to be 140 ℃, and taking out after 15 hours to obtain a hydrothermal reactant; transferring the hydrothermal reactant into a baking oven, controlling the temperature of the baking oven to be 110 ℃, taking out after 3 hours, and crushing to obtain composite diamond micro powder with the median particle diameter of 20 mu m;
The concentration of the ammonia water is 25wt%;
the particle size of the alumina is 1 mu m;
The particle size of the boron oxide is 1 mu m;
the grain diameter of the diamond micro powder with small grain diameter is 8 mu m;
2. Preparing coated diamond: mixing 100g of boron powder, 20g of gamma-aminopropyl triethoxysilane, 1000g of absolute ethyl alcohol and 1000g of water, stirring at 40 ℃ for 5 hours at a stirring speed of 100rpm, centrifuging, controlling the rotation speed of the centrifuging to be 5000rpm for 8 minutes, then using absolute ethyl alcohol to clean the precipitate for 3-4 times, transferring into a baking oven, controlling the temperature of the baking oven to be 110 ℃, and taking out after 2 hours to obtain modified boron powder; mixing 500g of large-particle-size diamond micro powder, 30g of distearoyl oxygen isopropyl borate and 3000g of absolute ethyl alcohol, stirring at a stirring speed of 100rpm for 1.5 hours at 30 ℃, centrifuging, controlling the rotating speed of the centrifuging to be 3000rpm for 5 minutes, cleaning a precipitate by using the absolute ethyl alcohol for 3 times, transferring into an oven, controlling the temperature of the oven to be 110 ℃, and taking out after 2 hours to obtain modified diamond micro powder; mixing modified boron powder with modified diamond micro powder, performing ball milling, controlling the rotation speed of ball milling to be 200rpm and the ball-material ratio to be 8:1, and obtaining coated diamond after 2 hours;
the particle size of the boron powder is 1 mu m;
the grain diameter of the large-grain diameter diamond micro powder is 80 mu m;
3. Mixing: according to the mass parts, mixing 35 parts of large-particle-size boron carbide micro powder, 15 parts of medium-particle-size boron carbide micro powder, 5 parts of small-particle-size boron carbide micro powder, 10 parts of composite diamond micro powder, 15 parts of coated diamond, 3 parts of carbon powder, 10 parts of phenolic resin, 10 parts of glycerol and 80 parts of water, and uniformly stirring to obtain mixed slurry;
The particle size of the large-particle size boron carbide micro powder is 50 mu m;
the particle size of the medium-particle-size boron carbide micro powder is 4 mu m;
the particle size of the small-particle-size boron carbide micro powder is 300nm;
the particle size of the carbon powder is 7 mu m;
4. Granulating: spraying and granulating the mixed slurry, sieving with a 60-mesh sieve, and taking the undersize as ceramic powder;
5. preparing a blank: transferring the ceramic powder into a die, flattening, pressing, and controlling the pressing pressure to be 25MPa to obtain a blank;
6. preparing a silicon plate: uniformly mixing 100 parts of silicon powder and 12 parts of phenolic resin according to parts by mass, and pressing into a silicon plate, wherein the mass of the silicon plate is controlled to be 2.4 times of that of a blank, and the shape of the silicon plate is the same as the siliconizing surface of the blank;
The grain diameter of the silicon powder is 60 mu m;
7. Sintering: placing a silicon plate on a green body, sintering in a vacuum furnace, controlling the sintering vacuum degree to be 50Pa, controlling the sintering temperature to be 1600 ℃, and naturally cooling to room temperature after 29 hours to obtain a sintered green body;
8. post-treatment: and (3) carrying out sand blasting and detection on the sintered blank to obtain the boron carbide/diamond composite bulletproof ceramic.
The embodiment also provides the boron carbide/diamond composite bulletproof ceramic prepared by the preparation method.
Example 2
A preparation method of boron carbide/diamond composite bulletproof ceramic specifically comprises the following steps:
1. Preparing composite diamond micro powder: mixing 72g of dodecyl trimethyl ammonium bromide, 110g of absolute ethyl alcohol and 520g of water, stirring at room temperature for 15min at a stirring speed of 400rpm, adding ammonia water to adjust the pH to 9.5, then adding 110g of tetraethoxysilane, 77g of aluminum oxide and 55g of boron oxide, stirring at a stirring speed of 400rpm at 75 ℃ for 14h, adding 110g of small-particle-size diamond micro powder, and continuing stirring for 2.5h to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle, putting the hydrothermal synthesis reaction kettle into a baking oven, controlling the temperature of the baking oven to be 150 ℃, and taking out the baking oven after 16 hours to obtain a hydrothermal reactant; transferring the hydrothermal reactant into a baking oven, controlling the temperature of the baking oven to be 120 ℃, taking out after 3.5 hours, and crushing to obtain composite diamond micro powder with the median particle diameter of 20 mu m;
The concentration of the ammonia water is 25wt%;
the particle size of the alumina is 1 mu m;
The particle size of the boron oxide is 1 mu m;
The grain diameter of the diamond micropowder with small grain diameter is 10 mu m;
2. Preparing coated diamond: mixing 105g of boron powder, 22g of gamma-aminopropyl triethoxysilane, 1200g of absolute ethyl alcohol and 1100g of water, stirring at 45 ℃ for 5.5 hours at a stirring speed of 200rpm, centrifuging, controlling the rotation speed of the centrifuging to 5500rpm for 9 minutes, cleaning the precipitate with the absolute ethyl alcohol for 3 times, transferring into an oven, controlling the temperature of the oven to 120 ℃, and taking out after 2.5 hours to obtain modified boron powder; mixing 550g of large-particle-size diamond micro powder, 32g of distearoyl oxygen isopropyl borate and 3500g of absolute ethyl alcohol, stirring at 40 ℃ for 1.8 hours at a stirring speed of 200rpm, centrifuging, controlling the rotation speed of the centrifuging to 3500rpm for 5.5 minutes, cleaning the precipitate by using the absolute ethyl alcohol for 3 times, transferring into an oven, controlling the temperature of the oven to 120 ℃, and taking out after 2.5 hours to obtain modified diamond micro powder; mixing the modified boron powder with the modified diamond micro powder, performing ball milling, controlling the rotation speed of the ball milling to be 250rpm, and obtaining coated diamond after the ball-material ratio is 9:1 and 2.5 hours;
the particle size of the boron powder is 1 mu m;
the grain diameter of the large-grain diameter diamond micro powder is 100 mu m;
3. mixing: according to the mass parts, mixing 38 parts of large-particle-size boron carbide micro powder, 17 parts of medium-particle-size boron carbide micro powder, 6 parts of small-particle-size boron carbide micro powder, 11 parts of composite diamond micro powder, 16 parts of coated diamond, 4 parts of carbon powder, 12 parts of phenolic resin, 12 parts of glycerol and 100 parts of water, and uniformly stirring to obtain mixed slurry;
The particle size of the large-particle size boron carbide micro powder is 50 mu m;
The particle size of the medium-particle-size boron carbide micro powder is 5 mu m;
the particle size of the small-particle-size boron carbide micro powder is 300nm;
The particle size of the carbon powder is 8 mu m;
4. Granulating: spraying and granulating the mixed slurry, sieving with an 80-mesh sieve, and taking the undersize as ceramic powder;
5. Preparing a blank: transferring the ceramic powder into a die, flattening, pressing, and controlling the pressing pressure to be 30MPa to obtain a blank;
6. Preparing a silicon plate: uniformly mixing 105 parts of silicon powder and 14 parts of phenolic resin according to parts by mass, and pressing into a silicon plate, wherein the mass of the silicon plate is controlled to be 2.5 times of that of a blank, and the shape of the silicon plate is the same as the siliconizing surface of the blank;
The grain diameter of the silicon powder is 60 mu m;
7. Sintering: placing a silicon plate on a green body, sintering in a vacuum furnace, controlling the sintering vacuum degree to be 80Pa, controlling the sintering temperature to be 1700 ℃, naturally cooling to room temperature after 30 hours, and obtaining a sintered green body;
8. post-treatment: and (3) carrying out sand blasting and detection on the sintered blank to obtain the boron carbide/diamond composite bulletproof ceramic.
The embodiment also provides the boron carbide/diamond composite bulletproof ceramic prepared by the preparation method.
Example 3
A preparation method of boron carbide/diamond composite bulletproof ceramic specifically comprises the following steps:
1. Preparing composite diamond micro powder: mixing 75g of dodecyl trimethyl ammonium bromide, 120g of absolute ethyl alcohol and 550g of water, stirring at room temperature for 20min at a stirring speed of 500rpm, adding ammonia water to adjust the pH to 10, then adding 120g of tetraethoxysilane, 80g of aluminum oxide and 60g of boron oxide, stirring at 80 ℃ for 15h at a stirring speed of 500rpm, adding 120g of small-particle-size diamond micro powder, and continuously stirring for 3h to obtain a mixed solution; transferring the mixed solution into a hydrothermal synthesis reaction kettle, putting the hydrothermal synthesis reaction kettle into a baking oven, controlling the temperature of the baking oven to 160 ℃, and taking out the baking oven after 18 hours to obtain a hydrothermal reactant; transferring the hydrothermal reactant into a baking oven, controlling the temperature of the baking oven to be 130 ℃, taking out after 4 hours, and crushing to obtain composite diamond micro powder with the median particle diameter of 25 mu m;
The concentration of the ammonia water is 25wt%;
the particle size of the alumina is 2 mu m;
The particle size of the boron oxide is 2 mu m;
The grain diameter of the diamond micropowder with small grain diameter is 10 mu m;
2. preparing coated diamond: mixing 110g of boron powder, 25g of gamma-aminopropyl triethoxysilane, 1500g of absolute ethyl alcohol and 1200g of water, stirring at 50 ℃ for 6 hours at a stirring speed of 300rpm, centrifuging, controlling the rotation speed of the centrifuging to 6000rpm for 10 minutes, cleaning the precipitate by using absolute ethyl alcohol for 4 times, transferring into an oven, controlling the temperature of the oven to 130 ℃ for 3 hours, and taking out to obtain modified boron powder; mixing 600g of large-particle-size diamond micro powder, 35g of distearoyl oxygen isopropyl borate and 4000g of absolute ethyl alcohol, stirring at 50 ℃ for 2 hours at a stirring speed of 300rpm, centrifuging, controlling the rotation speed of the centrifuging to be 4000rpm for 6 minutes, cleaning a precipitate by using the absolute ethyl alcohol for 4 times, transferring into an oven, controlling the temperature of the oven to be 130 ℃, and taking out after 3 hours to obtain modified diamond micro powder; mixing modified boron powder with modified diamond micro powder, performing ball milling, controlling the rotation speed of ball milling to 300rpm and the ball-to-material ratio to 10:1, and obtaining coated diamond after 3 hours;
The particle size of the boron powder is 2 mu m;
the grain diameter of the large-grain diameter diamond micro powder is 100 mu m;
3. Mixing: mixing 40 parts of large-particle-size boron carbide micro powder, 20 parts of medium-particle-size boron carbide micro powder, 7 parts of small-particle-size boron carbide micro powder, 12 parts of composite diamond micro powder, 18 parts of coated diamond, 5 parts of carbon powder, 15 parts of phenolic resin, 15 parts of glycerol and 110 parts of water according to parts by mass, and uniformly stirring to obtain mixed slurry;
the particle size of the large-particle size boron carbide micro powder is 60 mu m;
The particle size of the medium-particle-size boron carbide micro powder is 6 mu m;
The particle size of the small-particle-size boron carbide micro powder is 500nm;
the particle size of the carbon powder is 10 mu m;
4. Granulating: spraying and granulating the mixed slurry, sieving with a 100-mesh sieve, and taking the undersize as ceramic powder;
5. preparing a blank: transferring the ceramic powder into a die, flattening, pressing, and controlling the pressing pressure to be 35MPa to obtain a blank;
6. preparing a silicon plate: uniformly mixing 110 parts of silicon powder and 15 parts of phenolic resin according to parts by mass, and pressing into a silicon plate, wherein the mass of the silicon plate is controlled to be 2.7 times of that of a blank, and the shape of the silicon plate is the same as the siliconizing surface of the blank;
The grain diameter of the silicon powder is 80 mu m;
7. Sintering: placing a silicon plate on a green body, sintering in a vacuum furnace, controlling the sintering vacuum degree to be 100Pa, controlling the sintering temperature to be 1800 ℃, and naturally cooling to room temperature after 31 hours to obtain a sintered green body;
8. post-treatment: and (3) carrying out sand blasting and detection on the sintered blank to obtain the boron carbide/diamond composite bulletproof ceramic.
The embodiment also provides the boron carbide/diamond composite bulletproof ceramic prepared by the preparation method.
Comparative example 1
The preparation method of example 2 was modified to verify the effect of the preparation of the composite diamond micropowder of step 1, with the following specific modifications: omitting the step 1 to prepare composite diamond micropowder, and using a mixture of small-particle-diameter diamond micropowder with the particle diameter of 10 mu m and silicon oxide, aluminum oxide and boron oxide to replace 11 parts of composite diamond micropowder in the step 3;
Wherein, the mass ratio of the diamond micro powder with small particle size to the mixture is 5:6;
The mass ratio of the silicon oxide to the aluminum oxide to the boron oxide in the mixture is 3:7:5.
Comparative example 2
The preparation method of example 2 was modified to verify the effect of preparing coated diamond in step 2, with the following modifications: omitting step 2 to prepare coated diamond, and using boron powder with the particle size of 1 mu m and large-particle diamond micro powder with the particle size of 100 mu m to replace the addition of the coated diamond in the step 3 mixture;
wherein the mass ratio of the boron powder to the large-particle-size diamond micro powder is 1:5.
Test example 1
The boron carbide/diamond composite bulletproof ceramics prepared in examples 1 to 3 and comparative examples 1 to 2 were tested for elastic modulus, vickers hardness, flexural strength, thermal conductivity, and fracture toughness, and the test results were as follows:
test example 2
The boron carbide/diamond composite bulletproof ceramic prepared in examples 1 to 3 and comparative examples 1 to 2 were tested for the bulletproof property and neutron absorption capacity, specifically, the number of bulletproof guns and the degree of protrusion after the front 3 guns were tested, and the average degree of protrusion was calculated, respectively, as follows:
As can be seen from the results of test examples 1 and 2, in the preparation of the boron carbide/diamond composite bulletproof ceramic, in the preparation of the composite diamond micro powder in step 1, the small-particle-diameter diamond micro powder is coated by using gel, specifically, the silica sol is gelled after the silica sol, the alumina and the boron oxide are mixed, then the small-particle-diameter diamond micro powder is added, and after uniform stirring, the hydrothermal reaction is performed, so that the small-particle-diameter diamond micro powder coated with the silica, the alumina and the boron oxide on the surface is obtained. The aim of preparing the composite diamond micro powder is mainly that: firstly, agglomeration of diamond micropowder with small particle size is avoided; secondly, silicon oxide, aluminum oxide and boron oxide are used as cosolvent and are compounded on the surfaces of the diamond micropowder with small particle size, and in the sintering process, a crosslinking layer can be formed on the surfaces of the diamond micropowder with small particle size, free silicon is adsorbed, and the interface bonding strength between the diamond micropowder with small particle size and boron carbide is improved. Therefore, the step of preparing the composite diamond micropowder can improve the thermal conductivity, the elastic modulus, the bending strength, the fracture toughness, the anti-elastic performance and the neutron absorption capacity of the composite bulletproof ceramic.
In the preparation of the boron carbide/diamond composite bulletproof ceramic, gamma-aminopropyl triethoxysilane is used for modifying the surface of boron powder, nitrogen-containing groups are introduced, distearoyl isopropyl borate is used for modifying the surface of large-particle-size diamond micro powder, boron-containing groups are introduced, then the surface-modified boron powder and the surface-modified large-particle-size diamond micro powder are ball-milled, bonding is carried out between nitrogen and boron in the ball milling process, so that the surface of the large-particle-size diamond micro powder is coated with the boron powder, in sintering, the boron powder reacts with the large-particle-size diamond micro powder to generate boron carbide, and meanwhile, the large-particle-size diamond micro powder reacts with silicon to produce silicon carbide, so that the large-particle-size diamond micro powder is converted into a composite of boron carbide, silicon carbide and diamond, the interface bonding strength between the sintered large-size diamond micro powder and the boron carbide is improved, and the neutron absorption capacity of the sintered large-particle-size diamond micro powder is improved, and the thermal conductivity, the elastic modulus, the bending strength, the fracture toughness, the bulletproof capacity and the neutron absorption capacity of the composite bulletproof ceramic are improved.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the boron carbide/diamond composite bulletproof ceramic is characterized by comprising the following steps of: preparing composite diamond micro powder, preparing coated diamond, mixing, granulating, preparing a blank, preparing a silicon plate, sintering and performing aftertreatment;
mixing dodecyl trimethyl ammonium bromide, absolute ethyl alcohol and water, stirring at room temperature, adding ammonia water to adjust the pH value to 9-10, then adding tetraethoxysilane, aluminum oxide and boron oxide, stirring at 70-80 ℃, adding small-particle-size diamond micro powder, and continuously stirring to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution to obtain a hydrothermal reactant; drying and crushing the hydrothermal reactant to obtain composite diamond micro powder;
the preparation of coated diamond comprises the steps of mixing boron powder, gamma-aminopropyl triethoxysilane, first part of absolute ethyl alcohol and water, stirring at 40-50 ℃, centrifuging, cleaning and drying a precipitate to obtain modified boron powder; mixing large-particle diamond micropowder, distearoyl oxygen isopropyl borate and a second part of absolute ethyl alcohol, stirring at 30-50 ℃, centrifuging, cleaning, and drying the precipitate to obtain modified diamond micropowder; and mixing the modified boron powder with the modified diamond micro powder, and performing ball milling to obtain the coated diamond.
2. The method for preparing the boron carbide/diamond composite bulletproof ceramic according to claim 1, wherein in the preparation of the composite diamond micro powder, the mass ratio of dodecyl trimethyl ammonium bromide, absolute ethyl alcohol, water, tetraethoxysilane, alumina, boron oxide and small-particle-size diamond micro powder is 70-75:100-120:500-550:100-120:75-80:50-60:100-120;
The concentration of the ammonia water is 25wt%;
The particle size of the alumina is 1-2 mu m;
the particle size of the boron oxide is 1-2 mu m;
The grain diameter of the diamond micropowder with small grain diameter is 8-10 mu m;
the temperature of the hydrothermal reaction is 140-160 ℃ and the time is 15-18h.
3. The method for preparing the boron carbide/diamond composite bulletproof ceramic according to claim 1, wherein in the preparation of the coated diamond, the mass ratio of boron powder, gamma-aminopropyl triethoxysilane, first part of absolute ethyl alcohol, water, large-particle diamond micro powder, distearoyl oxyisopropyl borate and second part of absolute ethyl alcohol is 100-110:20-25:1000-1500:1000-1200:500-600:30-35:3000-4000;
The grain diameter of the boron powder is 1-2 mu m;
the grain diameter of the large-grain diameter diamond micropowder is 80-100 mu m.
4. The method for preparing the boron carbide/diamond composite bulletproof ceramic according to claim 1, wherein the mixed materials are obtained by uniformly mixing large-particle-size boron carbide micro powder, medium-particle-size boron carbide micro powder, small-particle-size boron carbide micro powder, composite diamond micro powder, coated diamond, carbon powder, phenolic resin, glycerol and water according to mass parts and stirring the mixture to obtain mixed slurry.
5. The method for preparing the boron carbide/diamond composite bulletproof ceramic according to claim 1, wherein the mass ratio of the large-particle-size boron carbide micro powder, the medium-particle-size boron carbide micro powder, the small-particle-size boron carbide micro powder, the composite diamond micro powder, the coated diamond, the carbon powder, the phenolic resin, the glycerol and the water in the mixed materials is 35-40:15-20:5-7:10-12:15-18:3-5:10-15:10-15:80-110;
the particle size of the large-particle size boron carbide micro powder is 50-60 mu m;
The particle size of the medium-particle-size boron carbide micro powder is 4-6 mu m;
the particle size of the small-particle size boron carbide micro powder is 300-500nm;
the particle size of the carbon powder is 7-10 mu m.
6. The method for producing a boron carbide/diamond composite ballistic resistant ceramic according to claim 1, wherein the granulating comprises spraying the mixed slurry, granulating, sieving, and taking the undersize as ceramic powder.
7. The method for preparing the boron carbide/diamond composite bulletproof ceramic according to claim 1, wherein the preparing green body is obtained by transferring ceramic powder into a die, and pressing after leveling;
in the preparation of the green body, the pressing pressure is 25-35MPa.
8. The method for preparing the boron carbide/diamond composite bulletproof ceramic according to claim 1, wherein the silicon plate is prepared by uniformly mixing silicon powder and phenolic resin in parts by mass and pressing the silicon powder into the silicon plate;
In the preparation of the silicon plate, the mass ratio of the silicon powder to the phenolic resin is 100-110:12-15;
The grain diameter of the silicon powder is 60-80 mu m;
The mass of the silicon plate is 2.4-2.7 times of that of the blank, and the shape of the silicon plate is the same as that of the siliconizing surface of the blank.
9. The method for preparing the boron carbide/diamond composite bulletproof ceramic according to claim 1, wherein the sintering is carried out by placing a silicon plate on a green body, sintering in a vacuum furnace, and naturally cooling to room temperature to obtain a sintered green body;
in the sintering, the vacuum degree of the sintering is 50-100Pa, the temperature is 1600-1800 ℃ and the time is 29-31h.
10. A boron carbide/diamond composite ballistic resistant ceramic produced by the method of any one of claims 1 to 9.
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