CN114671689A - Hot-pressing liquid-phase sintered boron carbide composite ceramic and preparation method thereof - Google Patents
Hot-pressing liquid-phase sintered boron carbide composite ceramic and preparation method thereof Download PDFInfo
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- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 80
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 238000007731 hot pressing Methods 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000007791 liquid phase Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 92
- 239000000843 powder Substances 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005469 granulation Methods 0.000 claims abstract description 9
- 230000003179 granulation Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007921 spray Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052786 argon Inorganic materials 0.000 claims description 7
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- 239000010439 graphite Substances 0.000 claims description 6
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- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
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- 238000000227 grinding Methods 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000280 densification Methods 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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Abstract
The invention provides a hot-pressing liquid-phase sintered boron carbide composite ceramic and a preparation method thereof, wherein the preparation method comprises the following steps: weighing the raw materials in percentage by mass: 69-81 wt% of boron carbide powder, 6-10 wt% of titanium carbide powder, 8-10 wt% of sintering aid, 0.3-0.5 wt% of dispersant, 3-5 wt% of binder and 2-5 wt% of plasticizer; uniformly mixing the raw materials, and performing spray granulation; prepressing to form a green body, and performing hot-pressing sintering to obtain the boron carbide composite ceramic, wherein the sintering temperature is 1840-1900 ℃, and the sintering pressure is 25-30 MPa. The method adopts the technical scheme that the in-situ reaction is matched with the hot-pressing sintering of the liquid-phase sintering aid, has the advantages of simple and convenient operation, low production cost and high efficiency, and can prepare the boron carbide composite ceramic with high strength and high performance by the synergistic enhancement of the in-situ reaction and the liquid-phase hot-pressing sintering, thereby having good application prospect.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a hot-pressing liquid-phase sintered boron carbide composite ceramic and a preparation method thereof.
Background
Boron carbide is an engineering ceramic material with excellent performance, has the advantages of high strength, high hardness and low density, has corrosion resistance, wear resistance and excellent neutron absorption capacity, and has good application prospect in high-tech fields such as electronics, aerospace, military industry and the like.
However, due to the inherent characteristics of boron carbide, boron carbide is mostly formed by covalent bonds, the index of the covalent bonds is as high as 93.94%, the inside of the ceramic is lack of a slip system, densification is difficult, the material has high brittleness, low toughness and low strength, and the prior art for producing boron carbide generally adopts a normal-pressure solid-phase sintering mode, needs a high sintering temperature, generally above 2000 ℃, has high preparation cost, and causes great limitation on the expansion of the application of boron carbide ceramic.
Disclosure of Invention
The invention aims to provide a novel preparation method of boron carbide ceramic, which solves the problems of large brittleness, low strength, difficult densification, high sintering temperature and high preparation cost of the traditional sintered boron carbide ceramic.
The invention provides a preparation method of hot-pressing liquid-phase sintered boron carbide composite ceramic, which comprises the following steps:
weighing the raw materials in percentage by mass: 69-81 wt% of boron carbide powder, 6-10 wt% of titanium carbide powder, 8-10 wt% of sintering aid, 0.3-0.5 wt% of dispersant, 3-5 wt% of binder and 2-5 wt% of plasticizer;
Uniformly mixing the raw materials, specifically adopting a ball milling pulping mode, taking boron carbide ceramic balls as medium balls during ball milling, wherein the ball diameter is 5-10mm, adding the raw materials and deionized water, and the mass of the medium balls is as follows: the total mass of the boron carbide powder, the titanium carbide powder and the sintering additive is as follows: deionized water with the mass ratio of 2:1: 1; then spraying the ball-milling slurry into a spray drying granulator for spray granulation;
prepressing to form a green body, and carrying out hot-pressing sintering to obtain the boron carbide composite ceramic, wherein the sintering temperature is 1840-1900 ℃, and the sintering pressure is 25-30 MPa.
Compared with the prior art, the invention realizes the strengthening and toughening of the boron carbide ceramic by adding the second phase and controlling the sintering process, and the boron carbide in the raw material system can react with the titanium carbide in situ to generate TiB2The generated hard phase has the functions of dispersing and strengthening the matrix, hindering the tip expansion of microcracks and inhibiting the growth of crystal grains, and a new phase generated through in-situ reaction is more tightly combined with the matrix and has an activation effect on sintering; the sintering process adopts liquid-phase hot-pressing sintering, can effectively realize the densification of the material due to the existence of the sintering aid, can obtain a high-density sintered body basically without air holes, and has lower sintering temperature compared with solid-phase sintering and normal-pressure sintering processes.
Further, the sintering aid is any combination of alumina, alumina and yttrium oxide, alumina and carbon black.
Furthermore, the sintering aid is alumina and yttrium oxide, and the mass ratio of the alumina to the yttrium oxide is 1.5-1.7.
Further, the sintering aid is alumina and carbon black, and the mass ratio of the alumina to the carbon black is 5-12.
The invention selects ceramic oxide as liquid phase sintering aid, titanium carbide as in-situ reaction activator, carbon black as crystal grain inhibitor, the ceramic oxide presents liquid phase at high temperature to sinter under normal pressure or pressurization condition, especially when hot pressing sintering method is adopted, high density sintered body without air hole basically can be obtained. The combination of three sintering aids of alumina, alumina and yttria, alumina and carbon black is designed, and the combination of the sintering aids not only has better high-temperature performance and mechanical property, but also can form a new phase with high performance and a eutectic body with lower temperature through proportioning design of partial combination, so that the sintering temperature can be further reduced, and the densification of the material can be realized.
Furthermore, the particle diameter D50 of the boron carbide powder is 0.3-0.8um, and the particle diameter D50 of the titanium carbide powder is 0.5-1 um.
Furthermore, the grain diameter D50 of the alumina is 0.2-0.5um, the grain diameter D50 of the yttrium oxide is 0.5-1um, and the grain diameter D50 of the carbon black is 0.2-0.5 um.
The invention adopts a liquid-phase hot-pressing sintering process, controls the particle size of the raw material, is difficult to sinter if the particle size is too large, has high sintering temperature, controls the particle size of the raw material particles in a proper range, is favorable for reducing the sintering temperature, and has higher performance of the silicon carbide sintered body with small particle size.
Further, the dispersing agent is selected from one or more of tetramethylammonium hydroxide, ammonium polyacrylate and triethanolamine, the binder is selected from one or more of polyvinyl alcohol, polyvinyl butyral and hydroxymethyl cellulose, and the plasticizer is selected from one or more of polyethylene glycol, glycerol and polyacrylic acid.
Further, the hot-pressing sintering process specifically comprises: vacuumizing the sintering furnace, wherein the vacuum degree is less than 0.001MPa, and heating to 1000 ℃ at the heating speed of 5 ℃/min; and introducing argon into the sintering furnace, sintering in an argon atmosphere, pressurizing, heating to the sintering temperature at the heating rate of 5 ℃/min, and preserving heat for 1-2 h. The vacuum sintering is carried out firstly, and then the sintering is carried out in a pressurized atmosphere, so that the strength loss of the ceramic material caused by high-temperature oxidation can be reduced, the graphite mould can be protected, and the production cost is saved.
The method adopts the technical scheme that the in-situ reaction is matched with the hot-pressing sintering of the liquid-phase sintering aid, has the advantages of simple and convenient operation, low production cost and high efficiency, and can prepare the boron carbide composite ceramic with high strength and high performance by the synergistic enhancement of the in-situ reaction and the liquid-phase hot-pressing sintering, thereby having good application prospect.
The hot-pressing liquid-phase sintered boron carbide composite ceramic provided by the invention is prepared by the preparation method, and has the bending strength of 480-550MPa and the fracture toughness of 5.3-6.7MPa1 /2。
Compared with the prior art, the method solves the problems of large brittleness, low strength and difficult densification of the traditional boron carbide ceramic, and the prepared boron carbide composite ceramic has high bending strength and fracture toughness, so that the application field of the boron carbide ceramic can be further expanded.
Drawings
FIG. 1 is a scanning electron microscope image of a fracture of a hot-hydraulic liquid-phase sintered boron carbide composite ceramic in example 2 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, the present invention is further described below by way of examples.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods or materials in connection with which they pertain. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
The embodiment of the invention discloses a hot-pressing liquid-phase sintered boron carbide composite ceramic and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, weighing the raw materials, and comprises the following components in percentage by mass: 69-81 wt% of boron carbide powder, 6-10 wt% of titanium carbide powder, 8-10 wt% of sintering aid, 0.3-0.5 wt% of dispersant, 3-5 wt% of binder and 2-5 wt% of plasticizer.
The sintering aid is any combination of alumina, alumina and yttrium oxide, alumina and carbon black. When the sintering aid is the combination of alumina and yttrium oxide, the mass ratio of the alumina to the yttrium oxide is controlled to be 1.5-1.7; when the sintering aid is the combination of alumina and carbon black, the mass ratio of the alumina to the carbon black is controlled to be 5-12.
The grain diameters of the boron carbide powder, the titanium carbide powder and the sintering aid powder are controlled, the grain diameter D50 of the boron carbide powder is 0.3-0.8um, the grain diameter D50 of the titanium carbide powder is 0.5-1um, the grain diameter D50 of the aluminum oxide is 0.2-0.5um, the grain diameter D50 of the yttrium oxide is 0.5-1um, and the grain diameter D50 of the carbon black is 0.2-0.5 um.
The dispersing agent is selected from one or more of tetramethyl ammonium hydroxide, ammonium polyacrylate and triethanolamine, the binder is selected from one or more of polyvinyl alcohol, polyvinyl butyral and hydroxymethyl cellulose, and the plasticizer is selected from one or more of polyethylene glycol, glycerol and polyacrylic acid.
S2, mixing the raw materials, specifically adopting a ball milling pulping mode, taking boron carbide ceramic balls as medium balls during ball milling, wherein the ball diameter is 5-10mm, adding the raw materials and deionized water, and the mass of the medium balls is as follows: the total mass of the boron carbide powder, the titanium carbide powder and the sintering aid is as follows: ball-milling the deionized water in a roller for 72 hours, wherein the mass of the deionized water is 2:1: 1; then carrying out spray granulation, and participating in industrial experience of a granulation process;
S3, prepressing to form a green body, prepressing to form the green body with the pressure range of 10-15Mpa, and then putting the green body in a graphite mould for hot-pressing sintering. The hot-pressing sintering process specifically comprises the following steps: vacuumizing the sintering furnace, wherein the vacuum degree is less than 0.001MPa, and heating to 1000 ℃ at the heating speed of 5 ℃/min; introducing argon into the sintering furnace, sintering in the argon atmosphere, starting pressurizing, raising the sintering pressure to 25-30MPa at the temperature raising speed of 5 ℃/min to the sintering temperature of 1840-1900 ℃, and preserving the temperature for 1-2h to obtain the boron carbide composite ceramic.
The preparation method adopts the technical scheme that the in-situ reaction is matched with the hot-pressing sintering of the liquid-phase sintering aid, has the advantages of simple and convenient operation, low production cost and high efficiency, and the prepared boron carbide composite ceramic has excellent performance.
In the following examples, bending strength of the material was measured by three-point bending, and fracture toughness of the material was measured by a single-side notched beam method.
Example 1
Weighing raw materials, wherein the raw materials comprise 80.7 parts of boron carbide powder, 6 parts of titanium carbide powder, 8 parts of aluminum oxide, 0.3 part of tetramethylammonium hydroxide, 5 parts of polyvinyl alcohol and 5 parts of glycerol. The particle diameter of the boron carbide powder D50 is 0.3um, the particle diameter of the titanium carbide D50 is 1um, and the particle diameter of the aluminum oxide D50 is 0.4 um.
Mixing the raw materials, adopting a ball milling pulping mode, taking boron carbide ceramic balls as medium balls during ball milling, wherein the ball diameter is 5-10mm, adding the raw materials and deionized water, and the mass of the medium balls is as follows: the boron carbide powder, the titanium carbide powder and the sintering auxiliary agent have the following mass portions: ball milling is carried out for 72h by a roller when the mass of the deionized water is 2:1:1, and then spray granulation is carried out.
Prepressing the mixture into a green body, prepressing the green body to form the mixture under the pressure of 10Mpa, and then putting the green body in a graphite mold for hot-pressing and sintering. The hot-pressing sintering process specifically comprises the following steps: vacuumizing the mould, wherein the vacuum degree is less than 0.001MPa, and heating to 1000 ℃ at the heating speed of 5 ℃/min; and introducing argon into the mold, sintering in an argon atmosphere, starting pressurizing, raising the temperature to the sintering temperature of 1880 ℃ at the temperature raising speed of 5 ℃/min, and preserving the temperature for 1h to obtain the boron carbide composite ceramic.
The boron carbide composite ceramic prepared in the example 1 is detected to have the bending strength of 489MPa and the fracture toughness of 5.3MPa1 /2。
Example 2
Weighing raw materials, wherein the raw materials comprise 78.6 parts of boron carbide powder, 8 parts of titanium carbide powder, 5 parts of aluminum oxide, 3 parts of yttrium oxide, 0.4 part of tetramethylammonium hydroxide, 3 parts of hydroxymethyl cellulose and 2 parts of polyethylene glycol. The grain diameter of the boron carbide powder D50 is 0.5um, the grain diameter of the titanium carbide D50 is 0.5um, the grain diameter of the aluminum oxide D50 is 0.4um, and the grain diameter of the yttrium oxide D50 is 1 um.
Mixing the raw materials, adopting a ball milling pulping mode, taking boron carbide ceramic balls as medium balls during ball milling, wherein the ball diameter is 5-10mm, adding the raw materials and deionized water, and the mass of the medium balls is as follows: the boron carbide powder, the titanium carbide powder and the sintering auxiliary agent have the following mass portions: ball milling is carried out for 72h by a roller when the mass of the deionized water is 2:1:1, and then spray granulation is carried out.
Prepressing the mixture into a green body, prepressing the green body to form the mixture under the pressure of 12Mpa, and then putting the green body in a graphite mold for hot-pressing and sintering. The hot-pressing sintering process specifically comprises the following steps: vacuumizing the mold, wherein the vacuum degree is less than 0.001MPa, and heating to 1000 ℃ at the heating speed of 5 ℃/min; and introducing argon into the mould, sintering in an argon atmosphere, starting pressurizing, raising the temperature to 1840 ℃ at the temperature rise speed of 5 ℃/min under the sintering pressure of 27MPa, and preserving the temperature for 1h to obtain the boron carbide composite ceramic.
The microstructure is shown in figure 1, and the inner part has no holes and high densification degree. The boron carbide composite ceramic prepared in the example 2 is detected to have the bending strength of 550MPa and the fracture toughness of 6.7MPa1/2。
Example 3
Weighing raw materials, including 69.5 parts of boron carbide powder, 10 parts of titanium carbide powder, 9 parts of alumina, 1 part of carbon black, 0.5 part of ammonium polyacrylate, 5 parts of polyvinyl butyral and 5 parts of polyethylene glycol. The particle size of boron carbide powder D50 ═ 0.4um, the particle size of titanium carbide D50 ═ 0.8um, the particle size of alumina D50 ═ 0.5um, and the particle size of carbon black D50 ═ 0.5 um.
Mixing the raw materials, adopting a ball milling pulping mode, taking boron carbide ceramic balls as medium balls during ball milling, wherein the ball diameter is 5-10mm, adding the raw materials and deionized water, and the mass of the medium balls is as follows: the boron carbide powder, the titanium carbide powder and the sintering auxiliary agent have the following mass portions: ball milling is carried out for 72h by a roller when the mass of the deionized water is 2:1:1, and then spray granulation is carried out.
Prepressing the mixture into a green body, prepressing the green body to form the green body under the pressure of 14Mpa, and then putting the green body in a mould for hot-pressing and sintering. The hot-pressing sintering process specifically comprises the following steps: vacuumizing the mould, wherein the vacuum degree is less than 0.001MPa, and heating to 1000 ℃ at the heating speed of 5 ℃/min; and introducing argon into the mould, sintering in an argon atmosphere, starting pressurizing, raising the temperature to 1900 ℃ at the temperature raising speed of 5 ℃/min, and preserving the temperature for 2 hours to obtain the boron carbide composite ceramic.
The boron carbide composite ceramic prepared in the example 3 is detected to have the bending strength of 527MPa and the fracture toughness of 6.2MPa1 /2。
Example 4
Weighing raw materials, wherein the raw materials comprise 72.6 parts of boron carbide powder, 9 parts of titanium carbide powder, 5.4 parts of aluminum oxide, 3.6 parts of yttrium oxide, 0.4 part of triethanolamine, 4 parts of hydroxymethyl cellulose and 5 parts of polyacrylic acid. The grain diameter of the boron carbide powder D50 is 0.8um, the grain diameter of the titanium carbide D50 is 0.6um, the grain diameter of the aluminum oxide D50 is 0.4um, and the grain diameter of the yttrium oxide D50 is 1 um.
Mixing the raw materials, adopting a ball milling pulping mode, taking boron carbide ceramic balls as medium balls during ball milling, wherein the ball diameter is 5-10mm, adding the raw materials and deionized water, and the mass of the medium balls is as follows: the total mass of the boron carbide powder, the titanium carbide powder and the sintering aid is as follows: ball milling is carried out for 72h by a roller when the mass of the deionized water is 2:1:1, and then spray granulation is carried out.
Prepressing the mixture into a green body, prepressing the green body to form the mixture under the pressure of 15Mpa, and then putting the green body in a graphite mold for hot-pressing and sintering. The hot-pressing sintering process specifically comprises the following steps: vacuumizing the sintering furnace, wherein the vacuum degree is less than 0.001MPa, and heating to 1000 ℃ at the heating speed of 5 ℃/min; and introducing argon into the sintering furnace, sintering in an argon atmosphere, starting pressurizing, raising the temperature to the sintering temperature of 1860 ℃ at the temperature rise speed of 5 ℃/min, and preserving the temperature for 1.5 hours to obtain the boron carbide composite ceramic.
The boron carbide composite ceramic prepared in example 4 is detected to have the bending strength of 520MPa and the fracture toughness of 5.4MPa1 /2。
Comparative example 1
The comparative example is different from example 1 in that the raw material includes 86.7 parts of boron carbide powder and does not contain titanium carbide powder, and other raw materials and the preparation method are the same.
The boron carbide composite ceramic prepared in comparative example 1 is detected to have the bending strength of 350MPa and the fracture toughness of 3.3MPa1 /2Compared with the boron carbide composite ceramic prepared in example 1, the material strength is obviously reduced.
Comparative example 2
The comparative example is different from example 2 in that the raw materials include 83.6 parts of boron carbide powder and 13 parts of titanium carbide powder, and do not contain a sintering aid, and other raw materials and the preparation method are the same.
The boron carbide composite ceramic prepared in comparative example 1 is detected to have the bending strength of 300MPa and the fracture toughness of 2.8MPa 1 /2Compared with the boron carbide composite ceramic prepared in example 2, the material strength is obviously reduced.
Although the present disclosure has been described with reference to the above embodiments, the scope of the present disclosure is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention as disclosed, and these changes and modifications will fall within the scope of the invention.
Claims (10)
1. A preparation method of hot-pressing liquid-phase sintered boron carbide composite ceramic is characterized by comprising the following steps:
weighing the raw materials in percentage by mass: 69-81 wt% of boron carbide powder, 6-10 wt% of titanium carbide powder, 8-10 wt% of sintering aid, 0.3-0.5 wt% of dispersant, 3-5 wt% of binder and 2-5 wt% of plasticizer;
uniformly mixing the raw materials, and performing spray granulation;
prepressing to form a green body, putting the green body into a graphite grinding tool, and performing hot-pressing sintering to obtain the boron carbide composite ceramic, wherein the sintering temperature is 1840-.
2. The method for preparing the hot-pressing liquid-phase sintered boron carbide composite ceramic according to claim 1, wherein the sintering aid is any one combination of alumina, alumina and yttria, alumina and carbon black.
3. The method for preparing the hot-pressing liquid-phase sintered boron carbide composite ceramic according to claim 2, wherein the sintering aid is alumina and yttria, and the mass ratio of the alumina to the yttria is 1.5-1.7.
4. The method for preparing the hot-pressing liquid-phase sintered boron carbide composite ceramic according to claim 2, wherein the sintering aid is alumina and carbon black, and the mass ratio of the alumina to the carbon black is 5-12.
5. The method for preparing the hot-pressing liquid-phase sintered boron carbide composite ceramic according to claim 1, wherein the particle size of the boron carbide powder D50 is 0.3-0.8um, and the particle size of the titanium carbide powder D50 is 0.5-1 um.
6. The method for preparing the hot-pressing liquid-phase sintered boron carbide composite ceramic according to claim 2, wherein the alumina particle size D50 is 0.2-0.5um, the yttria particle size D50 is 0.5-1um, and the carbon black particle size D50 is 0.2-0.5 um.
7. The method for preparing the hot-pressing liquid-phase sintered boron carbide composite ceramic according to claim 1, wherein the dispersant is one or more selected from tetramethylammonium hydroxide, ammonium polyacrylate and triethanolamine, the binder is one or more selected from polyvinyl alcohol, polyvinyl butyral and hydroxymethyl cellulose, and the plasticizer is one or more selected from polyethylene glycol, glycerol and polyacrylic acid.
8. The method for preparing the hot-pressing liquid-phase sintered boron carbide composite ceramic according to claim 1, wherein the hot-pressing sintering process specifically comprises: vacuumizing the sintering furnace, wherein the vacuum degree is less than 0.001MPa, and heating to 1000 ℃ at the heating speed of 5 ℃/min; and introducing argon into the sintering furnace, starting pressurizing, sintering in an argon atmosphere, heating to the sintering temperature at the heating rate of 5 ℃/min, and preserving heat for 1-2 h.
9. A hot-pressed liquid-phase sintered boron carbide composite ceramic produced by the production method according to any one of claims 1 to 8.
10. The hot-pressing liquid-phase sintered boron carbide composite ceramic of claim 9, wherein the bending strength of the hot-pressing liquid-phase sintered boron carbide composite ceramic is 480-550Mpa, and the fracture toughness thereof is 5.3-6.7Mpa1/2。
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