CN113121238B - High-performance boron carbide-based composite ceramic material and preparation method thereof - Google Patents
High-performance boron carbide-based composite ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance boron carbide-based composite ceramic material and a preparation method thereof. The high-performance boron carbide-based composite ceramic material is HfB formed by in-situ reaction 2 And SiC and added SiC nw For the reinforcing and toughening phase, B 4 C is a substrate and is formed by pressure sintering. The raw materials of the material comprise the following materials: hfSi 2 40-45% of powder and SiC nw 0.88-4.45 percent of the total weight of the composition and the balance of B 4 And C, powder. Preparing mixed powder by a mechanical powder mixing method, and performing discharge plasma sintering on the mixed powder to obtain a blank body, thereby finally obtaining the boron carbide composite ceramic material. The invention realizes B 4 The C composite ceramic is sintered at low temperature for a short time, and compared with the traditional boron carbide ceramic, the boron carbide-based composite ceramic material prepared by the method has higher density and excellent comprehensive mechanical property.
Description
Technical Field
The invention belongs to the technical field of ceramic matrix composite materials, and particularly relates to a high-performance boron carbide-based composite ceramic material and a preparation method thereof.
Background
Boron carbide (B) 4 C) The ceramic is an important non-oxide ceramic, has a series of excellent characteristics of low density, high hardness, good high-temperature thermal conductivity and thermal stability, larger neutron absorption cross section and the like, and has wide application prospects in the fields of wear resistance, protective armor, nuclear energy, military and the like.
In the boron carbide ceramic, the covalent bond content is as high as 93.94%, the sintering of boron carbide is difficult to densify due to the high covalent bond content, the sintering temperature is over 2200 ℃ generally, and the toughness and strength of the boron carbide ceramic obtained by sintering are not ideal. While boron carbide is resistantWhen the boron carbide powder is applied to the fields of grinding, protective armor and the like, the boron carbide is often required to have higher density and better mechanical property. Thus, B is reduced 4 The sintering temperature, the comprehensive mechanical property and the mechanical processing property of the C ceramic are of great significance to the application of the C ceramic.
Studies have shown that in B 4 Introducing proper amount of SiC or HfB into C 2 B can be improved to a certain extent by waiting for the second phase 4 Sintering property of C and improvement of B 4 The mechanical property of the C ceramic. However, if SiC, hfB 2 Directly mixed in the form of common powder, the higher temperature is still required for sintering and densifying the block, thereby limiting B 4 And the overall performance of the C ceramic composite material is improved.
Disclosure of Invention
Based on the background, the invention provides a high-performance boron carbide-based composite ceramic material and a preparation method thereof, and HfSi is prepared by 2 And SiC nw As additive to B 4 HfB generated by in-situ reaction in C matrix 2 And SiC nw The compactness and the mechanical property of the composite material are improved, and the high-performance B is realized 4 And C-based composite ceramic material is sintered at low temperature.
The specific scheme of the invention is as follows:
the invention provides a preparation method of a high-performance boron carbide-based composite ceramic material, which comprises the following steps: with B 4 C powder, hfSi 2 Powder, siC nw The boron carbide-based composite ceramic material is prepared by preparing mixed powder from the raw materials by a mechanical powder mixing method and sintering the mixed powder under pressure.
Preferably, the raw materials comprise the following components in percentage by mass: hfSi 2 40-45% of powder and SiC nw 0.88-4.45 percent of the total weight of the composition and the balance of B 4 C, powder; preferably HfSi 2 The mass percentage of the powder is 42.34-43.92%.
Preferably, B is 4 The grain diameter of the C powder is 0.5-5 mu m, and the purity is more than or equal to 97 percent; preferably, the HfSi 2 The particle size of the powder is 0.5-10 μm, and the purity is more than or equal to 98%; preferably, the SiC nw Has a purity of not less than 98% and a diameter of0.1-0.6 μm and a length of 50-100 μm.
Preferably, the pressure sintering is spark plasma sintering; the specific parameters of the spark plasma sintering are as follows: the sintering vacuum degree is less than 20Pa, the sintering temperature is 1600-1750 ℃, the sintering pressure is 45-55MPa, and the heat preservation time is 8-15min.
Preferably, a gradient temperature rise mode is adopted in the spark plasma sintering process to raise the temperature to the sintering temperature; specifically, heating to 650-800 ℃ at a heating rate of 80-100 ℃/min, and keeping the temperature for 5-10min; keeping the heating rate to continuously heat to 1400-1500 ℃; then heating to the sintering temperature at the heating rate of 20-50 ℃/min, and preserving the heat for 8-15min.
Preferably, gradually pressurizing to a sintering pressure in the spark plasma sintering process, specifically, the initial pressure is 1-3MPa, and when the temperature is raised to 650-800 ℃, pressurizing to 10-15MPa; when the temperature is raised to 1400-1500 ℃, the pressure is increased to the sintering pressure.
Preferably, after the sintering heat preservation is finished, the pressure is reduced to 0MPa at the speed of 30-50MPa/min, and the sintering heat preservation is carried out along with furnace cooling.
Preferably, the mechanical powder mixing method is wet or dry ball milling.
Preferably, the wet ball milling specifically comprises the following steps: (1) B is to be 4 C powder, hfSi 2 Putting the powder into a ball mill, and wet-milling for 8-10h by taking absolute ethyl alcohol as a medium; wherein the ball milling rotation speed is 300-400r/min, and the ball-to-material ratio is 4-5:1; (2) Adding SiC after ultrasonic dispersion nw Continuously wet grinding for 1-2h under the condition that the ball milling rotating speed is 150-200 r/min; more preferably, the SiC is ultrasonically dispersed nw In the process, deionized water is used as a dispersion medium, sodium hexametaphosphate is used as a dispersant, and ultrasonic dispersion is carried out for 30-60min; the added mass of the dispersing agent is SiC nw 4-6% of the mass.
Preferably, after wet ball milling, drying and sieving treatment are carried out; the drying temperature is 40-55 ℃, and the drying time is 10-15h; when sieving, the mesh number of the sieve is 180-240 meshes.
The invention also provides a high-performance boron carbide-based composite ceramic material prepared by the method.
Has the advantages that:
the invention uses B 4 C as a matrix, hfSi 2 The powder is used as sintering aid, and SiC is added nw And the boron carbide-based composite ceramic material with high density, good mechanical property and excellent sintering property is prepared by pressure sintering. Realizes the low-temperature and short-time densification sintering of the boron carbide-based composite ceramic material, and solves the problems of high sintering temperature, long heat preservation time and the like of the boron carbide-based ceramic
Wherein, hfSi 2 As a sintering aid, B is added in a specific proportion 4 In the C matrix, during the spark plasma sintering process, the in-situ reaction generates fine crystal grains in B 4 Uniformly distributed SiC and HfB in a C matrix 2 The equal-strength toughening phase promotes sintering densification, effectively inhibits the growth of crystal grains and solves the problem of B 4 C the ceramic sintering density is not high. Further, hfB was generated 2 Has higher conductivity, so that B 4 The C-based composite ceramic can be processed by wire electrical discharge machining, and the problem of B 4 C, the ceramic is difficult to machine. SiC nw By adding (B), B is greatly improved 4 The fracture toughness of C ceramic solves B 4 C, poor toughness of the ceramic.
Mixing SiC powder and HfB 2 Adding powder B directly 4 Compared with the mode of a C matrix, the invention has the advantages that the second phase introduced by the in-situ reaction is more uniformly distributed in the boron carbide, and the problems of SiC and HfB are solved 2 In B 4 The problem of the dispersion uniformity of the C matrix is solved, the interface of the second phase and the interface of the boron carbide are combined more firmly, the comprehensive performance of the boron carbide is improved, besides, the sintering temperature is reduced, the sintering heat preservation time is shortened, and the problem of B matrix dispersion uniformity is solved 4 The problems of high sintering temperature, long heat preservation time and the like of C ceramic are solved, and B is realized 4 The C ceramic is sintered at low temperature (1600-1750 ℃) and short time (8-15 min).
Drawings
FIG. 1 shows the addition of SiC in different mass percentages nw Preparation of B 4 XRD pattern of C base composite ceramic.
FIG. 2 shows the addition of different amounts of SiC nw Preparation of B 4 Scanning a fracture of the C-based composite ceramic;
wherein: (a) Corresponding to B prepared in example 1 4 C-based composite ceramics; (b) Corresponding to B prepared in example 2 4 C-based composite ceramics; (c) Prepared in accordance with example 3B 4 C-based composite ceramics.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
The performances of the examples of the invention and the comparative examples were tested as follows: (1) the relative density is measured by Archimedes drainage method; (2) the Vickers hardness is measured by using a Vickers hardness tester model HV 5; (3) The fracture toughness test method adopts a single-side notched beam method and an electronic universal material tester; (4) The bending strength test method adopts a three-point bending method and an electronic universal material tester.
Example 1
A preparation method of a high-performance boron carbide-based composite ceramic material comprises the following steps:
(1) Preparation of the Mixed powder
Weighing 55.20% by weight of B 4 C powder (purity 97%, average particle diameter 3 μm), 43.92% 2 Powder (purity 98%, average particle diameter 7 μm), 0.88% SiC nw (purity is more than or equal to 98%, diameter is 0.1-0.6 μm, length is 50-100 μm), weighing B 4 C powder and HfSi 2 Pouring the powder into a ball milling tank, taking absolute ethyl alcohol as a ball milling medium, and placing the ball milling tank into a planetary ball mill at the ball-material ratio of 4:1, wherein the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 8 hours until the powder is completely and uniformly mixed; then setting the rotating speed of the ball mill to be 160r/min, and adding the dispersed SiC nw Continuing ball milling for 2 hours, then placing the mixture in a vacuum drying oven for drying for 12 hours at 50 ℃, and sieving the mixture by a 200-mesh sieve to obtain mixed powder;
(2) Spark plasma sintering
Assembling the mixed powder to a graphite mould with the inner diameter of 20mm, putting the graphite mould into a discharge plasma sintering furnace, pre-pressing the graphite mould at the pressure of 1MPa, vacuumizing the sintering furnace to 15Pa at room temperature, heating to 700 ℃ at the speed of 90 ℃/min, keeping the temperature for 10min, increasing the pressure to 10MPa, then continuously heating to 1500 ℃, increasing the pressure to 50MPa, then increasing the temperature from 1500 ℃ to 1650 ℃ at the speed of 40 ℃/min, keeping the temperature for 10min, reducing the pressure to 0MPa at the speed of 50MPa/min after the heat preservation is finished, and cooling the sample along with the furnace.
After testing, B obtained in this example 4 The relative density, vickers hardness, fracture toughness and bending strength of the C-based composite ceramic material are respectively 95.2 percent, 25.7GPa and 7.7 MPa.m 1/2 、637.3MPa。
Example 2
A preparation method of a high-performance boron carbide-based composite ceramic material comprises the following steps:
(1) Preparation of the Mixed powder
Weighing 54.40% by weight of B 4 C powder (purity 97%, average particle diameter 3 μm), 42.95% 2 Powder (purity 98%, average particle diameter 7 μm) and 2.65% SiC nw (purity is more than or equal to 98%, diameter is 0.1-0.6 μm, length is 50-100 μm), weighing B 4 C powder and HfSi 2 Pouring the powder into a ball milling tank, taking absolute ethyl alcohol as a ball milling medium, and placing the ball milling tank into a planetary ball mill at the ball-material ratio of 4:1, wherein the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 8 hours until the powder is completely and uniformly mixed; then setting the rotating speed of the ball mill to be 160r/min, and adding the dispersed SiC nw Continuing ball milling for 2 hours, then placing the mixture in a vacuum drying oven for drying for 12 hours at 50 ℃, and sieving the mixture by a 200-mesh sieve to obtain mixed powder;
(2) Spark plasma sintering
Assembling the mixed powder to a graphite mould with the inner diameter of 20mm, putting the graphite mould into a discharge plasma sintering furnace, pre-pressing the graphite mould at the pressure of 1MPa, vacuumizing the sintering furnace to 15Pa at room temperature, heating to 700 ℃ at the speed of 90 ℃/min, keeping the temperature for 10min, increasing the pressure to 10MPa, then continuously heating to 1500 ℃, increasing the pressure to 50MPa, then increasing the temperature from 1500 ℃ to 1650 ℃ at the speed of 40 ℃/min, keeping the temperature for 10min, reducing the pressure to 0MPa at the speed of 30MPa/min after the heat preservation is finished, and cooling the sample along with the furnace.
After testing, B obtained in this example 4 The relative density, vickers hardness, fracture toughness and bending strength of the C-based composite ceramic material are respectively 97.4 percent, 28.2GPa and 8.9 MPa.m 1/2 、698.9MPa。
Example 3
A preparation method of a high-performance boron carbide-based composite ceramic material comprises the following steps:
(1) Preparation of the Mixed powder
Weighing 53.21% by mass of B 4 C powder (purity 97%, average particle diameter 1 μm), 42.34% 2 Powder (purity 98.5%, average particle diameter 1 μm) and 4.45% SiC nw (purity is more than or equal to 98%, diameter is 0.1-0.6 μm, length is 50-100 μm), weighing B 4 C powder and HfSi 2 Pouring the powder into a ball milling tank, taking absolute ethyl alcohol as a ball milling medium, and placing the ball milling tank into a planetary ball mill at the ball-material ratio of 5:1, wherein the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 8 hours until the powder is completely and uniformly mixed; then setting the rotating speed of the ball mill to be 160r/min, and adding the dispersed SiC nw Continuing ball milling for 2 hours, then placing the mixture in a vacuum drying oven for drying for 12 hours at 50 ℃, and sieving the mixture by a 200-mesh sieve to obtain mixed powder;
SiC nw ultrasonic dispersion treatment is required, deionized water is taken as a dispersion medium during ultrasonic treatment, sodium hexametaphosphate is taken as a dispersant, and SiC is added as mass of the dispersant nw 4% of the mass, and ultrasonic dispersion for 40min.
(2) Spark plasma sintering
Assembling the mixed powder to a graphite mould with the inner diameter of 20mm, putting the graphite mould into a discharge plasma sintering furnace, pre-pressing the graphite mould at the pressure of 1MPa, vacuumizing the sintering furnace to 10Pa at room temperature, heating to 800 ℃ at the speed of 80 ℃/min, keeping the temperature for 5min, increasing the pressure to 15MPa, then continuously heating to 1400 ℃, increasing the pressure to 45MPa, then increasing the temperature from 1400 ℃ to 1600 ℃ at the speed of 20 ℃/min, keeping the temperature for 8min, reducing the pressure to 0MPa at the speed of 50MPa/min after the heat preservation is finished, and cooling the sample along with the furnace.
After testing, B obtained in this example 4 Relative density, vickers hardness and fracture toughness of C-based composite ceramic materialThe flexural strengths thereof were 94.6%, 26.3GPa and 8.1 MPa.m, respectively 1/2 、660.5MPa。
Comparative example 1
This comparative example prepared pure B by spark plasma sintering 4 The process of the C ceramic comprises the following steps:
b is to be 4 Assembling C powder (with purity of 97% and average particle size of 3 μm) to a graphite mold with an inner diameter of 20mm, placing the graphite mold into a discharge plasma sintering furnace, pre-pressing the graphite mold at a pressure of 1MPa, vacuumizing the sintering furnace to 15Pa at room temperature, heating to 700 ℃ at a speed of 90 ℃/min, keeping the temperature for 10min, increasing the pressure to 10MPa, then continuously heating to 1500 ℃, increasing the pressure to 50MPa, then increasing the temperature from 1500 ℃ to 1650 ℃ at a heating speed of 40 ℃/min, keeping the temperature for 10min, reducing the pressure to 0MPa at a speed of 50MPa/min, and cooling the sample with the furnace.
After testing, B obtained in this example 4 The relative density, vickers hardness, fracture toughness and bending strength of the C-based composite ceramic material are 82.9 percent, 15.2GPa and 2.7 MPa.m 1/2 、207.6MPa。
Comparative example 2
This comparative example prepared pure B by spark plasma sintering 4 C-HfB 2 The ceramic process is as follows:
(1) Preparation of the Mixed powder
Weighing 55.69% by mass of B 4 C powder (purity 97%, average particle diameter 1 μm), 44.31% 2 Powder (purity 98.5%, average particle diameter 1 μm), B 4 C powder and HfSi 2 Pouring the powder into a ball milling tank, taking absolute ethyl alcohol as a ball milling medium, and ball-to-material ratio of 5:1, placing the ball milling tank into a planetary ball mill, wherein the rotating speed of the ball mill is 360r/min, ball milling is carried out for 8 hours until the ball milling tank is completely and uniformly mixed, then placing the ball milling tank into a vacuum drying oven, drying the ball milling tank for 12 hours at 50 ℃, and sieving the ball milling tank with a 200-mesh sieve to obtain mixed powder;
(2) Spark plasma sintering
Assembling the mixed powder to a graphite die with the inner diameter of 20mm, putting the graphite die into a discharge plasma sintering furnace, pre-pressing the graphite die at the pressure of 1MPa, vacuumizing the sintering furnace to 10Pa at room temperature, heating to 800 ℃ at the speed of 80 ℃/min, preserving heat for 5min, adding the pressure to 15MPa, then continuously heating to 1400 ℃, adding the pressure to 45MPa, then heating from 1400 ℃ to 1600 ℃ at the speed of 20 ℃/min, preserving heat for 8min, reducing the pressure to 0MPa at the speed of 50MPa/min after the heat preservation is finished, and cooling the sample along with the furnace.
After testing, B obtained in this example 4 The relative density, vickers hardness, fracture toughness and bending strength of the C-based composite ceramic material are 99.46%, 29.9GPa and 4.93 MPa.m 1/2 、573.2MPa。
Comparative example 3
A preparation method of a boron carbide-based composite ceramic material comprises the following steps:
(1) Preparation of the Mixed powder
Weighing 47.07% by weight of B 4 C powder (purity 97%, average particle diameter 3 μm), 37.79% SiC powder (purity 98%, average particle diameter 7 μm), 15.14% HfB 2 Pouring the powder (with the purity of 98 percent and the average particle size of 7 mu m) into a ball milling tank, taking absolute ethyl alcohol as a ball milling medium, and setting the ball milling tank into a planetary ball mill at the ball-material ratio of 4:1, wherein the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 8 hours until the powder is completely and uniformly mixed; drying in a vacuum drying oven at 50 deg.C for 12 hr, and sieving with 200 mesh sieve to obtain mixed powder;
(2) Spark plasma sintering
Assembling the mixed powder to a graphite mould with the inner diameter of 20mm, putting the graphite mould into a discharge plasma sintering furnace, pre-pressing the graphite mould at the pressure of 1MPa, vacuumizing the sintering furnace to 15Pa at room temperature, heating to 700 ℃ at the speed of 90 ℃/min, keeping the temperature for 10min, increasing the pressure to 10MPa, then continuously heating to 1500 ℃, increasing the pressure to 50MPa, then increasing the temperature from 1500 ℃ to 1650 ℃ at the speed of 40 ℃/min, keeping the temperature for 10min, reducing the pressure to 0MPa at the speed of 50MPa/min after the heat preservation is finished, and cooling the sample along with the furnace.
After testing, B obtained in this example 4 The relative density, vickers hardness, fracture toughness and bending strength of the C-based composite ceramic material are respectively 94.73 percent, 22.3GPa and 3.9 MPa.m 1/2 、387.2MPa。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (11)
1. A preparation method of a high-performance boron carbide-based composite ceramic material is characterized by comprising the following steps: with B 4 C powder, hfSi 2 Powder, siC nw Preparing the raw materials into mixed powder by adopting a mechanical powder mixing method, and performing pressure sintering on the mixed powder to obtain a boron carbide-based composite ceramic material;
the raw materials comprise the following components in percentage by mass: hfSi 2 40-45% of powder and SiC nw 0.88-4.45 percent of the total weight of the composition and the balance of B 4 C, powder; hfSi 2 And B 4 C is generated in situ in B 4 Uniformly distributed SiC and HfB in C matrix 2 。
2. The method for preparing a high-performance boron carbide-based composite ceramic material according to claim 1, wherein HfSi is 2 The mass percentage of the powder is 42.34-43.92%.
3. The method for producing a high-performance boron carbide-based composite ceramic material according to claim 1 or 2, wherein B is 4 The grain diameter of the C powder is 0.5-5 mu m, and the purity is more than or equal to 97 percent; the HfSi 2 The particle size of the powder is 0.5-10 μm, and the purity is more than or equal to 98%; the SiC nw The purity of the product is more than or equal to 98 percent, the diameter is 0.1-0.6 μm, and the length is 50-100 μm.
4. The method for producing a high-performance boron carbide-based composite ceramic material according to claim 1 or 2, wherein the pressure sintering is spark plasma sintering; the specific parameters of the spark plasma sintering are as follows: the sintering vacuum degree is less than 20Pa, the sintering temperature is 1600-1750 ℃, the sintering pressure is 45-55MPa, and the heat preservation time is 8-15min.
5. The method for preparing a high-performance boron carbide-based composite ceramic material according to claim 4, wherein the temperature is increased to the sintering temperature in a gradient temperature increasing manner during the spark plasma sintering process; specifically, heating to 650-800 ℃ at a heating rate of 80-100 ℃/min, and keeping the temperature for 5-10min; keeping the heating rate to continuously heat to 1400-1500 ℃; then heating to the sintering temperature at the heating rate of 20-50 ℃/min, and preserving the heat for 8-15min.
6. The method for producing a high-performance boron carbide-based composite ceramic material according to claim 4, wherein the pressure is gradually increased to the sintering pressure in the spark plasma sintering process, specifically, the initial pressure is 1 to 3MPa, and the pressure is increased to 10 to 15MPa when the temperature is increased to 650 to 800 ℃; when the temperature is increased to 1400-1500 ℃, pressurizing to sintering pressure; after the sintering and heat preservation are finished, the pressure is reduced to 0MPa at the speed of 30-50MPa/min, and the furnace is cooled.
7. The method for preparing a high-performance boron carbide-based composite ceramic material according to claim 1 or 2, wherein the mechanical powder mixing method is wet or dry ball milling.
8. The method for preparing a high-performance boron carbide-based composite ceramic material according to claim 7, wherein the wet ball milling specifically comprises the following steps: (1) B is to be 4 C powder, hfSi 2 Putting the powder into a ball mill, and wet-milling for 8-10h by taking absolute ethyl alcohol as a medium; wherein the ball milling rotation speed is 300-400r/min, and the ball-to-material ratio is 4-5:1; (2) Adding SiC after ultrasonic dispersion nw And continuously wet grinding for 1-2h under the condition that the ball milling rotating speed is 150-200 r/min.
9. The method for producing a high-performance boron carbide-based composite ceramic material according to claim 8, wherein SiC is ultrasonically dispersed nw In the process, deionized water is used as a dispersion medium, sodium hexametaphosphate is used as a dispersant, and ultrasonic dispersion is carried out for 30-60min; the added mass of the dispersing agent is SiC nw 4-6% of the mass.
10. The method for preparing a high-performance boron carbide-based composite ceramic material according to claim 8, wherein the drying and sieving treatment is performed after the wet ball milling; the drying temperature is 40-55 ℃, and the drying time is 10-15h; when sieving, the mesh number of the sieve is 180-240 meshes.
11. A high-performance boron carbide-based composite ceramic material, which is prepared by the method according to any one of claims 1 to 10.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5505899A (en) * | 1993-06-17 | 1996-04-09 | Elektroschmelzwerk Kempten Gmbh | Process for producing bodies based on boron carbide by pressureless sintering |
| CN101265108A (en) * | 2008-04-16 | 2008-09-17 | 哈尔滨工业大学 | Boride-silicon carbide-boron carbide ternary ceramic-base composite material and preparation method thereof |
| CN102503427A (en) * | 2011-11-10 | 2012-06-20 | 哈尔滨工业大学 | Preparation method of high-toughness boride-carbide composite ceramic |
| CN104529459A (en) * | 2014-12-03 | 2015-04-22 | 武汉理工大学 | B4C-HfB2-SiC ternary high-temperature eutectic composite ceramic material and preparation method |
| JP2016132607A (en) * | 2015-01-21 | 2016-07-25 | 新日鐵住金株式会社 | Ceramic composite material and manufacturing method therefor |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5505899A (en) * | 1993-06-17 | 1996-04-09 | Elektroschmelzwerk Kempten Gmbh | Process for producing bodies based on boron carbide by pressureless sintering |
| CN101265108A (en) * | 2008-04-16 | 2008-09-17 | 哈尔滨工业大学 | Boride-silicon carbide-boron carbide ternary ceramic-base composite material and preparation method thereof |
| CN102503427A (en) * | 2011-11-10 | 2012-06-20 | 哈尔滨工业大学 | Preparation method of high-toughness boride-carbide composite ceramic |
| CN104529459A (en) * | 2014-12-03 | 2015-04-22 | 武汉理工大学 | B4C-HfB2-SiC ternary high-temperature eutectic composite ceramic material and preparation method |
| JP2016132607A (en) * | 2015-01-21 | 2016-07-25 | 新日鐵住金株式会社 | Ceramic composite material and manufacturing method therefor |
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