CN113698210A - Titanium diboride-boron nitride-silicon carbide ceramic composite material prepared by hot-pressing sintering and preparation method thereof - Google Patents
Titanium diboride-boron nitride-silicon carbide ceramic composite material prepared by hot-pressing sintering and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a titanium diboride-boron nitride-silicon carbide ceramic composite material prepared by hot-pressing sintering and a preparation method thereof, belonging to the technical field of ceramic materials. It is made of raw material TiB2the-BN-SiC powder is sintered by a hot-pressing sintering technology, and the raw material mixed powder comprises 24-25.8% of titanium diboride powder, 72% of boron nitride powder and 2.2-4% of silicon carbide powder by volume percentage. The TiB provided by the invention2the-BN-SiC complex phase ceramic has good thermal stability, excellent resistance characteristic and excellent mechanical property.
Description
Technical Field
The invention relates to a ceramic composite material and a preparation method thereof, in particular to TiB prepared by hot-pressing sintering2-BN-SiC ceramic composite material and method for producing the sameA preparation method.
Background
TiB2-BN complex phase ceramic with TiB2And BN excellent properties such as good conductivity, thermal shock resistance, easy machinability, corrosion resistance and the like, and the TiB with required resistivity can be obtained by controlling the proportion, the grain diameter ratio, the sintering temperature and the sintering system between the two2-BN complex phase conductive ceramic.
In the metal evaporation industry, ceramics with appropriate resistivity and temperature coefficient of resistance are key materials for preparing evaporation boats. However, the evaporation boat is also required to have excellent mechanical properties and thermal stability, and the working conditions of the evaporation boat used for metal evaporation are extreme, for example, the working temperature of the evaporation boat when evaporating aluminum materials is above 1450 ℃, and the evaporation boat is at normal temperature when not in use, so that the evaporation boat must undergo multiple cold and hot cycles, and therefore, good thermal stability is an important property for prolonging the life of the boat body. The excellent mechanical property is an important factor for keeping the boat body firm and not easy to crack in the using process. However, at present, national TiB2The stability of the-BN ceramic still has a great problem, in 2008, Chenyonghong and the like improve the corrosion resistance and the thermal stability of the ceramic by adding AlN, and the resistivity of an obtained sample meets the requirement but does not meet the requirements on compactness and mechanical property. SiC has the characteristics of high hardness, high grinding performance, high temperature resistance, oxidation resistance and the like, and the SiC is added into TiB2TiB can be excluded from the-BN system2The oxygen-rich layer on the surface can improve TiB2The sintering density and the SiC in dispersion distribution can improve the TiB to a great extent2Fracture toughness of the material. In addition, since SiC has semiconductor characteristics, more electron-hole pairs are generated at an increased temperature, the carrier density increases, and the resistivity decreases, so that addition of an appropriate amount of SiC can be made to TiB2The resistivity of the BN ceramic plays a role in regulation and stabilization.
TiB was found by literature investigation2Less research on the-BN-SiC system, TiB of the prior research2The electrical resistivity of BN-based ceramic materials far exceeds the required range when the BN-based ceramic materials satisfy the excellent mechanical properties of the materialsThe electrical resistivity and the mechanical property can not reach the optimum at the same time, so that the preparation of the ceramic with better mechanical strength, moderate thermal stability and the electrical resistivity meeting the required range is urgently needed to be solved in the metal evaporation industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides TiB prepared by hot-pressing sintering2-BN-SiC ceramic composite material and a preparation method thereof. The TiB2the-BN-SiC ceramic has good thermal stability, excellent resistance characteristic and excellent mechanical property.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
TiB prepared by hot-pressing sintering2-BN-SiC complex phase ceramic made of TiB as raw material2the-BN-SiC powder is sintered by a hot-pressing sintering technology, and the raw material mixed powder comprises 24-25.8% of titanium diboride powder, 72% of boron nitride powder and 2.2-4% of silicon carbide powder by volume percentage.
According to the scheme, the hot-pressing sintering comprises the following steps: placing the raw material mixed powder in hot-pressing sintering equipment (HP), heating to 1000-1200 ℃ under a vacuum condition, continuously heating and pressurizing to a sintering temperature under an inert atmosphere, carrying out heat preservation sintering at the temperature, and naturally cooling to obtain TiB2-BN-SiC ceramic composite material.
According to the scheme, TiB prepared by hot-pressing sintering2The apparent relative density of the-BN-SiC complex phase ceramic is more than 95.5 percent, the bending strength is 185-195MPa, and the thermal expansion coefficient is 5.0 multiplied by 10-6-5.5×10-6The resistivity is 10-600m omega cm.
According to the scheme, the average particle size of the titanium diboride powder in the mixed powder is 6um, and the purity is more than 98.5 percent; the average granularity of the boron nitride powder is 0.5um, and the purity is more than 99 percent; the average granularity of the silicon carbide powder is 0.92um, and the purity is more than 99 percent.
The above TiB2The preparation method of the-BN-SiC ceramic composite material comprises the following steps:
providing raw material mixed powder, wherein the raw material mixed powder comprises 24-25.8% of titanium diboride powder, 72% of boron nitride powder and 2.2-4% of silicon carbide powder by volume percentage;
placing the mixed powder obtained in the previous step in hot-pressing sintering equipment (HP), heating to 1000-1200 ℃ under a vacuum condition, continuously heating and pressurizing to a sintering temperature under an argon atmosphere, carrying out heat preservation sintering at the temperature, and naturally cooling to obtain TiB2-BN-SiC ceramic composite material.
According to the scheme, the preparation method of the mixed powder comprises the following steps: weighing titanium diboride powder, boron nitride powder and silicon carbide powder as raw materials for later use; putting the weighed powder into a polyethylene plastic bottle of a drum mixer, adding an ethanol solution as a dispersion medium to mix, and then sieving to remove grinding balls to obtain an ethanol solution of mixed powder; removing the ethanol solvent by adopting a rotary evaporation mode to obtain mixed powder; and (3) drying the mixed powder in a vacuum drying oven for 24-48h, grinding, sieving and granulating to obtain the mixed powder.
According to the scheme, the weight ratio of the mixed grinding balls to the mixed powder is 5:1, and the total volume of the powder, the grinding balls and the ethanol is less than two thirds of the volume of the polyethylene plastic tank and more than one third of the volume of the polyethylene plastic tank.
According to the scheme, the rotating speed of the drum type material mixing instrument is 50-100r/min, the material mixing time is 24 hours, and the grinding balls are agate balls.
According to the scheme, the heating rate of the vacuum heating to 1000-1200 ℃ in the hot-pressing sintering process is 5-15 ℃/min.
According to the scheme, the initial pressure of the hot-pressing sintering is 10-12 MPa.
According to the scheme, in the hot-pressing sintering process, the pressure is continuously increased to 30-40 Mpa.
According to the scheme, the pressurizing rate in the hot-pressing sintering is 0.25-0.31 MPa/min.
According to the scheme, the inert atmosphere is argon.
According to the scheme, the sintering temperature is 1850-1950 ℃. The sintering time is 90-120 min.
The invention uses TiB2BN and SiC are taken as raw materials, and a hot pressing sintering technology is combinedThe proportion of the three raw materials is adjusted, the TiB with good thermal stability, resistivity meeting the range of 10-600m omega cm, more preferably 10-200m omega cm and excellent mechanical property is prepared by a method of keeping a vacuum state in a forehearth at the temperature of 1000-1200 ℃ and gradually pressurizing in the subsequent temperature rise process and a hot-pressing sintering process2-BN-SiC complex phase ceramics. The invention can regulate and control TiB through regulating and controlling the raw material proportion including the volume ratio of titanium diboride and silicon carbide and the like2The conductive performance, the mechanical performance and the thermal performance of the BN-SiC composite ceramic are met so as to meet the working requirements under different environments.
Specifically, the TiB is prepared by adopting a hot-pressing sintering technology and selecting silicon carbide with semiconductor characteristics as a third phase2The BN-SiC composite ceramic is prepared by raising the temperature in an initial vacuum state in hot-pressing sintering, so that the air in large gaps in powder is discharged in a low-temperature environment, introducing protective gas when the temperature is raised to the activation temperature of the powder, and simultaneously applying axial pressure, so that the initial stage of oxidation hot-pressing sintering caused by air entering due to pressure difference is prevented, and simultaneously, the application of the axial pressure can be based on plastic flow and particle rearrangement, and the densified composite ceramic material is favorably obtained. Continuous pressurization in the hot-pressing sintering temperature rise process is beneficial to plastic flow and ion rearrangement of ceramic powder, and the compactness, mechanical property and thermodynamic property of the composite ceramic are improved. The technical route has better reference significance for producing the conductive ceramic with high-temperature and impact resistance.
The invention has the beneficial effects that:
the invention provides TiB with good thermal stability, excellent resistance characteristic and excellent mechanical property2the-BN-SiC complex phase ceramic can be used as a conductive evaporation boat ceramic material and a corrosion-resistant electrode material used in the evaporation aluminizing industry.
The method has simple process, uniform and stable performance of the sintered product, and can better control the performance of the complex phase ceramic.
Drawings
FIG. 1 shows TiB in comparative example 1 of the present invention2SEM secondary electron image (a) of surface of BN-SiC ceramic composite material and cross section thereofSEM secondary electron image (b).
FIG. 2 shows TiB in example 2 of the present invention2An SEM secondary electron image (a) of the surface of the BN-SiC ceramic composite material and an SEM secondary electron image (b) of a cross section thereof.
FIG. 3 shows TiB prepared by hot pressing sintering according to the present invention2A process flow diagram of the-BN-SiC ceramic composite material.
FIG. 4 shows a TiB of the present invention2-BN-SiC ceramic resistivity four-probe test schematic.
The test method comprises the following steps:
in the formula of U23Voltage (mV), I, received from the sample for probes 2 and 314Current (mA) was passed through the sample at points 1 and 4, S was the length (cm) between the two probes, and the distance between the two probes in this laboratory was 0.2 cm.
FIG. 5 shows different TiB at 1850 ℃ sintering temperature in the present invention2TiB in proportion of-SiC2Apparent relative density and open porosity of the-SiC-BN composite ceramic.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Comparative example 1:
TiB described in this example2The preparation method of the-BN-SiC ceramic composite material comprises the following specific steps:
1) weighing 21% of titanium diboride powder, 72% of boron nitride powder and 7% of silicon carbide powder according to the volume percentage for later use;
2) putting the weighed powder into a polyethylene plastic bottle of a drum mixer, adding an ethanol solution as a dispersion medium to mix, wherein the total volume of the powder, grinding balls and ethanol is one half of the volume of the plastic bottle, the rotating speed of the drum mixer is 100r/min, the mixing time is 24h, the adopted grinding balls are agate balls, and filtering to remove the grinding balls to obtain the ethanol solution of the mixed powder;
3) removing the ethanol solvent by adopting a rotary evaporation mode to obtain mixed powder;
4) drying the mixed powder in a vacuum drying oven at 60 ℃ for 24h, grinding, sieving with a 100-mesh sieve, and granulating to obtain mixed powder;
5) putting the mixed powder obtained in the last step into a cylindrical graphite die with an inner hole of phi 48mm, wrapping the die with lining graphite paper and a plurality of layers of graphite felt pads outside, putting the die into hot-pressing sintering equipment (HP) to be pre-pressurized to 12MPa, starting to heat to 1000 ℃ at a speed of 10 ℃/min when the vacuum degree is reduced to be below 10Pa, continuously pressurizing to 30MPa in an argon atmosphere, heating to a sintering temperature of 1850 ℃, preserving heat for 90min at the temperature, and naturally cooling to obtain TiB2-BN-SiC ceramic composite material.
The TiB obtained2The properties of the-BN-SiC ceramic composite are as follows: an apparent relative density of 95.91%, an open porosity of 1.65%, a resistivity of 37429.6m omega cm at room temperature, an elastic modulus of 87.5GPa, a bending strength of 171.12MPa, a thermal conductivity of 28.32W/m.K at 600 ℃ and Ar atmosphere, and an average thermal expansion coefficient of 5.0 x 10 at 1100 DEG C-6/K。
Example 1:
TiB described in this example2The preparation method of the-BN-SiC ceramic composite material comprises the following specific steps:
1) weighing 24% of titanium diboride powder, 72% of boron nitride powder and 4% of silicon carbide powder according to volume percentage for later use;
2) putting the weighed powder into a polyethylene plastic bottle of a drum mixer, adding an ethanol solution as a dispersion medium to mix, wherein the total volume of the powder, grinding balls and ethanol is one half of the volume of the plastic bottle, the rotating speed of the drum mixer is 100r/min, the mixing time is 24h, the adopted grinding balls are agate balls, and filtering to remove the grinding balls to obtain the ethanol solution of the mixed powder;
3) removing the ethanol solvent by adopting a rotary evaporation mode to obtain mixed powder;
4) drying the mixed powder in a vacuum drying oven at 60 ℃ for 24h, grinding, sieving with a 100-mesh sieve, and granulating to obtain mixed powder;
5) putting the mixed powder obtained in the last step into a cylindrical graphite die with an inner hole of phi 48mm, wrapping the die with lining graphite paper and a plurality of layers of graphite felt pads outside, putting the die into hot-pressing sintering equipment (HP) to be pre-pressurized to 12MPa, starting to heat to 1000 ℃ at a speed of 10 ℃/min when the vacuum degree is reduced to be below 10Pa, continuously pressurizing to 30MPa in an argon atmosphere, heating to a sintering temperature of 1850 ℃, preserving heat for 90min at the temperature, and naturally cooling to obtain TiB2-BN-SiC ceramic composite material.
The TiB obtained2The properties of the-BN-SiC ceramic composite are as follows: an apparent relative density of 96.02%, an open porosity of 1.54%, a resistivity at room temperature of 526 m.OMEGA.cm, an elastic modulus of 86.7GPa, a bending strength of 190.11MPa, a thermal conductivity at 600 ℃ under Ar atmosphere of 29.84W/m.K, and an average thermal expansion coefficient at 1100 ℃ of 5.20 × 10-6/K。
Example 2:
TiB described in this example2The preparation method of the-BN-SiC ceramic composite material comprises the following specific steps:
1) weighing 25.2 percent of titanium diboride powder, 72 percent of boron nitride powder and 2.8 percent of silicon carbide powder according to volume percentage for later use;
2) putting the weighed powder into a polyethylene plastic bottle of a drum mixer, adding an ethanol solution as a dispersion medium to mix, wherein the total volume of the powder, grinding balls and ethanol is one half of the volume of the plastic bottle, the rotating speed of the drum mixer is 100r/min, the mixing time is 24h, the adopted grinding balls are agate balls, and filtering to remove the grinding balls to obtain the ethanol solution of the mixed powder;
3) removing the ethanol solvent by adopting a rotary evaporation mode to obtain mixed powder;
4) drying the mixed powder in a vacuum drying oven at 60 ℃ for 24h, grinding, sieving with a 100-mesh sieve, and granulating to obtain mixed powder;
5) putting the mixed powder obtained in the last step into a cylindrical graphite mold with an inner hole of phi 48mm, wherein the mold is provided with graphite paper with a lining, and the graphite paper is arranged outsideWrapping with multilayer graphite felt pad, placing in hot-pressing sintering equipment (HP), pre-pressurizing to 12MPa, heating to 1000 deg.C at a rate of 10 deg.C/min when vacuum degree is reduced to below 10Pa, continuously pressurizing to 30MPa in argon atmosphere, heating to sintering temperature of 1850 deg.C, maintaining at the temperature for 90min, and naturally cooling to obtain TiB2-BN-SiC ceramic composite material.
The TiB obtained2The properties of the-BN-SiC ceramic composite are as follows: an apparent relative density of 95.78%, an open porosity of 1.42%, a resistivity at room temperature of 78 m.OMEGA.cm, an elastic modulus of 87GPa, a bending strength of 190MPa, a thermal conductivity at 600 ℃ under Ar atmosphere of 30.18W/m.K, and an average thermal expansion coefficient at 1100 ℃ of 5.29 × 10-6/K。
Example 3:
TiB described in this example2The preparation method of the-BN-SiC ceramic composite material comprises the following specific steps:
1) weighing 25.8 percent of titanium diboride powder, 72 percent of boron nitride powder and 2.2 percent of silicon carbide powder according to volume percentage for later use;
2) putting the weighed powder into a polyethylene plastic bottle of a drum mixer, adding an ethanol solution as a dispersion medium to mix, wherein the total volume of the powder, grinding balls and ethanol is one half of the volume of the plastic bottle, the rotating speed of the drum mixer is 100r/min, the mixing time is 24h, the adopted grinding balls are agate balls, and filtering to remove the grinding balls to obtain the ethanol solution of the mixed powder;
3) removing the ethanol solvent by adopting a rotary evaporation mode to obtain mixed powder;
4) drying the mixed powder in a vacuum drying oven at 60 ℃ for 24h, grinding, sieving with a 100-mesh sieve, and granulating to obtain mixed powder;
5) placing the mixed powder obtained in the previous step into a cylindrical graphite mold with an inner hole of phi 48mm, wrapping the mold with a lining of graphite paper and a multilayer graphite felt pad outside, placing the mold in a hot-pressing sintering device (HP) to pre-pressurize to 12MPa, starting to heat to 1000 ℃ at a rate of 10 ℃/min when the vacuum degree is reduced to below 10Pa, continuously pressurizing to 30MPa in an argon atmosphere, heating to a sintering temperature of 1850 ℃, and maintaining the temperatureHeating for 90min, and naturally cooling to obtain TiB2-BN-SiC ceramic composite material.
The TiB obtained2The properties of the-BN-SiC ceramic composite are as follows: an apparent relative density of 95.54%, an open porosity of 1.29%, a resistivity at room temperature of 44 m.OMEGA.cm, an elastic modulus of 86.9GPa, a bending strength of 189.79MPa, a thermal conductivity at 600 ℃ under Ar atmosphere of 32.26W/m.K, and an average thermal expansion coefficient at 1100 ℃ of 5.5 × 10-6/K。
The TiB of the present invention will be described in detail with reference to the following drawings2Phase composition, compactness and microstructure of the-BN-SiC ceramic composite material.
FIG. 1 and FIG. 2 show TiB in comparative example 1 and example 2, respectively2SEM secondary electron images of the surface and cross-section of the BN-SiC ceramic composite. White-grey large-grain TiB in the figure2And SiC, wherein the black flaky crystal grain is BN, the flaky crystal grain (BN) presents a texture state through preferred orientation growth, and the flaky crystal grain (BN) is combined with the grey white large crystal grain (TiB) compactly2) The lack of tight binding results in porosity at the sample surface. It can be seen from the figure that the surface of comparative example 1 has some larger voids and the grain distribution is not uniform, while the sample of example 2 has less voids on the surface, and the reduction of voids reduces the fracture stress concentration on the ceramic surface, which directly results in the increase of the flexural strength of example 2. In addition, TiB can be found2And the SiC crystal grains are distributed in the sample of the embodiment 2 in a larger area and more uniformly, so that the conductivity of the ceramic is greatly increased, and the resistivity of the ceramic is sharply reduced. The main part of the material is a flaky product, granular crystal grains are dispersedly distributed among flaky crystal grains, and fracture modes are the threading fracture and the granular TiB of the flaky BN crystal grains2And SiC, it can be seen from the figure that the fracture of comparative example 1, in which the lamellar fracture is generated by BN crystal grains less than that of example 2, enhances the flexural strength of the ceramic by the transgranular fracture of this BN lamellar.
FIG. 5 shows different TiB at 1850 ℃ sintering temperature2TiB in proportion of-SiC2Apparent relative density and open porosity map of-SiC-BN composite ceramic showingTiB2The volume ratio of-SiC is 6:1, the relative density of the composite ceramic is the maximum, and the density of the sintered body is slightly increased. This may be because of TiB2Volume content of TiB in the proportion2The sintering between crystal grains is easier, the contact probability between heterogeneous particles is reduced, and the pores are reduced.
The synthesis shows that the composite ceramic product with excellent resistance property, mechanical property and thermal expansion property is obtained by sintering by using a hot-pressing sintering process and regulating and controlling the raw material proportion, and the requirements of regulation and control are met.
Claims (10)
1. TiB prepared by hot-pressing sintering2-BN-SiC complex phase ceramic, characterized in that: from the starting material TiB2the-BN-SiC powder is sintered by a hot-pressing sintering technology, and the raw material mixed powder comprises 24-25.8% of titanium diboride powder, 72% of boron nitride powder and 2.2-4% of silicon carbide powder by volume percentage.
2. The complex phase ceramic as claimed in claim 1, wherein: the hot-pressing sintering comprises the following steps: placing the raw material mixed powder in hot-pressing sintering equipment, heating to 1000-1200 ℃ under a vacuum condition, continuously heating and pressurizing to a sintering temperature under an inert atmosphere, carrying out heat preservation sintering at the temperature, and then naturally cooling to obtain TiB2-BN-SiC ceramic composite material.
3. The complex phase ceramic as claimed in claim 1, wherein: TiB prepared by hot-pressing sintering2The apparent relative density of the-BN-SiC complex phase ceramic is more than 95.5 percent, the bending strength is 185-195MPa, and the thermal expansion coefficient is 5.0 multiplied by 10-6-5.5×10-6The resistivity is 10-600m omega cm.
4. The complex phase ceramic as claimed in claim 1, wherein: the average granularity of the titanium diboride powder in the mixed powder is 6um, and the purity is more than 98.5 percent; the average granularity of the boron nitride powder is 0.5um, and the purity is more than 99 percent; the average granularity of the silicon carbide powder is 0.92um, and the purity is more than 99 percent.
5. The TiB of claim 12The preparation method of the-BN-SiC ceramic composite material comprises the following steps:
providing raw material mixed powder, wherein the raw material mixed powder comprises 24-25.8% of titanium diboride powder, 72% of boron nitride powder and 2.2-4% of silicon carbide powder by volume percentage;
placing the mixed powder obtained in the previous step into hot-pressing sintering equipment, heating to 1000-1200 ℃ under a vacuum condition, continuously heating and pressurizing to a sintering temperature under an argon atmosphere, carrying out heat preservation sintering at the temperature, and then naturally cooling to obtain TiB2-BN-SiC ceramic composite material.
6. The complex phase ceramic as claimed in claim 1, wherein: the initial pressure of the hot-pressing sintering is 10-12 MPa.
7. The complex phase ceramic as claimed in claim 1, wherein: and continuously pressurizing to 30-40Mpa in the hot-pressing sintering process.
8. The complex phase ceramic as claimed in claim 1, wherein: the pressurizing rate is 0.25-0.31 MPa/min.
9. The complex phase ceramic as claimed in claim 1, wherein: the sintering temperature is 1850 ℃ and 1950 ℃.
10. The complex phase ceramic as claimed in claim 1, wherein: the sintering time is 90-120 min.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200604132A (en) * | 2004-05-24 | 2006-02-01 | Denki Kagaku Kogyo Kk | Ceramics, method for production thereof and use thereof |
| CN101037566A (en) * | 2005-12-22 | 2007-09-19 | 莫门蒂夫性能材料股份有限公司 | Wear resistant low friction coating composition, coated components, and method for coating thereof |
| CN101265107A (en) * | 2008-04-22 | 2008-09-17 | 武汉理工大学 | Multi-element diphase ceramic material used for conductive crucible and preparation method thereof |
| CN101734916A (en) * | 2009-12-14 | 2010-06-16 | 哈尔滨工业大学 | Boron nitride-titanium diboride ceramic composite material and preparation method thereof |
| CN103145422A (en) * | 2013-03-06 | 2013-06-12 | 武汉理工大学 | High-hardness ceramic composite material of boron carbide-titanium boride-silicon carbide and preparation method thereof |
| CN105198443A (en) * | 2015-10-21 | 2015-12-30 | 哈尔滨工业大学 | Transition phase assisted low-temperature sintering method of boron nitride multi-phase ceramic |
| CN110128146A (en) * | 2019-05-14 | 2019-08-16 | 武汉理工大学 | One kind having multi-functional boron carbide-based complex phase ceramic and its reactive hot press sintering preparation method |
| CN112521159A (en) * | 2020-03-20 | 2021-03-19 | 山东晶亿新材料有限公司 | Boron nitride composite ceramic and preparation method and application thereof |
-
2021
- 2021-09-02 CN CN202111027636.1A patent/CN113698210A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200604132A (en) * | 2004-05-24 | 2006-02-01 | Denki Kagaku Kogyo Kk | Ceramics, method for production thereof and use thereof |
| CN101037566A (en) * | 2005-12-22 | 2007-09-19 | 莫门蒂夫性能材料股份有限公司 | Wear resistant low friction coating composition, coated components, and method for coating thereof |
| CN101265107A (en) * | 2008-04-22 | 2008-09-17 | 武汉理工大学 | Multi-element diphase ceramic material used for conductive crucible and preparation method thereof |
| CN101734916A (en) * | 2009-12-14 | 2010-06-16 | 哈尔滨工业大学 | Boron nitride-titanium diboride ceramic composite material and preparation method thereof |
| CN103145422A (en) * | 2013-03-06 | 2013-06-12 | 武汉理工大学 | High-hardness ceramic composite material of boron carbide-titanium boride-silicon carbide and preparation method thereof |
| CN105198443A (en) * | 2015-10-21 | 2015-12-30 | 哈尔滨工业大学 | Transition phase assisted low-temperature sintering method of boron nitride multi-phase ceramic |
| CN107721433A (en) * | 2015-10-21 | 2018-02-23 | 哈尔滨工业大学 | Boron nitride complex phase ceramic and its sintering method and application |
| CN110128146A (en) * | 2019-05-14 | 2019-08-16 | 武汉理工大学 | One kind having multi-functional boron carbide-based complex phase ceramic and its reactive hot press sintering preparation method |
| CN112521159A (en) * | 2020-03-20 | 2021-03-19 | 山东晶亿新材料有限公司 | Boron nitride composite ceramic and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 田仕: "TiB2-BN-SiC复相陶瓷的制备与性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
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