CN108585881A - A kind of high heat conductivity silicon nitride ceramics and preparation method thereof - Google Patents

A kind of high heat conductivity silicon nitride ceramics and preparation method thereof Download PDF

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CN108585881A
CN108585881A CN201810612015.1A CN201810612015A CN108585881A CN 108585881 A CN108585881 A CN 108585881A CN 201810612015 A CN201810612015 A CN 201810612015A CN 108585881 A CN108585881 A CN 108585881A
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silicon nitride
nitride ceramics
high heat
powder
preparation
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叶枫
杨春萍
张标
叶健
刘强
高晔
叶凯
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Harbin Institute of Technology
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Abstract

A kind of high heat conductivity silicon nitride ceramics of present invention offer and preparation method thereof by the way that silicon nitride powder is carried out deoxidation treatment, natural cooling, and gained beta-silicon nitride powder are ground up, sieved to solve the relatively low technical problem of existing thermal conductivity；It is mixed under the action of blending agent with sintering aid, dry after mixing, sieving obtains powder；Compression moulding obtains silicon nitride ceramics green compact；Most afterwards through gas pressure sintering, obtain silicon nitride ceramic material, compared with the prior art, pass through the deoxidation treatment to beta-silicon nitride powder, so that original powder oxygen content is lower, lattice oxygen content degree higher is reduced in sintering process, it is more advantageous to and avoids phon scattering, to improve the thermal conductivity of silicon nitride ceramics, the silicon nitride ceramics of preparation has high heat conductance, good thermal shock resistance and high temperature resistance, it is safe to use, it is a kind of silicon nitride ceramic substrate material with excellent power, heat, electric comprehensive performance.

Description

A kind of high heat conductivity silicon nitride ceramics and preparation method thereof
Technical field
The present invention relates to ceramic materials preparation technology field, more particularly to a kind of high heat conductivity silicon nitride ceramics and its preparation Method.
Background technology
Silicon nitride (Si3N4) has intensity height, good toughness, heat shock resistance, corrosion-resistant and wear-resistant etc. performances, in aviation boat It, machinery, nuclear energy, chemical industry, ocean engineering, the fields such as armor facing have a wide range of applications.Middle period nineteen nineties Before, the thermal conductivity of the polycrystalline silicon nitride ceramics that document is reported at room temperature is very low, and only 20-70W/mK is far below Other non-oxide ceramics (SiC 270W/mK, AlN 320W/mK).Nineteen ninety-five, Haggerty et al. predict β- Si3N4 ceramics thermal conductivities can reach 200-320W/mK, this discovery has expanded silicon nitride ceramics in electric vehicle, integrated electricity Road and the application for needing high heat-dissipation, high-insulation and high heat-resistant circuitry baseplate material field.
Although silicon nitride theory thermal conductivity is higher, the thermal conductivity of sintered silicon nitride ceramic is far below theoretical value, tradition Sintering technology so as to nitrogenize in silicon crystal lattice that crystal grain is tiny, β phase contents are relatively low and the content of Grain-Boundary Phase there are excessive impurity and defect Excessively high, these factors lead to the lower thermal conductivity of sintered silicon nitride ceramic, it is difficult to the extensive use as ceramic substrate material.
There are two ways to preparing silicon nitride ceramic substrate at present, one is silicon powder nitride method is used, by silica flour and burning is helped Green compact are pressed into after agent mixing, in the nitrogen pressure of micro-positive pressure (0.1-0.5MPa), temperature carries out under the conditions of being 1100-1400 DEG C 4-10h is nitrogenized, the material after nitridation is sintered 2-60h under 1900 DEG C, 0.9-1MPa nitrogen pressures.Nitrogen prepared by the method SiClx ceramic substrate can lead to lower dielectric properties, while being carried out again after silicon powder nitride since there are remaining silicon for nitridation process There are Residual Pores for meeting in agglomerated material, and density is relatively low, the raising to affect the mechanical properties with thermal conductivity.Another method is direct The use of silicon nitride powder is raw material, green compact is pressed into after being mixed with sintering aid, in high temperature (1700-2000 DEG C), 0.9-1MPa nitrogen 2-60h is sintered under atmospheric pressure, this method need to use high purity silicon nitride silica flour, and of high cost, industrialization difficulty is big.
In view of drawbacks described above, creator of the present invention proposes the present invention by prolonged research and practice.
Invention content
In order to solve the silicon nitride ceramics technical problem relatively low as the thermal conductivity of ceramic substrate material, the present invention provides one The preparation method of kind high heat conductivity silicon nitride ceramics comprising following steps：
Silicon nitride powder is carried out deoxidation treatment, natural cooling, and gained beta-silicon nitride powder is ground up, sieved by the first step；
Second step mixes beta-silicon nitride powder described in the first step with sintering aid under the action of blending agent, mixing knot Dry after beam, sieving, obtains powder；
Third walks, and the powder pressing is molded, silicon nitride ceramics green compact are obtained；
The silicon nitride ceramics green compact are carried out gas pressure sintering, obtain silicon nitride ceramic material by the 4th step.
Preferably, the technique of deoxidation treatment described in the first step is, the silicon nitride powder and carbon dust are respectively put into different It in crucible, is positioned in tube furnace, with the heating rate of 5-10 DEG C/min, in reaction atmosphere at a temperature of 1200 DEG C -1400 DEG C Handle 4-8h.
Preferably, the reaction atmosphere is nitrogen or ammonia.
Preferably, sintering aid described in second step is binary complex sintering aids, and the binary complex sintering aids packet Include rare earth oxide and alkaline earth metal compound.
Preferably, the rare earth oxide is Y2O3、Yb2O3、Gd2O3、Nd2O3In one kind, the alkaline earth metal compound It is MgO, MgSiN2Or MgF2In one kind.
Preferably, mole of beta-silicon nitride powder described in second step, the rare earth oxide and the alkaline earth metal compound Than for 95-89:4-6:1-5.
Preferably, blending agent described in second step is isopropanol, and the weight of the isopropanol and the beta-silicon nitride powder Than for 1-1.5:1.
Preferably, process dry described in second step is, first rotarily dried at 55-75 DEG C, then in vacuum drying oven In it is 3-5 hours dry with 110-130 DEG C.
Preferably, the process conditions that third walks the compression moulding are, first use punching block dry-pressing formed, then carry out cold etc. quiet It is molded, forming pressure 200-500MPa, molding time 100-300s.
Preferably, in the 4th step, the process conditions of the gas pressure sintering are, using nitrogen as sintering atmosphere, air pressure 0.9- Under conditions of 1.5Mpa, it is warming up to 1700-2000 DEG C with the rate of 5-15 DEG C/min, and keep the temperature 1.5-20h.
Beneficial effects of the present invention are：
1, pass through the deoxidation treatment to beta-silicon nitride powder so that original powder oxygen content is lower, is reduced in sintering process Lattice oxygen content degree higher, is more advantageous to and avoids phon scattering, to improve the thermal conductivity of silicon nitride ceramics.
2, silicon nitride ceramics prepared by the present invention has high heat conductance, good thermal shock resistance and high temperature resistance, makes It is a kind of silicon nitride ceramic substrate material with excellent power, heat, electric comprehensive performance with safety.
3, silicon nitride ceramics bending strength prepared by the present invention is up to 700-900MPa, fracture toughness 6.5-8MPa1/2, heat Conductance is more than 100W/mK, and linear expansion coefficient is close with silicon, meets the requirement of ceramic substrate material, it is ensured that as electronics The reliability of encapsulating material.
Description of the drawings
Fig. 1 is a kind of workflow of the preparation method first step of high heat conductivity silicon nitride ceramics in the embodiment of the present invention 1 Schematic diagram；
Fig. 2 is a kind of back scattering picture of high heat conductivity silicon nitride ceramics prepared in the embodiment of the present invention 1.
Specific implementation mode
Embodiment 1
The present embodiment provides a kind of preparation methods of high heat conductivity silicon nitride ceramics comprising following steps：
The silicon nitride powder and the carbon dust are respectively put into boron nitride crucible, are positioned over alumina tube by the first step In stove, with the heating rate of 5-10 DEG C/min, 4-8h is handled at a temperature of 1200 DEG C -1400 DEG C in nitrogen reaction atmosphere, is reacted After furnace temperature natural cooling, processed powder is ground up, sieved；
Second step mixes beta-silicon nitride powder described in the first step with sintering aid under the action of blending agent, mixing knot Dry after beam, sieving, obtains powder；Wherein, the sintering aid is binary complex sintering aids, and the binary is complex sintered Auxiliary agent includes rare earth oxide and alkaline earth metal compound, and the rare earth oxide is Y2O3、Yb2O3、Gd2O3、Nd2O3In one Kind, the alkaline earth metal compound is MgO, MgSiN2Or MgF2In one kind, and the beta-silicon nitride powder, the rare-earth oxidation The molar ratio of object and the alkaline earth metal compound is 95-89:4-6:1-5；The blending agent is isopropanol, the isopropanol Weight ratio with the beta-silicon nitride powder is 1-1.5:1, incorporation time is 20-26 hours, is first revolved at 55-75 DEG C after mixing Become a cadre dry, it is then 3-5 hours dry with 110-130 DEG C in vacuum drying oven, cross 100 mesh nylon mesh after dry；
Third walks, and the powder is dry-pressing formed using punching block, then carries out cold isostatic compaction, forming pressure 200- 500MPa, molding time 100-300s obtain silicon nitride ceramics green compact after molding；
The silicon nitride ceramics green compact are carried out gas pressure sintering by the 4th step, and the process conditions of the gas pressure sintering are, with nitrogen Gas is sintering atmosphere, and under conditions of air pressure is 0.9-1.5Mpa, 1700-2000 DEG C is warming up to the rate of 5-15 DEG C/min, and 1.5-20h is kept the temperature, silicon nitride ceramic material is obtained.
Beta-silicon nitride powder is carried out to deoxidation treatment in the present embodiment in nitrogen, is prepared using processed beta-silicon nitride powder High heat conductivity silicon nitride ceramics are one of the committed steps for improving silicon nitride ceramics thermal conductivity.
Fig. 1 is referred to,
Fig. 1 is a kind of workflow signal of the preparation method first step of high heat conductivity silicon nitride ceramics in the present embodiment Figure；
Fig. 2 is a kind of back scattering picture of high heat conductivity silicon nitride ceramics prepared in the present embodiment.
Under the high temperature conditions, reaction gas and carbon and powder surface SiO2It is reacted, generates silicon nitride, chemical equation is 3SiO2+6C+2N2=Si3N4+ 6CO makes powder surface SiO2Layer is thinning, and powder oxygen content reduces, and has in later stage sintering process Conducive to the oxygen content reduced in lattice and in Grain-Boundary Phase, to improve the thermal conductivity of silicon nitride.
Therefore, the present embodiment provides a kind of preparation methods of high heat conductivity silicon nitride ceramics by being taken off to beta-silicon nitride powder Oxygen processing so that original powder oxygen content is lower, and lattice oxygen content degree higher is reduced in sintering process, is more advantageous to and avoids Phon scattering, to improve the thermal conductivity of silicon nitride ceramics.Meanwhile silicon nitride ceramics bending strength manufactured in the present embodiment is up to 700-900MPa, fracture toughness 6.5-8MPa1/2, for thermal conductivity more than 100W/mK, linear expansion coefficient is close with silicon, meets pottery The requirement of porcelain baseplate material, it is ensured that as the reliability of electronic package material, and with high heat conductance, good thermal shock resistance Energy and high temperature resistance, it is safe to use, it is a kind of silicon nitride ceramic substrate material with excellent power, heat, electric comprehensive performance.
Embodiment 2
It is in place of the present embodiment and the difference of embodiment 1, nitrogen reaction atmosphere ammonia reaction atmosphere described in the first step It substitutes, other are same as Example 1.Ammonia processing equally can carry out deoxidation, ammonia and beta-silicon nitride powder to beta-silicon nitride powder The silicon dioxide layer on surface is reacted, and reaction mechanism is different from embodiment 1, but the purpose of deoxidation is identical with result, can also carry The thermal conductivity of high sintered silicon nitride.
Embodiment 3
The present embodiment provides a kind of preparation methods of high heat conductivity silicon nitride ceramics comprising following steps：
The silicon nitride powder and the carbon dust are respectively put into boron nitride crucible, are positioned over alumina tube by the first step In stove, with the heating rate of 5 DEG C/min, 4h is handled at a temperature of 1200 DEG C DEG C in nitrogen reaction atmosphere, after reaction furnace temperature Processed powder is ground up, sieved by natural cooling；
Second step mixes beta-silicon nitride powder described in the first step with sintering aid under the action of blending agent, mixing knot Dry after beam, sieving, obtains powder；Wherein, the sintering aid is binary complex sintering aids, and the binary is complex sintered Auxiliary agent includes rare earth oxide and alkaline earth metal compound, and the rare earth oxide is Y2O3, the alkaline earth metal compound is MgO, and the molar ratio of the beta-silicon nitride powder, the rare earth oxide and the alkaline earth metal compound is 95:4:1, it is described Blending agent is isopropanol, and the weight ratio of the isopropanol and the beta-silicon nitride powder is 1:1, incorporation time is 20 hours, is mixed It is first rotarily dried at 55 DEG C after conjunction, it is then 3 hours dry with 110 DEG C in vacuum drying oven, cross 100 mesh nylon after dry Sieve；
Third walks, and the powder is dry-pressing formed using punching block, then carries out cold isostatic compaction, forming pressure 200MPa, Molding time 100s obtains silicon nitride ceramics green compact after molding；
The silicon nitride ceramics green compact are carried out gas pressure sintering by the 4th step, and the process conditions of the gas pressure sintering are, with nitrogen Gas is that sintering atmosphere is warming up to 1700 DEG C with the rate of 5 DEG C/min, and keep the temperature 1.5h, obtains under conditions of air pressure is 0.9Mpa Silicon nitride ceramic material.
Therefore, the present embodiment provides a kind of preparation methods of high heat conductivity silicon nitride ceramics by being taken off to beta-silicon nitride powder Oxygen processing so that original powder oxygen content is lower, and lattice oxygen content degree higher is reduced in sintering process, is more advantageous to and avoids Phon scattering, to improve the thermal conductivity of silicon nitride ceramics.Meanwhile silicon nitride ceramics bending strength manufactured in the present embodiment is up to 700-900MPa, fracture toughness 6.5-8MPa1/2, for thermal conductivity more than 100W/mK, linear expansion coefficient is close with silicon, meets pottery The requirement of porcelain baseplate material, it is ensured that as the reliability of electronic package material, and with high heat conductance, good thermal shock resistance Energy and high temperature resistance, it is safe to use, it is a kind of silicon nitride ceramic substrate material with excellent power, heat, electric comprehensive performance.
Embodiment 4
The present embodiment provides a kind of preparation methods of high heat conductivity silicon nitride ceramics comprising following steps：
The silicon nitride powder and the carbon dust are respectively put into boron nitride crucible, are positioned over alumina tube by the first step In stove, with the heating rate of 10 DEG C/min, 8h is handled at a temperature of 1400 DEG C in nitrogen reaction atmosphere, after reaction furnace temperature from It is so cooling, processed powder is ground up, sieved；
Second step mixes beta-silicon nitride powder described in the first step with sintering aid under the action of blending agent, mixing knot Dry after beam, sieving, obtains powder；Wherein, the sintering aid is binary complex sintering aids, and the binary is complex sintered Auxiliary agent includes rare earth oxide and alkaline earth metal compound, and the rare earth oxide is Yb2O3, the alkaline earth metal compound is MgSiN2, and the molar ratio of the beta-silicon nitride powder, the rare earth oxide and the alkaline earth metal compound is 90:4:2, institute Blending agent is stated as isopropanol, the weight ratio of the isopropanol and the beta-silicon nitride powder is 1:1.5, incorporation time is 26 small When, it is first rotarily dried at 55 DEG C after mixing, it is then 5 hours dry with 130 DEG C in vacuum drying oven, cross 100 mesh after dry Nylon mesh；
Third walks, and the powder is dry-pressing formed using punching block, then carries out cold isostatic compaction, forming pressure 500MPa, Molding time 300s obtains silicon nitride ceramics green compact after molding；
The silicon nitride ceramics green compact are carried out gas pressure sintering by the 4th step, and the process conditions of the gas pressure sintering are, with nitrogen Gas is that sintering atmosphere is warming up to 2000 DEG C with the rate of 15 DEG C/min, and keep the temperature 20h, obtains under conditions of air pressure is 1.5Mpa Silicon nitride ceramic material.
Therefore, the present embodiment provides a kind of preparation methods of high heat conductivity silicon nitride ceramics by being taken off to beta-silicon nitride powder Oxygen processing so that original powder oxygen content is lower, and lattice oxygen content degree higher is reduced in sintering process, is more advantageous to and avoids Phon scattering, to improve the thermal conductivity of silicon nitride ceramics.Meanwhile silicon nitride ceramics bending strength manufactured in the present embodiment is up to 700-900MPa, fracture toughness 6.5-8MPa1/2, for thermal conductivity more than 100W/mK, linear expansion coefficient is close with silicon, meets pottery The requirement of porcelain baseplate material, it is ensured that as the reliability of electronic package material, and with high heat conductance, good thermal shock resistance Energy and high temperature resistance, it is safe to use, it is a kind of silicon nitride ceramic substrate material with excellent power, heat, electric comprehensive performance.
Embodiment 5
The present embodiment provides a kind of preparation methods of high heat conductivity silicon nitride ceramics comprising following steps：
The silicon nitride powder and the carbon dust are respectively put into boron nitride crucible, are positioned over alumina tube by the first step In stove, with the heating rate of 8 DEG C/min, 6.5h is handled at a temperature of 1280 DEG C in nitrogen reaction atmosphere, after reaction furnace temperature Processed powder is ground up, sieved by natural cooling；
Second step mixes beta-silicon nitride powder described in the first step with sintering aid under the action of blending agent, mixing knot Dry after beam, sieving, obtains powder；Wherein, the sintering aid is binary complex sintering aids, and the binary is complex sintered Auxiliary agent includes rare earth oxide and alkaline earth metal compound, and the rare earth oxide is Gd2O3, the alkaline earth metal compound is MgSiN2, and the molar ratio of the beta-silicon nitride powder, the rare earth oxide and the alkaline earth metal compound is 91:5:3, institute Blending agent is stated as isopropanol, the weight ratio of the isopropanol and the beta-silicon nitride powder is 1:1.2, incorporation time is 24 small When, it is first rotarily dried at 55 DEG C after mixing, it is then 4 hours dry with 120 DEG C in vacuum drying oven, cross 100 mesh after dry Nylon mesh；
Third walks, and the powder is dry-pressing formed using punching block, then carries out cold isostatic compaction, forming pressure 400MPa, Molding time 180s obtains silicon nitride ceramics green compact after molding；
The silicon nitride ceramics green compact are carried out gas pressure sintering by the 4th step, and the process conditions of the gas pressure sintering are, with nitrogen Gas is that sintering atmosphere is warming up to 1850 DEG C with the rate of 12 DEG C/min, and keep the temperature 9h, obtains under conditions of air pressure is 1.1Mpa Silicon nitride ceramic material.
Therefore, the present embodiment provides a kind of preparation methods of high heat conductivity silicon nitride ceramics by being taken off to beta-silicon nitride powder Oxygen processing so that original powder oxygen content is lower, and lattice oxygen content degree higher is reduced in sintering process, is more advantageous to and avoids Phon scattering, to improve the thermal conductivity of silicon nitride ceramics.Meanwhile silicon nitride ceramics bending strength manufactured in the present embodiment is up to 700-900MPa, fracture toughness 6.5-8MPa1/2, for thermal conductivity more than 100W/mK, linear expansion coefficient is close with silicon, meets pottery The requirement of porcelain baseplate material, it is ensured that as the reliability of electronic package material, and with high heat conductance, good thermal shock resistance Energy and high temperature resistance, it is safe to use, it is a kind of silicon nitride ceramic substrate material with excellent power, heat, electric comprehensive performance.
Embodiment 6
It is in place of the present embodiment and the difference of embodiment 3, the sintering aid is binary complex sintering aids, and described Binary complex sintering aids include rare earth oxide and alkaline earth metal compound, and the rare earth oxide is Nd2O3, the alkaline earth Metallic compound is MgF2, and the molar ratio of the beta-silicon nitride powder, the rare earth oxide and the alkaline earth metal compound It is 93:5:4, other are same as Example 5.
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, It still can be with technical scheme described in the above embodiments is modified, or is carried out to which part technical characteristic etc. With replacing, all within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this Within the protection domain of invention.

Claims (10)

1. a kind of preparation method of high heat conductivity silicon nitride ceramics, which is characterized in that
Silicon nitride powder is carried out deoxidation treatment, natural cooling, and gained beta-silicon nitride powder is ground up, sieved by the first step；
Second step mixes beta-silicon nitride powder described in the first step with sintering aid, after mixing under the action of blending agent Dry, sieving, obtains powder；
Third walks, and the powder pressing is molded, silicon nitride ceramics green compact are obtained；
The silicon nitride ceramics green compact are carried out gas pressure sintering, obtain silicon nitride ceramic material by the 4th step.
2. the preparation method of high heat conductivity silicon nitride ceramics as described in claim 1, which is characterized in that deoxidation described in the first step The technique of processing is to be respectively put into the silicon nitride powder and carbon dust in different crucibles, be positioned in tube furnace, with 5-10 DEG C/heating rate of min, in reaction atmosphere 4-8h is handled at a temperature of 1200 DEG C -1400 DEG C.
3. the preparation method of high heat conductivity silicon nitride ceramics as claimed in claim 2, which is characterized in that the reaction atmosphere is Nitrogen or ammonia.
4. the preparation method of high heat conductivity silicon nitride ceramics as described in claim 1, which is characterized in that be sintered described in second step Auxiliary agent is binary complex sintering aids, and the binary complex sintering aids include rare earth oxide and alkaline earth metal compound.
5. the preparation method of high heat conductivity silicon nitride ceramics as claimed in claim 4, which is characterized in that the rare earth oxide It is Y2O3、Yb2O3、Gd2O3、Nd2O3In one kind, the alkaline earth metal compound is MgO, MgSiN2Or MgF2In one kind.
6. the preparation method of high heat conductivity silicon nitride ceramics as described in claim 4 or 5, which is characterized in that described in second step The molar ratio of beta-silicon nitride powder, the rare earth oxide and the alkaline earth metal compound is 95-89:4-6:1-5.
7. the preparation method of high heat conductivity silicon nitride ceramics as described in claim 1, which is characterized in that mixed described in second step Medium is isopropanol, and the weight ratio of the isopropanol and the beta-silicon nitride powder is 1-1.5:1.
8. the preparation method of high heat conductivity silicon nitride ceramics as claimed in claim 7, which is characterized in that dry described in second step Process be, first rotarily dried at 55-75 DEG C, it is then 3-5 hours dry with 110-130 DEG C in vacuum drying oven.
9. a kind of preparation method of high heat conductivity silicon nitride ceramics as described in claim 1, which is characterized in that described in third step The process conditions of compression moulding are first to use punching block dry-pressing formed, then carry out cold isostatic compaction, forming pressure 200- 500MPa, molding time 100-300s.
10. a kind of preparation method of high heat conductivity silicon nitride ceramics as described in claim 1, which is characterized in that in the 4th step, The process conditions of the gas pressure sintering are, using nitrogen as sintering atmosphere, air pressure be 0.9-1.5Mpa under conditions of, with 5-15 DEG C/ The rate of min is warming up to 1700-2000 DEG C, and keeps the temperature 1.5-20h.
CN201810612015.1A 2018-06-14 2018-06-14 A kind of high heat conductivity silicon nitride ceramics and preparation method thereof Pending CN108585881A (en)

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CN109627014A (en) * 2019-01-14 2019-04-16 中国科学院上海硅酸盐研究所 A kind of high-intensitive, high-termal conductivity Si3N4Ceramic material and preparation method thereof
CN110937903A (en) * 2019-11-07 2020-03-31 中国科学院上海硅酸盐研究所 High-strength and high-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN111196728A (en) * 2019-11-20 2020-05-26 中国科学院上海硅酸盐研究所 High-strength, high-toughness and high-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN111196730A (en) * 2019-11-20 2020-05-26 中国科学院上海硅酸盐研究所 High-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN111302809A (en) * 2019-11-20 2020-06-19 中国科学院上海硅酸盐研究所 High-thermal-conductivity and high-strength silicon nitride ceramic material and preparation method thereof
CN111362704A (en) * 2020-03-19 2020-07-03 西安澳秦新材料有限公司 High-thermal-conductivity silicon nitride ceramic and preparation method thereof
CN111620697A (en) * 2020-06-08 2020-09-04 浙江锐克特种陶瓷有限公司 Silicon nitride substrate material prepared based on hot-pressing sintering method
CN111943683A (en) * 2020-08-14 2020-11-17 威海圆环先进陶瓷股份有限公司 Silicon nitride conductive ceramic and preparation method thereof
CN112142476A (en) * 2020-09-28 2020-12-29 中国科学院上海硅酸盐研究所 Silicon thermal reduction method for improving thermal conductivity and mechanical property of silicon nitride ceramic substrate material
CN112159237A (en) * 2020-09-28 2021-01-01 中国科学院上海硅酸盐研究所 High-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN112209722A (en) * 2020-09-08 2021-01-12 衡阳凯新特种材料科技有限公司 Silicon nitride composite material, preparation method thereof and heating element
CN112573936A (en) * 2020-12-14 2021-03-30 哈尔滨工业大学 Preparation method of silicon nitride ceramic substrate
CN112811922A (en) * 2021-01-20 2021-05-18 中国科学院上海硅酸盐研究所 Silicon nitride ceramic substrate of copper-clad plate and preparation method thereof
CN112830788A (en) * 2021-01-20 2021-05-25 中国科学院上海硅酸盐研究所 Silicon nitride ceramic material and preparation method thereof
CN113277863A (en) * 2021-06-18 2021-08-20 衡阳凯新特种材料科技有限公司 Ceramic composite material and preparation method thereof, bulletproof plate and armor protection equipment
CN113480319A (en) * 2021-08-20 2021-10-08 广东工业大学 Low-dielectric-constant silicon carbide and high-performance silicon nitride ceramic substrate and preparation method thereof
CN113735594A (en) * 2021-08-25 2021-12-03 北京科技大学 Method for preparing high-thermal-conductivity silicon nitride ceramic through hot-pressing sintering
CN113800918A (en) * 2021-09-18 2021-12-17 湖南工业大学 Trace in-situ carbon-induced Si3N4Heat-conducting ceramic material and preparation method thereof
CN114751754A (en) * 2022-05-23 2022-07-15 江苏方大正塬生态环境科技有限公司 Preparation method of silicon nitride ceramic substrate biscuit
CN114800775A (en) * 2022-05-23 2022-07-29 江苏方大正塬生态环境科技有限公司 GSPL-SNST silicon nitride tape casting biscuit and preparation method thereof
CN115477540A (en) * 2022-10-14 2022-12-16 衡阳凯新特种材料科技有限公司 High-thermal-conductivity silicon nitride ceramic material and preparation method and application thereof
CN115594511A (en) * 2022-11-03 2023-01-13 江苏省陶瓷研究所有限公司（Cn） Method for preparing silicon nitride ceramic by reaction sintering
CN115650733A (en) * 2022-10-31 2023-01-31 洛阳理工学院 Silicon carbide-added high-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN115703683A (en) * 2021-08-17 2023-02-17 赛默肯(苏州)电子新材料有限公司 High-strength high-heat-conductivity large-size silicon nitride ceramic and preparation method thereof
CN115849917A (en) * 2022-11-25 2023-03-28 宁波银瓷新材料有限公司 High-thermal-conductivity silicon nitride substrate material and processing technology thereof
CN116553936A (en) * 2023-04-17 2023-08-08 衡阳凯新特种材料科技有限公司 Ultrahigh-temperature vacuum-resistant silicon nitride ceramic material and preparation method thereof

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CN109627014A (en) * 2019-01-14 2019-04-16 中国科学院上海硅酸盐研究所 A kind of high-intensitive, high-termal conductivity Si3N4Ceramic material and preparation method thereof
CN109627014B (en) * 2019-01-14 2021-07-13 中国科学院上海硅酸盐研究所 Si with high strength and high thermal conductivity3N4Ceramic material and preparation method thereof
CN110937903B (en) * 2019-11-07 2021-06-15 中国科学院上海硅酸盐研究所 High-strength and high-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN110937903A (en) * 2019-11-07 2020-03-31 中国科学院上海硅酸盐研究所 High-strength and high-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN111196728A (en) * 2019-11-20 2020-05-26 中国科学院上海硅酸盐研究所 High-strength, high-toughness and high-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN111196730A (en) * 2019-11-20 2020-05-26 中国科学院上海硅酸盐研究所 High-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN111302809A (en) * 2019-11-20 2020-06-19 中国科学院上海硅酸盐研究所 High-thermal-conductivity and high-strength silicon nitride ceramic material and preparation method thereof
CN111362704A (en) * 2020-03-19 2020-07-03 西安澳秦新材料有限公司 High-thermal-conductivity silicon nitride ceramic and preparation method thereof
CN111620697A (en) * 2020-06-08 2020-09-04 浙江锐克特种陶瓷有限公司 Silicon nitride substrate material prepared based on hot-pressing sintering method
CN111943683A (en) * 2020-08-14 2020-11-17 威海圆环先进陶瓷股份有限公司 Silicon nitride conductive ceramic and preparation method thereof
CN112209722A (en) * 2020-09-08 2021-01-12 衡阳凯新特种材料科技有限公司 Silicon nitride composite material, preparation method thereof and heating element
CN112142476B (en) * 2020-09-28 2021-10-01 中国科学院上海硅酸盐研究所 Silicon thermal reduction method for improving thermal conductivity and mechanical property of silicon nitride ceramic substrate material
CN112159237B (en) * 2020-09-28 2021-10-01 中国科学院上海硅酸盐研究所 High-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN112159237A (en) * 2020-09-28 2021-01-01 中国科学院上海硅酸盐研究所 High-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN112142476A (en) * 2020-09-28 2020-12-29 中国科学院上海硅酸盐研究所 Silicon thermal reduction method for improving thermal conductivity and mechanical property of silicon nitride ceramic substrate material
CN112573936B (en) * 2020-12-14 2022-12-09 哈尔滨工业大学 Preparation method of silicon nitride ceramic substrate
CN112573936A (en) * 2020-12-14 2021-03-30 哈尔滨工业大学 Preparation method of silicon nitride ceramic substrate
CN112811922A (en) * 2021-01-20 2021-05-18 中国科学院上海硅酸盐研究所 Silicon nitride ceramic substrate of copper-clad plate and preparation method thereof
CN112830788B (en) * 2021-01-20 2021-11-02 中国科学院上海硅酸盐研究所 Silicon nitride ceramic material and preparation method thereof
CN112811922B (en) * 2021-01-20 2021-11-02 中国科学院上海硅酸盐研究所 Silicon nitride ceramic substrate of copper-clad plate and preparation method thereof
WO2022156637A1 (en) * 2021-01-20 2022-07-28 中国科学院上海硅酸盐研究所 Method for preparing silicon nitride ceramic material
WO2022156634A1 (en) * 2021-01-20 2022-07-28 中国科学院上海硅酸盐研究所 Preparation method for copper plate-covered silicon nitride ceramic substrate
CN112830788A (en) * 2021-01-20 2021-05-25 中国科学院上海硅酸盐研究所 Silicon nitride ceramic material and preparation method thereof
CN113277863A (en) * 2021-06-18 2021-08-20 衡阳凯新特种材料科技有限公司 Ceramic composite material and preparation method thereof, bulletproof plate and armor protection equipment
CN115703683A (en) * 2021-08-17 2023-02-17 赛默肯(苏州)电子新材料有限公司 High-strength high-heat-conductivity large-size silicon nitride ceramic and preparation method thereof
CN115703683B (en) * 2021-08-17 2023-10-20 赛默肯(苏州)电子新材料有限公司 High-strength high-heat-conductivity large-size silicon nitride ceramic and preparation method thereof
CN113480319A (en) * 2021-08-20 2021-10-08 广东工业大学 Low-dielectric-constant silicon carbide and high-performance silicon nitride ceramic substrate and preparation method thereof
CN113735594A (en) * 2021-08-25 2021-12-03 北京科技大学 Method for preparing high-thermal-conductivity silicon nitride ceramic through hot-pressing sintering
CN113800918A (en) * 2021-09-18 2021-12-17 湖南工业大学 Trace in-situ carbon-induced Si3N4Heat-conducting ceramic material and preparation method thereof
CN113800918B (en) * 2021-09-18 2022-12-09 湖南工业大学 Trace in-situ carbon-induced Si3N4 heat-conducting ceramic material and preparation method thereof
CN114751754A (en) * 2022-05-23 2022-07-15 江苏方大正塬生态环境科技有限公司 Preparation method of silicon nitride ceramic substrate biscuit
CN114800775A (en) * 2022-05-23 2022-07-29 江苏方大正塬生态环境科技有限公司 GSPL-SNST silicon nitride tape casting biscuit and preparation method thereof
CN115477540A (en) * 2022-10-14 2022-12-16 衡阳凯新特种材料科技有限公司 High-thermal-conductivity silicon nitride ceramic material and preparation method and application thereof
CN115650733A (en) * 2022-10-31 2023-01-31 洛阳理工学院 Silicon carbide-added high-thermal-conductivity silicon nitride ceramic material and preparation method thereof
CN115650733B (en) * 2022-10-31 2024-01-16 洛阳理工学院 Silicon carbide-added high-heat-conductivity silicon nitride ceramic material and preparation method thereof
CN115594511A (en) * 2022-11-03 2023-01-13 江苏省陶瓷研究所有限公司（Cn） Method for preparing silicon nitride ceramic by reaction sintering
CN115849917A (en) * 2022-11-25 2023-03-28 宁波银瓷新材料有限公司 High-thermal-conductivity silicon nitride substrate material and processing technology thereof
CN116553936A (en) * 2023-04-17 2023-08-08 衡阳凯新特种材料科技有限公司 Ultrahigh-temperature vacuum-resistant silicon nitride ceramic material and preparation method thereof

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Application publication date: 20180928