CN116813353A - Silicon nitride-based composite powder and preparation method and sintering method thereof - Google Patents
Silicon nitride-based composite powder and preparation method and sintering method thereof Download PDFInfo
- Publication number
- CN116813353A CN116813353A CN202310627086.XA CN202310627086A CN116813353A CN 116813353 A CN116813353 A CN 116813353A CN 202310627086 A CN202310627086 A CN 202310627086A CN 116813353 A CN116813353 A CN 116813353A
- Authority
- CN
- China
- Prior art keywords
- silicon nitride
- based composite
- powder
- composite powder
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 170
- 239000000843 powder Substances 0.000 title claims abstract description 138
- 238000005245 sintering Methods 0.000 title claims abstract description 130
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 28
- -1 amino compound Chemical class 0.000 claims abstract description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- PMXLLFCEIKHJCZ-UHFFFAOYSA-N iminosilicon Chemical compound [Si]=N PMXLLFCEIKHJCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000005049 silicon tetrachloride Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011863 silicon-based powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/587—Fine ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/591—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by reaction sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/62635—Mixing details
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62828—Non-oxide ceramics
- C04B35/62836—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/401—Alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention provides silicon nitride-based composite powder, a preparation method and a sintering method thereof. The silicon nitride-based composite powder consists of silicon nitride powder and a sintering aid coated on the surface of the silicon nitride powder, and is prepared by dissolving an amino compound prepared from the sintering aid in a liquid ammonia solution, mixing the silicon nitride and precursor powder thereof, realizing the combination with the sintering aid through the adsorption of the silicon nitride and precursor powder thereof, and finally pyrolyzing the silicon nitride loaded with the sintering aid and the precursor powder thereof in an environment of 500-1500 ℃ to obtain the silicon nitride-based composite powder. The sintering method is that the silicon nitride-based composite powder coated with the low-content sintering aid is used as a raw material, and the silicon nitride-based composite powder is sintered at 1500-1700 ℃ to obtain a compact silicon nitride sintered body with excellent mechanical properties under the condition of low content of the sintering aid.
Description
Technical Field
The invention relates to the technical field of ceramic material preparation, in particular to silicon nitride-based composite powder, a preparation method and a sintering method thereof.
Background
Because of the existence of Si-N covalent bonds in the silicon nitride, the bonding force among atoms is strong, so that the silicon nitride has various excellent properties such as high hardness, high strength, self-lubrication, high temperature resistance, corrosion resistance and good high temperature stability. Because of its excellent properties, silicon nitride is considered as an important structural ceramic and is widely used in the technical field of high precision tips of bearings, mechanical seal rings, turbine blades and the like. Since silicon nitride is a strongly covalent bond compound, the diffusion coefficient is small, and the volume diffusion and grain boundary diffusion rate required for densification are both small, the sintering driving force is small, which makes it difficult to achieve densification of silicon nitride ceramics by conventional solid phase sintering. The sintering aid and the silicon nitride powder surface oxide layer are added to form a low-temperature liquid phase to achieve the purpose of liquid phase sintering, so that densification sintering of the silicon nitride ceramic is promoted. However, after sintering, the sintering aid exists in the form of a second phase at the grain boundaries, which has an adverse effect on the mechanical and thermal properties of the silicon nitride ceramic. Therefore, how to reduce the content of the sintering aid on the premise of obtaining a highly dense ceramic becomes a key problem in the preparation process of the silicon nitride sintered body.
At present, in the process of preparing silicon nitride by sintering, silicon nitride powder/silicon powder is mostly used as a raw material, rare earth oxide and alkaline earth oxide are used as sintering aids, the combination of the sintering aids and the silicon nitride powder is realized by a mechanical mixing mode, and then densification sintering is carried out by a hot pressing/air pressure sintering process. In this sintering process, the uniformity of mixing the silicon nitride powder with the sintering aid is poor, and the amount of the sintering aid required is large in order to ensure the compactness of the sintered body. In addition, impurities (such as oxygen impurities in the solvent, etc.) are introduced during the mixing of the sintering aid with the silicon nitride powder, which have adverse effects on both the manufacturing cost and the sintered body performance.
By searching, the publication of application number 2021104240822 provides a method for preparing high-purity silicon nitride powder by an ammonolysis method, adding a solvent and silicon tetrachloride into a reaction vessel, and dissolving liquid ammonia into the solvent to obtain a silicon nitride precursor, and then burning, crushing and roasting the silicon precursor to obtain silicon nitride. Application number 2008101166738A process for preparing nano silicon nitride ceramic powder features that liquid ammonia is used as reaction medium, silicon halide is used as raw material, alkali metal K or Na is used as reducer, liquid ammonia is used to synthesize nano silicon nitride ceramic powder at low temp. The publication No. 2018102070948 provides a method for producing silicon nitride powder, which takes silicon tetrachloride and ammonia gas as raw materials to react and synthesize a precursor Si (NH) of the silicon nitride 2 Solid, pure Si (NH) is obtained 2 And (3) powder. The publication No. 2015106261175 provides a method for preparing nanoscale high-purity silicon nitride, which uses silicon tetrachloride and ammonia as raw materials, and synthesizes a precursor Si (NH) of silicon nitride by a liquid-phase reaction between silicon tetrachloride and ammonia dissolved in an organic hydrocarbon 2 After that, si (NH) is obtained by purification 2 Powder, finally, precursor Si (NH) 2 And (3) carrying out pyrolysis on the powder to obtain the nanoscale high-purity silicon nitride. However, the above applications are all focused on preparing high purity silicon nitride, and the prepared silicon nitride powder still needs to realize the loading of the sintering aid by a mechanical mixing mode in the subsequent sintering process. On one hand, the mixing uniformity of the sintering aid and the silicon nitride powder is poor, and a large amount of sintering aid is needed to realize densification sintering. On the other hand, new impurities are introduced during the mixing process, which adversely affects the properties of the final silicon nitride product.
The present invention is essentially different from the above-described published application. Specifically, the silicon nitride powder prepared by the invention is not high-purity silicon nitride in the disclosure, but silicon nitride-based composite powder with the surface loaded with a metal nitride coating capable of promoting sintering. The mode of forming the metal nitride sintering aid on the surface of the silicon nitride powder in situ can realize more uniform mixing on one hand, effectively improve the sintering activity of the silicon nitride powder and reduce the sintering temperature on the premise of reducing the addition amount of the sintering aid. On the other hand, the impurity introduced in the mixing process of the silicon nitride powder and the sintering aid in the traditional sintering process is avoided, and the performance of the silicon nitride ceramic is improved.
Disclosure of Invention
1. Technical problem to be solved by the invention
Aiming at the problems that the use amount of the sintering aid cannot be reduced on the premise of ensuring the compactness of a sintered body and impurities are introduced in the mixing process of the sintering aid and the silicon nitride powder by adopting a mechanical mixing mode of the silicon nitride powder/the silicon powder and the sintering aid in the conventional technology at present, the invention aims to provide the silicon nitride-based composite powder, the preparation method and the sintering method thereof, and the silicon nitride-based composite powder is used for preparing the sintered body by sintering, so that the compact silicon nitride sintered body with excellent mechanical properties can be obtained under the condition of few sintering aids.
The invention creatively loads the sintering auxiliary agent required in the subsequent sintering process of the silicon nitride ceramic product on the surface of the silicon nitride and the precursor powder thereof in the form of amino compound through adsorption, and forms a metal nitride coating on the surface of the silicon nitride powder through the amino compound adsorbed on the surface through the subsequent heat treatment process to be used as the sintering auxiliary agent. On one hand, the preparation process of the silicon nitride ceramic is simplified, the introduction of impurities in the mixing process of the silicon nitride powder and the sintering aid is avoided, and on the other hand, the in-situ mixing of the silicon nitride powder and the sintering aid is realized through surface liquid phase adsorption, so that the content of the sintering aid is reduced, and the preparation cost is reduced and the performance of a sintered body is improved.
2. Technical proposal
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the inventors of the present invention conducted breakthrough studies on the preparation process of a silicon nitride sintered body and the sintering characteristics of silicon nitride powder as a raw material thereof, and as a result, found that, in the preparation process of silicon nitride powder, rare earth metal, alkali metal or alkaline earth metal sintering aids were dissolved in a liquid ammonia solution to be mixed with silicon nitride and its precursor powder, and the combination with the sintering aids was achieved by the in-situ adsorption of the silicon nitride and its precursor powder. And then preparing the silicon nitride-based composite powder by a pyrolysis process, thereby obtaining silicon nitride powder uniformly compounded with a sintering aid, and finding that a compact silicon nitride sintered body with excellent mechanical properties can be obtained by sintering the powder at 1500-1700 ℃ to complete the invention.
The invention provides a preparation method of silicon nitride-based composite powder, which comprises the following steps:
s1, dissolving a sintering aid: mixing a sintering aid with liquid ammonia, preparing the sintering aid into an amino compound, and dissolving the amino compound in the liquid ammonia solution;
s2, loading of sintering auxiliary agent: mixing silicon nitride and precursor powder thereof with the liquid ammonia solution containing the amino compound prepared in the step S1, fully stirring, and completely volatilizing the liquid ammonia to enable the sintering aid to be loaded on the surfaces of the silicon nitride and precursor powder thereof in the form of the amino compound through adsorption;
s3, preparing silicon nitride-based composite powder: and (3) pyrolyzing the silicon nitride loaded with the sintering aid and the precursor powder prepared in the step (S2) at the temperature of 500-1500 ℃ to obtain the silicon nitride-based composite powder.
Further, the silicon nitride and the precursor powder thereof are one or a combination of more of silicon nitride precursors of amino silicon, imino silicon, amorphous silicon nitride and crystalline silicon nitride powder.
Further, the sintering aid is one or more of rare earth metal, alkali metal or alkaline earth metal, preferably one or more of La, Y, sm, eu, yb, li, ca, mg.
Further, the sintering aid accounts for 0.5-5 wt% of the silicon nitride and the precursor powder thereof.
Further, the pyrolysis process is performed in a vacuum environment or a protective gas environment, the absolute pressure of the vacuum environment is less than 2Pa, the protective gas is one or a combination of more of argon, nitrogen, ammonia and hydrogen, and the protective gas pressure is 50-150 kPa.
Further, the average grain diameter of the silicon nitride-based composite powder obtained by pyrolysis is 100-500 nm, and the surface layer of the silicon nitride-based composite powder is coated with metal nitride formed by a sintering aid in the heat treatment process.
The sintering method of the silicon nitride-based composite powder provided by the invention is characterized in that the silicon nitride-based composite powder obtained by adopting the preparation method is used as a raw material, and after the powder is molded, the silicon nitride-based composite powder is sintered at 1500-1700 ℃ to obtain a compact silicon nitride sintered body, wherein the relative density of the silicon nitride sintered body is more than 99.5%, the second phase content is less than 6.5wt%, and the flexural strength is more than 1100MPa.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) According to the preparation method of the silicon nitride-based composite powder, the sintering aid is dissolved in liquid ammonia and mixed with the silicon nitride and the precursor powder thereof, in-situ mixing of the sintering aid and the silicon nitride and the precursor powder thereof is realized through in-situ adsorption, and finally the silicon nitride-based composite powder loaded with the sintering aid and capable of being directly sintered is obtained through pyrolysis in an environment of 500-1500 ℃, so that a compact silicon nitride sintered body with excellent mechanical properties is provided, and in particular, the silicon nitride-based composite powder with low sintering aid content capable of being directly sintered to obtain the compact silicon nitride sintered body with excellent mechanical properties is provided.
(2) According to the preparation method of the silicon nitride-based composite powder, silicon nitride and precursor powder thereof are compounded with the rare earth metal, alkali metal or alkaline earth metal sintering aid dissolved in liquid ammonia, so that the sintering aid and the silicon nitride powder are uniformly mixed, the content of the sintering aid is reduced on the premise of ensuring the compactness of a sintered body, oxygen impurities introduced in the mixing process of the silicon nitride powder and the sintering aid in the traditional process are avoided, and the preparation method has obvious advantages compared with the traditional process in terms of manufacturing cost and the performance of the sintered body.
Drawings
FIG. 1 is a flow chart of a method of sintering a silicon nitride-based composite powder.
Detailed Description
For a further understanding of the present invention, the present invention will be described in detail with reference to the drawings.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The preparation method of the silicon nitride-based composite powder comprises the following steps:
s1, dissolving a sintering aid: mixing a sintering aid with liquid ammonia, preparing the sintering aid into an amino compound, and dissolving the amino compound in the liquid ammonia solution;
s2, loading of sintering auxiliary agent: mixing silicon nitride and precursor powder thereof with the liquid ammonia solution containing the amino compound prepared in the step S1, fully stirring, and completely volatilizing the liquid ammonia to enable the sintering aid to be loaded on the surfaces of the silicon nitride and precursor powder thereof in the form of the amino compound through adsorption;
s3, preparing silicon nitride-based composite powder: and (3) pyrolyzing the silicon nitride loaded with the sintering aid and the precursor powder prepared in the step (S2) at the temperature of 500-1500 ℃ to obtain the silicon nitride-based composite powder. Specifically, the average grain diameter of the silicon nitride-based composite powder obtained by pyrolysis is 100-500 nm. The surface layer of the silicon nitride-based composite powder is coated with metal nitride formed by the sintering aid in the heat treatment process.
Wherein the silicon nitride and the precursor powder thereof are one or a combination of more of silicon nitride precursors of amino silicon, imino silicon, amorphous silicon nitride and crystalline silicon nitride powder. The preparation of silicon nitride and its precursor powders may be accomplished in a variety of ways conventional in the industry, including: silicon halide and liquid ammonia are used as raw materials, a silicon nitride precursor is prepared through ammonolysis reaction, and the prepared precursor is repeatedly cleaned and filtered by the liquid ammonia to remove ammonium chloride byproducts. Further comprises: the preparation and the like by utilizing the reaction of gas-phase silicon halide and ammonia gas are common knowledge in the industry and are not described in detail herein. The crystalline silicon nitride powder may be prepared by any known method including an ammonolysis method, a silicon powder nitriding method and a self-propagating method.
In the present invention, the sintering aid used comprises one or more combinations of rare earth metals, alkali metals or alkaline earth metals, preferably La, Y, sm, eu, yb, li, ca, mg. They may be used alone or in suitable combination according to the purpose, and are not to be taken as an exhaustive list. These metals can be dissolved in liquid ammonia to form amino compounds, which adhere to the surface of silicon nitride and its precursor powder by adsorption, and after pyrolysis, the corresponding nitrides are formed on the surface of the silicon nitride powder. The sintering aid accounts for 0.5 to 5 weight percent of the silicon nitride and the precursor powder thereof, and is specifically such as 0.5 weight percent, 0.8 weight percent, 1.2 weight percent, 2.0 weight percent, 4.0 weight percent, 5.0 weight percent and the like, and is not described one by one.
In the invention, the pyrolysis process is carried out in a vacuum environment, an inert protective atmosphere or a nitrogen-containing reductive protective atmosphere, wherein the absolute pressure of the vacuum environment is less than 2Pa, and the inert atmosphere is nitrogen atmosphere and argon atmosphere, preferably nitrogen atmosphere. The nitrogen-containing reducing atmosphere refers to an ammonia atmosphere or a mixed atmosphere of nitrogen and hydrogen/ammonia. Preferably an ammonia gas atmosphere, more preferably a mixed atmosphere of nitrogen and ammonia gas. The atmosphere is preferably completely free of oxygen. The protective gas pressure is 50-150 kPa, such as 50kPa, 80kPa, 100kPa, 1200kPa, 150kPa.
Next, a method for sintering the silicon nitride-based composite powder of the present invention, namely, a method for producing a corresponding silicon nitride sintered body will be described: the silicon nitride-based composite powder obtained by the preparation method is used as a raw material, after the powder is molded, the powder is sintered in an environment of 1500-1700 ℃ to obtain a compact silicon nitride sintered body, the relative density of the silicon nitride sintered body is more than 99.5%, the second phase content is lower than 6.5%, the bending strength is higher than 1100MPa, wherein the second phase refers to a new phase formed after the sintering aid reacts with the silicon nitride.
Silicon nitride is a difficult-to-sinter material, and conventional techniques require mixing silicon nitride powder with a sintering aid, and the conventional mixing method is wet, for example, mixing silicon nitride powder, a sintering aid, an additive for molding, and the like by ball milling using water as a dispersion medium. The surface of the silicon nitride powder prepared by the method is wrapped with the nitride sintering aid, so that the mixing process is not needed, the preparation process is simplified, impurities (particularly oxygen impurities in a solvent) introduced in the mixing process are avoided, and the performance of the sintered body is improved.
In the present invention, the powder molding method is not limited, and known powder molding techniques such as press molding, injection molding, and isostatic molding may be used.
In the present invention, the method for sintering the silicon nitride-based composite powder is not limited as long as the sintered body can be densified, and normal pressure sintering or gas pressure sintering under an inert gas atmosphere may be employed, and known techniques for simultaneous molding and sintering such as hot isostatic pressing, spark plasma sintering, and hot press sintering may be employed.
In the invention, the sintering parameters such as sintering temperature, pressure and the like are lower than those of the traditional method because the sintering aid and the silicon nitride powder are uniformly mixed, and the method has important significance in reducing the sintering cost of the silicon nitride sintered body.
The invention is further described below with reference to examples.
Example 1
Injecting liquid ammonia and toluene (specifically, the volume ratio of the liquid ammonia to the toluene is 8:1) into a reactor at the temperature of minus 50 ℃, continuously stirring in the reactor, and slowly injecting SiCl dissolved in the upper part of the reactor 4 Toluene solution (specifically SiCl) 4 The volume ratio of toluene to toluene is 1: 3). In SiCl 4 During the injection of the solution, white reaction products appear in the reactor. After the reaction is finished, stirring is stopped, and the reaction product is settled at the bottom of the reactor by standing. And conveying the precipitate in the reactor to a filtering device, and filtering to obtain a reaction product. The ammonia is taken as solvent, and ammonium chloride byproducts mixed in the reaction product are cleaned out to obtain pure silicon nitride precursor Si (NH) 2 . To the Si (NH) obtained 2 Slowly adding liquid ammonia (La occupies Si (NH)) dissolved with rare earth metal La 2 The mass ratio of (C) is 0.5wt%, liquid ammonia and Si (NH) 2 The volume ratio of (2) is 10: 1) Stirring thoroughlyCompletely volatilizing and drying the liquid ammonia to obtain Si (NH) loaded with LaN precursor 2 。
The obtained Si (NH) loaded with LaN precursor 2 Delivering the mixture into a heating furnace, calcining for 60min at 1000 ℃ under the nitrogen circulation atmosphere (the oxygen content is lower than 50 ppm), and calcining for 120min at 1500 ℃ to obtain the crystalline silicon nitride-based composite powder.
The average grain diameter of the obtained silicon nitride-based composite powder is 200nm, and the surface of the silicon nitride-based composite powder is coated with a LaN thin layer.
And (3) carrying out hot-pressing sintering on the obtained silicon nitride-based composite powder, wherein the sintering temperature is 1650 ℃, the sintering pressure is 30MPa, and the sintering time is 120min to obtain a silicon nitride sintered body with the relative density of 99.72% and the bending strength of 1103 MPa.
Similarly, see Table 1 for a table of specific preparation conditions of the silicon nitride powders and the characteristics of the final silicon nitride sintered body in examples 1 to 20 and comparative examples 1 to 4.
Example 21
To contain amorphous Si 3 N 4 Slowly adding liquid ammonia (the mass ratio of Y to amorphous silicon nitride is 0.5wt percent) in which rare earth metal Y is dissolved into a container of the powder, fully stirring the liquid ammonia, completely volatilizing the liquid ammonia, and drying the liquid ammonia to obtain the amorphous silicon nitride loaded with NY precursor.
The obtained amorphous silicon nitride loaded with the NY precursor is conveyed into a heating furnace and calcined for 180min at 1000 ℃ under the nitrogen circulation atmosphere (the oxygen content is lower than 50 ppm) to obtain the crystalline silicon nitride-based composite powder.
The obtained silicon nitride powder has an average particle diameter of 200nm and is coated with a thin layer of NY.
The obtained silicon nitride powder is sintered by hot pressing at 1600 ℃ under 30MPa for 120min to obtain a silicon nitride sintered body with the relative density of 99.72% and the bending strength of 1110 MPa.
Similarly, see table 1 for specific conditions for preparing the silicon nitride-based composite powder and the final silicon nitride sintered body characteristic information in examples 21 to 28.
The type and content of the silicon nitride powder surface sintering aid can be achieved by dissolving different types and qualities of sintering aids in liquid ammonia. Except for this, silicon nitride-based composite powders of examples 2 to 20 and comparative examples 1 to 6, in which the types and contents of sintering aids are shown in Table 1, were prepared in exactly the same manner as in example 1. The silicon nitride powders in comparative examples 5 and 6 were prepared in the same manner as in example 1, except that no sintering aid was added to the liquid ammonia.
TABLE 1 silicon nitride powder preparation conditions and silicon nitride sintered compact characteristic information table
Note that: -indicating the absence of the process
Comparative example 5
10g of silicon nitride powder which does not contain a sintering aid and is prepared according to the same method as in example 1, 2g of metal yttrium, mixing the silicon nitride powder with the sintering aid by using a ball mill with water as a solvent, and performing hot-pressing sintering on the mixed powder at the sintering temperature of 1700 ℃ under the sintering pressure of 30MPa for 120min to obtain a silicon nitride sintered body with the compactness of 92.8% and the bending strength of 702 MPa.
Comparative example 6
10g of silicon nitride powder containing no sintering aid prepared in the same manner as in example 1 was taken and Y 2 O 3 8g of MgO mixed sintering aid, mixing silicon nitride powder with the sintering aid by using a ball mill by taking water as a solvent, and carrying out hot pressing sintering on the mixed powder at the sintering temperature of 1700 ℃ under the sintering pressure of 30MPa for 120min to obtain the silicon nitride sintered body with the compactness of 97.4% and the bending strength of 890 MPa.
The invention and its embodiments have been described above by way of illustration and not limitation, but rather one of the embodiments of the invention is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.
Claims (10)
1. A method for preparing silicon nitride-based composite powder, which is characterized by comprising the following steps:
s1, dissolving a sintering aid: mixing a sintering aid with liquid ammonia, preparing the sintering aid into an amino compound, and dissolving the amino compound in the liquid ammonia solution;
s2, loading of sintering auxiliary agent: mixing silicon nitride and precursor powder thereof with the liquid ammonia solution containing the amino compound prepared in the step S1, fully stirring, and completely volatilizing the liquid ammonia to enable the sintering aid to be loaded on the surfaces of the silicon nitride and precursor powder thereof in the form of the amino compound through adsorption;
s3, preparing silicon nitride-based composite powder: and (3) pyrolyzing the silicon nitride loaded with the sintering aid and the precursor powder prepared in the step (S2) at the temperature of 500-1500 ℃ to obtain the silicon nitride-based composite powder.
2. The method for producing a silicon nitride-based composite powder according to claim 1, wherein: the silicon nitride and the precursor powder thereof are one or a combination of more of silicon nitride precursors of amino silicon, imino silicon, amorphous silicon nitride and crystalline silicon nitride powder.
3. The method for producing a silicon nitride-based composite powder according to claim 1, wherein: the sintering aid is one or a combination of more of rare earth metal, alkali metal or alkaline earth metal.
4. A method for producing a silicon nitride-based composite powder according to claim 3, wherein: the sintering aid comprises one or more combinations of rare earth metals, alkali metals or alkaline earth metals, preferably one or more combinations of La, Y, sm, eu, yb, li, ca, mg.
5. The method for producing a silicon nitride-based composite powder according to claim 1, wherein: the sintering aid accounts for 0.5-5 wt% of the silicon nitride and the precursor powder thereof.
6. The method for producing a silicon nitride-based composite powder according to claim 1, wherein: the pyrolysis process is carried out in a vacuum environment or a protective gas environment, the absolute pressure of the vacuum environment is less than 2Pa, the protective gas is one or a combination of more of argon, nitrogen, ammonia and hydrogen, and the pressure of the protective gas is 50-150 kPa.
7. The method for producing a silicon nitride-based composite powder according to claim 1, wherein: the average grain diameter of the silicon nitride-based composite powder obtained by pyrolysis is 100-500 nm.
8. A method for producing a silicon nitride-based composite powder according to any one of claims 1 to 7, characterized in that: the surface layer of the silicon nitride-based composite powder is coated with metal nitride formed by a sintering aid in the heat treatment process.
9. A silicon nitride-based composite powder, characterized in that: obtained by the process according to any one of claims 1 to 8.
10. A sintering method of silicon nitride-based composite powder is characterized in that: the silicon nitride-based composite powder obtained by the preparation method according to any one of claims 1 to 8 is used as a raw material, and after powder molding, the compact silicon nitride sintered body is obtained by sintering at 1500-1700 ℃ in the environment, wherein the relative density of the silicon nitride sintered body is more than 99.5%, the content of the second phase is less than 6.5%, and the flexural strength is more than 1100MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310627086.XA CN116813353A (en) | 2023-05-30 | 2023-05-30 | Silicon nitride-based composite powder and preparation method and sintering method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310627086.XA CN116813353A (en) | 2023-05-30 | 2023-05-30 | Silicon nitride-based composite powder and preparation method and sintering method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116813353A true CN116813353A (en) | 2023-09-29 |
Family
ID=88117686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310627086.XA Pending CN116813353A (en) | 2023-05-30 | 2023-05-30 | Silicon nitride-based composite powder and preparation method and sintering method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116813353A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB359559A (en) * | 1930-07-25 | 1931-10-26 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of alkali metal cyanates |
| EP0227324A2 (en) * | 1985-12-23 | 1987-07-01 | Ford Motor Company Limited | Method of making ultrapure silicon nitride/oxynitride powder |
| CN101318637A (en) * | 2008-07-15 | 2008-12-10 | 北京科技大学 | Process for producing nano-silicon nitride ceramics powder |
| CN105969332A (en) * | 2016-05-16 | 2016-09-28 | 浙江理工大学 | Synthesis method for coating M2Si5N8: Eu<2+> luminescent material with boron nitride |
| CN110590377A (en) * | 2019-10-29 | 2019-12-20 | 中钢集团洛阳耐火材料研究院有限公司 | High beta-phase compact silicon nitride ceramic and low-temperature preparation method |
-
2023
- 2023-05-30 CN CN202310627086.XA patent/CN116813353A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB359559A (en) * | 1930-07-25 | 1931-10-26 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of alkali metal cyanates |
| EP0227324A2 (en) * | 1985-12-23 | 1987-07-01 | Ford Motor Company Limited | Method of making ultrapure silicon nitride/oxynitride powder |
| CN101318637A (en) * | 2008-07-15 | 2008-12-10 | 北京科技大学 | Process for producing nano-silicon nitride ceramics powder |
| CN105969332A (en) * | 2016-05-16 | 2016-09-28 | 浙江理工大学 | Synthesis method for coating M2Si5N8: Eu<2+> luminescent material with boron nitride |
| CN110590377A (en) * | 2019-10-29 | 2019-12-20 | 中钢集团洛阳耐火材料研究院有限公司 | High beta-phase compact silicon nitride ceramic and low-temperature preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1997018162A1 (en) | Synthesis of 312 phases and composites thereof | |
| WO1997018162A9 (en) | Synthesis of 312 phases and composites thereof | |
| JPH1149572A (en) | Ceramic composite particles and their production | |
| JP3667062B2 (en) | Method for producing sintered boron carbide | |
| KR100500495B1 (en) | Aluminium nitride ceramics, members for use in a system for producing semiconductors, and corrosion resistant members | |
| JPH09268072A (en) | Production of silicon nitride sintered compact | |
| KR20220038898A (en) | Cubic boron nitride powder and method of fabrication the same | |
| CN116813353A (en) | Silicon nitride-based composite powder and preparation method and sintering method thereof | |
| RU2239613C1 (en) | Method of manufacturing silicon nitride-based products | |
| WO2020241700A1 (en) | Silicon nitride powder and method for producing same, and method for producing silicon nitride sintered body | |
| JP2662863B2 (en) | Method for producing silicon nitride based sintered body | |
| JP3023435B2 (en) | High purity silicon carbide sintered body and method for producing the same | |
| JPH01160870A (en) | Silicon nitride sintered compact and production thereof | |
| JPH01145380A (en) | Production of silicon nitride sintered form | |
| JPH1179848A (en) | Silicon carbide sintered compact | |
| JPH0733528A (en) | Composite sintered ceramic, its production and semiconductor production jig made therefrom | |
| JP3124866B2 (en) | Method for producing silicon nitride based sintered body | |
| JPS6126566A (en) | Method of sintering sic composite body | |
| JPH09278524A (en) | Production of silicon carbide sintered compact | |
| JPS63151682A (en) | Silicon nitride sintered body and manufacture | |
| JP3536494B2 (en) | Nitrogen-containing silane compounds | |
| JP2811493B2 (en) | Silicon nitride sintered body | |
| JPS61122167A (en) | High strength silicon nitride base sintered body and manufacture | |
| JPH07206526A (en) | Production of silicon nitride sintered compact | |
| JPH0512297B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |