CN111547724A - Superfine titanium carbide powder and preparation method thereof - Google Patents
Superfine titanium carbide powder and preparation method thereof Download PDFInfo
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- CN111547724A CN111547724A CN202010432111.5A CN202010432111A CN111547724A CN 111547724 A CN111547724 A CN 111547724A CN 202010432111 A CN202010432111 A CN 202010432111A CN 111547724 A CN111547724 A CN 111547724A
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- 239000000843 powder Substances 0.000 title claims abstract description 70
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 13
- 239000011975 tartaric acid Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention relates to superfine titanium carbide powder and a preparation method thereof. The method comprises the following steps: drying metallurgical-grade metatitanic acid at the temperature of 100-400 ℃, and calcining at the temperature of 300-400 ℃ to obtain TiO2Powder; the TiO is2The particle size of the powder is 0.01-0.05 μm; TiO22Uniformly mixing the powder with tartaric acid powder, and preparing superfine titanium carbide powder by low-temperature vacuum carbonization; the Fisher size of the superfine titanium carbide powder is less than 0.8 mu m. Has the advantages that: the superfine titanium carbide powder with the Fisher size less than 0.8 mu m is prepared by the method, and chemical components such as impurities and the like meet requirements.
Description
Technical Field
The invention belongs to the field of preparation of new materials for powder metallurgy, and relates to ultrafine titanium carbide powder and a preparation method thereof.
Background
TiC is the lightest density (4.9 g/cm) of the refractory metal carbides3) Highest hardness (3200 Kg/cm)2) And the material with the most abundant resources, and also has the properties of high melting point and high elastic modulus. Has been widely applied in the field of hard alloy. The application mainly comprises the following steps: 1. as the hard phase of the steel bonded alloy, a large amount of TiC is adopted as the hard phase in the brands of TM52, TM60 and the like; 2. as a hard phase of the cermet with TiN; 3. and the compound carbide of titanium, tungsten, tantalum and the like is formed as a solvent. TiC will necessarily find wider application as a substitute for WC due to the increasing invaluability of tungsten resources and the relative cheapness of titanium resources.
As the application requirements of hard alloy are continuously improved, higher requirements are also provided for the metallographic structure of the material. In order to obtain a more homogeneous and fine metallurgical structure of the steel-bonded gold and cermet, the TiC powder, one of the components, must also be more fine and homogeneous.
The preparation method of TiC powder commonly applied in the market at present is to calcine TiO at high temperature2The powder and the solid carbon black are subjected to ball milling and mixing and are carbonized at high temperature in a carbon tube furnace, the method has high carbonization temperature (1900-. Few reports on the preparation of superfine TiC powder at home and abroad are also mainly focused on gas-phase carbonization or utilization of gas-phase TiCl4The TiC is prepared by carbonization, and the methods have the defects of long working procedure, high cost, difficulty in realizing industrialization and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides superfine titanium carbide powder and a preparation method thereof. The method has the advantages of short process, low cost, easy realization of industrialization and the like.
A method for preparing superfine titanium carbide powder comprises the following steps:
(1)drying metallurgical-grade metatitanic acid at the temperature of 100-400 ℃, and calcining at the temperature of 300-400 ℃ to obtain TiO2Powder; the TiO is2The particle size of the powder is 0.01-0.05 μm;
(2)TiO2uniformly mixing the powder with tartaric acid powder, and preparing superfine titanium carbide powder by low-temperature vacuum carbonization; the Fisher size of the superfine titanium carbide powder is less than 0.8 mu m.
Further, the impurity content of the titanium carbide powder is Fe: <0.01, Ca: <0.01, Al <0.01, Si <0.02, Na <0.01, Mo < 0.01.
Further, the calcination time in the step (1) is 3 to 7 hours.
Further, the mixing time in the step (2) is 3 to 10 hours.
Further, the low-temperature vacuum carbonization process in the step (2) comprises the following steps: slowly raising the temperature at 80-200 ℃ for 3-8 hours; then carrying out carbonization reaction at 1250-1550 ℃ for 6-15 hours; and (3) after carbonization, the vacuum degree is less than 5Pa, and then the furnace is cooled for 15-20 hours.
Further, the TiO in the step (2)2The weight ratio of the powder to the tartaric acid powder is 1 (4.5-4.6).
Has the advantages that: the superfine titanium carbide powder with the Fisher size less than 0.8 mu m is prepared by the method, and chemical components such as impurities and the like meet requirements.
Detailed Description
The invention firstly prepares nano-scale TiO2Powder and use of highly active and high specific surface area tartaric acid decomposing carbon as TiO2Reducing the carbonized carbon source to refine the granularity of the raw material powder, and then carbonizing the raw material powder at low temperature in a vacuum furnace to realize the purpose of preparing the superfine TiC powder.
The invention provides a superfine titanium carbide powder, the Fisher size of which is less than 0.8 mu m.
A method for preparing superfine titanium carbide powder comprises the following steps:
(1) the metallurgical-grade metatitanic acid purchased in the market is dried at the temperature of 100-400 ℃ and calcined at the temperature of 300-400 ℃ to obtainTiO2Powder; the TiO is2The particle size of the powder is 0.01-0.05 μm;
(2)TiO2uniformly mixing the powder with tartaric acid powder, and preparing superfine titanium carbide powder by low-temperature vacuum carbonization; the Fisher size of the superfine titanium carbide powder is less than 0.8 mu m.
The impurity content of the titanium carbide powder obtained by the method is required to be Fe: <0.01, Ca: <0.01, Al <0.01, Si <0.02, Na <0.01, Mo < 0.01.
In the step (1), metallurgical-grade metatitanic acid is dried at the temperature of 100 ℃ and 120 ℃ for the purpose of evaporating moisture in metatitanic acid. After drying, the powder is calcined in a rotary furnace at low temperature to prevent TiO from being generated2And (4) coarsening the powder. The calcination temperature is 300-400 ℃ and the calcination time is 3-7 hours, the purpose is to decompose metatitanic acid into TiO2And H2O and desulfurization. After the low-temperature drying and calcining, TiO2The nitrogen adsorption particle size of the powder is 0.01-0.05. mu.m.
In the step (2) of the present application, TiO was subjected to ball milling in a 380 liter dry ball mill2The powder and the tartaric acid powder are uniformly mixed, the mixing time of each batch is 3-10 hours, and the mixing amount is 40-100 Kg. And (3) carrying out low-temperature vacuum carbonization after uniformly mixing, wherein the charging amount of each furnace is 20-60 kg during vacuum carbonization. Slowly heating at low temperature (80-200 deg.C) for 3-8 hr to make carbon decomposed by tartaric acid as TiO2Reducing the carbonized carbon source. And during the carbonization reaction, the carbonization temperature is 1250-1550 ℃, and the heat preservation time is 6-15 hours. And (3) after carbonization, the vacuum degree is less than 5Pa, and then the furnace is cooled for 15-20 hours.
The invention mainly prepares nano-scale TiO2The purpose of preparing the superfine TiC powder is realized by three ways of generating a high-activity carbon source and reducing the carbonization temperature in the powder and carbonization processes.
The basic principle of the invention is as follows: preparing an oxidic carbon reduced powder product, the particle size of the powder being determined by two factors: 1, the granularity of the raw material, and the powder with small granularity can be prepared only when the granularity of the raw material is small. 2, reducing the reaction temperature as much as possible in the reduction carbonization process, but ensuring the reaction to be complete. The measures adopted for this purpose are as follows: improving the activity of the substances in the reaction process, and pumping the gas generated in the reaction process by using a vacuum pump during carbonization.
Mixing nano-scale TiO2When the powder is mixed with tartaric acid and reacted, the heat-insulating treatment is implemented at low temp. (80-200 deg.C) so as to make tartaric acid decompose high-activity carbon and use it as TiO2Reducing the carbonized carbon source. Due to TiO2The powder is nano-scale, the carbon is high in activity, the reaction diffusion distance is shortened, the reaction temperature is reduced, and the growth of crystal grains is effectively prevented.
In vacuum carbonization, TiO2+C→TiC+CO↑
During vacuum carbonization, the generated CO gas is continuously pumped away, so that the reaction is carried out at a lower temperature, and the growth of particles is avoided.
The present application is illustrated below with reference to specific examples.
Example 1:
drying metatitanic acid in an oven (100 ℃), calcining at low temperature (380 ℃) in a rotary furnace, and calcining the TiO2The particle size was 0.02. mu.m. 32 kg of TiO are added2The powder was mixed with a certain proportion (specific amount is 144 kg) of tartaric acid for 6 hours, and then vacuum carbonized at a maximum temperature of 1430 ℃ for 13 hours. And (5) discharging and ball milling after cooling along with the furnace. The Fsss particle size is measured by sampling to be 0.73 μm, and the chemical composition meets the requirement. The chemical indexes are shown in Table 1.
Example 2:
drying metatitanic acid in an oven (115 ℃) and then calcining at low temperature (350 ℃) in a rotary furnace, wherein TiO is calcined2The particle size was 0.03. mu.m. 35 kg of TiO2The powder was mixed with a proportion (specific amount: 147.2 kg) of tartaric acid for 7 hours, then vacuum carbonized at a maximum temperature of 1480 ℃ for 14 hours. And (5) discharging and ball milling after cooling along with the furnace. The Fsss particle size is measured by sampling to be 0.78 μm, and the chemical composition meets the requirement. The chemical indexes are shown in Table 1.
TABLE 1 superfine TiC powder Performance index
| C | O | N | Ca | Al | Fe | Mo | Na | Si | Fsss(μm) | |
| Example 1 | 19.25 | 0.50 | 0.021 | <0.01 | <0.01 | 0.063 | <0.01 | <0.01 | <0.01 | 0.73 |
| Example 2 | 19.35 | 0.58 | 0.024 | <0.01 | <0.01 | 0.025 | <0.01 | <0.01 | <0.01 | 0.78 |
As can be seen from Table 1, examples 1 and 2 are excellent in C, O, N content, satisfactory in impurity content, and excellent in particle size.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims, and not by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. A method for preparing superfine titanium carbide powder is characterized by comprising the following steps:
(1) drying metallurgical-grade metatitanic acid at the temperature of 100-400 ℃, and calcining at the temperature of 300-400 ℃ to obtain TiO2Powder; the TiO is2The particle size of the powder is 0.01-0.05 μm;
(2)TiO2uniformly mixing the powder with tartaric acid powder, and preparing superfine titanium carbide powder by low-temperature vacuum carbonization; the Fisher size of the superfine titanium carbide powder is less than 0.8 mu m.
2. The method of preparing ultrafine titanium carbide powder according to claim 1, wherein the titanium carbide powder has an impurity content of Fe: <0.01, Ca: <0.01, Al <0.01, Si <0.02, Na <0.01, Mo < 0.01.
3. The method for preparing ultrafine titanium carbide powder according to claim 1, wherein the calcination time in step (1) is 3 to 7 hours.
4. The method for preparing ultrafine titanium carbide powder according to claim 1, wherein the mixing time in the step (2) is 3 to 10 hours.
5. The method for preparing ultrafine titanium carbide powder according to claim 1, wherein the low-temperature vacuum carbonization in the step (2) comprises: slowly raising the temperature at 80-200 ℃ for 3-8 hours; then carrying out carbonization reaction at 1250-1550 ℃ for 6-15 hours; and (3) after carbonization, the vacuum degree is less than 5Pa, and then the furnace is cooled for 15-20 hours.
6. The method for preparing ultrafine titanium carbide powder according to claim 1, wherein the weight ratio of the TiO2 powder to the tartaric acid powder in step (2) is 1 (4.5-4.6).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115818646A (en) * | 2022-12-14 | 2023-03-21 | 昆明理工大学 | Preparation method of titanium carbide powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004323968A (en) * | 2003-04-29 | 2004-11-18 | Korea Mach Res Inst | METHOD FOR MANUFACTURING ULTRAFINE TiC-TRANSITION METAL BASED COMPOSITE POWDER |
| CN102153084A (en) * | 2011-02-28 | 2011-08-17 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing submicron titanium carbide powder |
| CN102910628A (en) * | 2011-08-05 | 2013-02-06 | 中国科学院上海硅酸盐研究所 | Synthetic method for high-melting-point transition metal carbide ultrafine powder |
| CN103130506A (en) * | 2013-03-15 | 2013-06-05 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing superfine titanium carbonitride |
| CN110357639A (en) * | 2019-07-29 | 2019-10-22 | 株洲红芯新材料科技有限公司 | Super fine titanium carbonitride powder end and preparation method thereof |
-
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- 2020-05-20 CN CN202010432111.5A patent/CN111547724A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004323968A (en) * | 2003-04-29 | 2004-11-18 | Korea Mach Res Inst | METHOD FOR MANUFACTURING ULTRAFINE TiC-TRANSITION METAL BASED COMPOSITE POWDER |
| CN102153084A (en) * | 2011-02-28 | 2011-08-17 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing submicron titanium carbide powder |
| CN102910628A (en) * | 2011-08-05 | 2013-02-06 | 中国科学院上海硅酸盐研究所 | Synthetic method for high-melting-point transition metal carbide ultrafine powder |
| CN103130506A (en) * | 2013-03-15 | 2013-06-05 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing superfine titanium carbonitride |
| CN110357639A (en) * | 2019-07-29 | 2019-10-22 | 株洲红芯新材料科技有限公司 | Super fine titanium carbonitride powder end and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SEN WEI ET AL: "Preparation of TiC powders by carbothermal reduction method in vacuum", 《TRANS. NONFERROUS MET. SOC. CHINA》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115818646A (en) * | 2022-12-14 | 2023-03-21 | 昆明理工大学 | Preparation method of titanium carbide powder |
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Application publication date: 20200818 |