CN115285995A - Tungsten carbide powder production process - Google Patents
Tungsten carbide powder production process Download PDFInfo
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- CN115285995A CN115285995A CN202210837446.4A CN202210837446A CN115285995A CN 115285995 A CN115285995 A CN 115285995A CN 202210837446 A CN202210837446 A CN 202210837446A CN 115285995 A CN115285995 A CN 115285995A
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- Prior art keywords
- tungsten carbide
- carbon
- carbide powder
- gas
- organic resin
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- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000843 powder Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 48
- 239000003112 inhibitor Substances 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229920006122 polyamide resin Polymers 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 abstract description 4
- 239000010937 tungsten Substances 0.000 abstract description 4
- 239000012298 atmosphere Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000035484 reaction time Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 229910052580 B4C Inorganic materials 0.000 description 7
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical group B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 4
- 238000005255 carburizing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005245 sintering Methods 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
- C01B32/949—Tungsten or molybdenum carbides
Abstract
The invention discloses a tungsten carbide powder production process, which relates to the technical field of tungsten carbide production, and comprises the following steps: heating the raw material containing tungsten oxide and organic resin to at least 600 ℃, then heating to the maximum temperature of 850 ℃ to perform a first gas-phase carburization reaction with reducing gas, and finally heating to 1200-1600 ℃ to perform a second gas-phase carburization reaction with carbon-containing gas. According to the production process of the tungsten carbide powder, the organic resin is mixed in the raw materials, and when the raw materials are heated, the organic resin starts to carbonize to provide a gaseous carbon source, and further has certain reducibility to react with tungsten in an oxygen-free environment to form the tungsten carbide powder. And when the carbon source is heated at a low temperature, the organic resin consumes the residual low-content oxygen to produce carbon monoxide, and the carbon monoxide also has reducibility in subsequent high-temperature reactions, so that the stability of a reducing atmosphere is ensured, and the carbon source is also ensured.
Description
Technical Field
The invention relates to the technical field of tungsten carbide production, in particular to a tungsten carbide powder production process.
Background
The tungsten carbide powder (WC) is a main raw material for producing hard alloy, is a black hexagonal crystal, has metallic luster, has hardness similar to that of diamond, and is a good conductor of electricity and heat. The material is widely used as a high-speed cutting lathe tool, a kiln structural material, a jet engine part, a metal ceramic material, a resistance heating element and the like.
The traditional process is to produce tungsten carbide from black tungsten concentrate or white tungsten concentrate, and usually many procedures such as ammonium paratungstate production, tungsten powder preparation and carbonization are required, so that the production cost is high, the process is long, and the traditional reduction sintering temperature is as high as 1800 ℃.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a production process of tungsten carbide powder.
The technical solution of the invention is as follows: a production process of tungsten carbide powder comprises the following steps:
heating the raw material containing tungsten oxide and organic resin to at least 600 ℃, then heating to the maximum temperature of 850 ℃ to perform a first gas-phase carburization reaction with reducing gas, and finally heating to 1200-1600 ℃ to perform a second gas-phase carburization reaction with carbon-containing gas.
In a preferred embodiment of the present invention, a grain inhibitor is added to the raw material in an amount of 1 to 5wt% based on the raw material.
In a preferred embodiment of the present invention, the grain inhibitor is a raw material containing at least B element.
In a preferred embodiment of the present invention, the organic resin is one or more of an acrylic resin, a phenolic resin, a rosin resin, and a polyamide resin.
As a preferable embodiment of the present invention, the organic resin accounts for 1 to 6wt% of the raw material.
As a preferable embodiment of the present invention, the reducing gas includes hydrogen.
As a preferred embodiment of the present invention, the carbon-containing gas includes hydrogen, carbon monoxide, and methane.
In a preferred embodiment of the present invention, the total volume of carbon monoxide and methane is 1-3% of the volume of the carbon-containing gas.
The invention has the beneficial effects that:
(1) According to the production process of the tungsten carbide powder, the organic resin is mixed in the raw materials, and when the raw materials are heated, the raw materials begin to carbonize to provide a gaseous carbon source, and further the gaseous carbon source has certain reducibility in an oxygen-free environment to react with tungsten to form the tungsten carbide powder. And when the carbon source is heated at a low temperature, the organic resin consumes the residual low-content oxygen to produce carbon monoxide, and the carbon monoxide also has reducibility in subsequent high-temperature reactions, so that the stability of a reducing atmosphere is ensured, and the carbon source is also ensured.
(2) According to the production process of the tungsten carbide powder, the B element in the grain inhibitor can enable the raw material to form a liquid state at a low temperature, so that the heating time is shortened, the growth of grains at a high temperature is reduced, and the grains are refined.
(3) According to the production process of the tungsten carbide powder, two times of gas phase carburization are adopted, so that the residue of free carbon is reduced, and the performance of the tungsten carbide powder is improved. The carbon source of the primary gas-phase carburizing reaction is organic resin, the carbon source of the secondary gas-phase carburizing reaction is carbon-containing gas, the primary reduction carburizing reaction of the traditional reaction is divided into two steps, the carbonization reaction rate is reduced, the cracking in the crystal grain forming process is reduced, and meanwhile, the reaction is more thorough.
Detailed Description
The invention is described in detail below with reference to examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and many insubstantial modifications and variations of the invention can be made by an engineer skilled in the art based on the teachings of the invention.
Example 1
A production process of tungsten carbide powder comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 600 deg.C in flowing nitrogen atmosphere, wherein flow rate of nitrogen is 30cm 3 And/s, heating to the maximum temperature of 850 ℃ to perform primary gas phase carburization reaction with reducing gas at the flow rate of 300cm 3 S, transThe reaction time is 4 hours, and finally the temperature is increased to 1200 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, wherein the flow velocity of the carbon-containing gas is 230cm 3 The reaction time is 2 h/s.
The raw materials are added with a grain inhibitor accounting for 1wt% of the raw materials.
The grain inhibitor is boron carbide.
The organic resin is acrylic resin.
The organic resin accounts for 1wt% of the raw materials.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide and methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1.
Example 2
A production process of tungsten carbide powder comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 650 deg.C under flowing nitrogen atmosphere, wherein flow rate of nitrogen is 35cm 3 And/s, heating to the maximum temperature of 850 ℃ to perform primary gas phase carburization reaction with reducing gas at the flow rate of 400cm 3 The reaction time is 3 hours, finally the temperature is increased to 1300 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, the flow velocity of the carbon-containing gas is 250cm 3 The reaction time is 2 h/s.
The raw materials are added with a grain inhibitor which accounts for 3wt% of the raw materials.
The grain inhibitor is boron carbide.
The organic resin is one or more of acrylic resin, phenolic resin, rosin resin and polyamide resin
The organic resin accounts for 3wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide and methane. The total volume of carbon monoxide and methane is 2% by volume of the carbon-containing gas.
Example 3
A production process of tungsten carbide powder comprises the following steps:
heating raw materials containing tungsten oxide and organic resin to 700 deg.C under flowing nitrogen atmosphere, wherein the flow rate of nitrogen is 30cm 3 And/s, heating to 850 deg.C, and performing a gas-phase carburization reaction with a reducing gas at a flow rate of 350cm 3 S, the reaction time is 2h, and finally the temperature is raised to 1500 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, the flow velocity of the carbon-containing gas is 280cm 3 The reaction time is 1h per second.
The raw materials are added with a grain inhibitor which accounts for 4wt% of the raw materials.
The grain inhibitor is boron carbide.
The organic resin is rosin resin.
The organic resin accounts for 5wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide and methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1.
Example 4
A production process of tungsten carbide powder comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 650 deg.C under flowing nitrogen atmosphere, wherein flow rate of nitrogen is 33cm 3 And/s, heating to the maximum temperature of 850 ℃ to perform primary gas phase carburization reaction with reducing gas at the flow rate of 350cm 3 The reaction time is 3 hours, and finally the temperature is raised to 1600 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, the flow rate of the carbon-containing gas is 230cm 3 The reaction time is 2 h/s.
The raw materials are added with a grain inhibitor accounting for 2wt% of the raw materials.
The grain inhibitor is boron carbide.
The organic resin is a mixture of acrylic resin, phenolic resin and rosin resin with the mass ratio of 1.
The organic resin accounts for 3wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide and methane. The total volume of the carbon monoxide and the methane accounts for 3% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1.
Example 5
A production process of tungsten carbide powder comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 670 deg.C in flowing nitrogen atmosphere, wherein flow rate of nitrogen is 35cm 3 And/s, heating to 850 deg.C, and performing a gas-phase carburization reaction with reducing gas at flow rate of 310cm 3 The reaction time is 4 hours, finally the temperature is increased to 1500 ℃, the secondary gas phase carburization reaction is carried out on the mixture and carbon-containing gas, the flow velocity of the carbon-containing gas is 230cm 3 The reaction time is 2 h/s.
The raw materials are added with a grain inhibitor accounting for 5wt% of the raw materials.
The grain inhibitor is boron carbide.
The organic resin is polyamide resin.
The organic resin accounts for 4wt% of the raw material.
The reducing gas comprises hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide and methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1.
COMPARATIVE EXAMPLE 1 (Primary reduction)
A production process of tungsten carbide powder comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 670 deg.C in flowing nitrogen atmosphere, wherein flow rate of nitrogen is 35cm 3 And/s, heating to 1800 deg.c, and gas phase carburizing with reducing gas in the flow rate of 360cm 3 The reaction time was 4 h/s.
The raw materials are added with a grain inhibitor accounting for 5wt% of the raw materials.
The grain inhibitor is boron carbide.
The organic resin is polyamide resin.
The organic resin accounts for 4wt% of the raw material.
The reducing gas is hydrogen.
Comparative example 2 (No inhibitor)
A production process of tungsten carbide powder comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 670 deg.C in flowing nitrogen atmosphere, wherein flow rate of nitrogen is 35cm 3 And/s, heating to the maximum temperature of 850 ℃ to perform a gas phase carburization reaction with a reducing gas at a flow rate of 310cm 3 The reaction time is 4 hours, finally the temperature is increased to 1500 ℃, the secondary gas phase carburization reaction is carried out on the mixture and carbon-containing gas, the flow velocity of the carbon-containing gas is 230cm 3 The reaction time is 2 h/s.
The organic resin is polyamide resin.
The organic resin accounts for 4wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide and methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1.
Comparative example 3 (carbon Black as carbon Source)
A production process of tungsten carbide powder comprises the following steps:
heating raw material containing tungsten oxide and carbon black to 670 deg.C under flowing nitrogen atmosphere, wherein flow rate of nitrogen is 35cm 3 And/s, heating to the maximum temperature of 850 ℃ to perform a gas phase carburization reaction with a reducing gas at a flow rate of 310cm 3 The reaction time is 4 hours, finally the temperature is increased to 1500 ℃, the secondary gas phase carburization reaction is carried out on the mixture and carbon-containing gas, the flow velocity of the carbon-containing gas is 230cm 3 The reaction time is 2 h/s.
The raw materials are added with a grain inhibitor accounting for 5wt% of the raw materials.
The grain inhibitor is boron carbide.
The carbon black accounted for 4wt% of the feedstock.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide and methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1.
The samples of the above examples and comparative examples were subjected to the following performance tests, and the test results are shown in Table 1.
(1) And (4) detecting free carbon by adopting an SK-S double-tube high-temperature carbon determinator.
(2) Oxygen content was measured using a TCH-600 Nitrogen-oxygen analyzer manufactured by LECO, USA.
TABLE 1 results of Performance test of examples and comparative examples
From the above table, it can be seen that the example forms outperform the comparative examples, for the following main reasons: the analysis of comparative example 1 shows that the use of two times of gas phase carburization in the examples reduces the free carbon residue, thereby improving the performance of the tungsten carbide powder. The carbon source of the primary gas-phase carburization reaction is organic resin, the carbon source of the secondary gas-phase carburization reaction is carbon-containing gas, the primary reduction carburization reaction of the traditional reaction is divided into two steps, the carbonization reaction rate is reduced, the cracking in the crystal grain forming process is reduced, meanwhile, the reaction is more thorough, the purity of tungsten carbide is higher, the oxygen content is very low, and the reduction atmosphere is very excellent. The analysis of the comparative example 2 shows that the B element in the grain inhibitor can enable the raw material to form a liquid state at low temperature, thereby reducing the heating time and reducing the growth of grains at high temperature, so that the grains are refined and the reaction process is accelerated. The analysis of comparative example 3 shows that the performance of using organic carbon as a carbon source can be achieved and possibly superior to the performance of using carbon black as a carbon source, and thus, a new scheme using an organic carbon source as a carbon source can be used.
The above additional technical features can be freely combined and used in superposition by those skilled in the art without conflict.
The above description is only a preferred embodiment of the present invention, and the technical solutions that achieve the objects of the present invention by substantially the same means are within the protection scope of the present invention.
Claims (8)
1. A production process of tungsten carbide powder is characterized by comprising the following steps:
heating the raw material containing tungsten oxide and organic resin to at least 600 ℃, then heating to the maximum temperature of 850 ℃ to perform primary gas phase carburization reaction with reducing gas, and finally heating to 1200-1600 ℃ to perform secondary gas phase carburization reaction with carbon-containing gas.
2. The process for producing tungsten carbide powder according to claim 1, wherein a grain inhibitor is added to the raw material in an amount of 1 to 5wt% based on the raw material.
3. The process for producing tungsten carbide powder according to claim 2, wherein the grain inhibitor is a raw material containing at least B element.
4. The process for producing tungsten carbide powder according to claim 1, wherein the organic resin is one or more of acrylic resin, phenol resin, rosin resin, and polyamide resin.
5. The process for producing tungsten carbide powder according to claim 1, wherein the organic resin is 1 to 6wt% of the raw material.
6. The process for producing tungsten carbide powder according to claim 1, wherein the reducing gas comprises hydrogen.
7. The process for producing tungsten carbide powder according to claim 1, wherein the carbon-containing gas includes hydrogen, carbon monoxide and methane.
8. The process for producing tungsten carbide powder according to claim 7, wherein the total volume of carbon monoxide and methane is 1 to 3% by volume of the carbon-containing gas.
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|---|---|---|---|---|
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| CN108892141A (en) * | 2018-09-06 | 2018-11-27 | 北京科技大学 | A kind of high-purity, ultrafine tungsten carbide preparation method |
-
2022
- 2022-07-15 CN CN202210837446.4A patent/CN115285995B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5372797A (en) * | 1991-11-20 | 1994-12-13 | The Dow Chemical Company | Low temperature method for synthesizing micrograin tungsten carbide |
| CN1247520A (en) * | 1997-03-31 | 2000-03-15 | Omg美国公司 | Method to produce transition metal carbide from partially reduced transition metal compound |
| CN1326424A (en) * | 1998-11-13 | 2001-12-12 | H·C·施塔克公司 | Method for producing wolfram carbides by gas-phase carburetion |
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| CN108892141A (en) * | 2018-09-06 | 2018-11-27 | 北京科技大学 | A kind of high-purity, ultrafine tungsten carbide preparation method |
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