CN111154993A - Preparation method of tungsten carbide-titanium carbide solid solution - Google Patents
Preparation method of tungsten carbide-titanium carbide solid solution Download PDFInfo
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- CN111154993A CN111154993A CN201911361031.9A CN201911361031A CN111154993A CN 111154993 A CN111154993 A CN 111154993A CN 201911361031 A CN201911361031 A CN 201911361031A CN 111154993 A CN111154993 A CN 111154993A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
- C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
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Abstract
The invention provides a preparation method of a tungsten carbide-titanium carbide solid solution. The method comprises the following steps: (1) adding TiO into the mixture2Mixing the powder, WC powder, nano tungsten powder and carbon black, and performing jet milling to prepare superfine mixed powder; (2) putting the superfine mixed powder obtained in the step (1) into a mixer, fully and uniformly stirring, putting into a graphite boat, introducing nitrogen into a carbon tube in the graphite boat, and heating and sintering to obtain a sintered product; (3) and (3) carrying out airflow crushing on the sintered product obtained in the step (2), and sieving to obtain the tungsten carbide-titanium carbide solid solution. The invention can prepare tungsten carbide-titanium carbide solid solution with low oxygen and nitrogen contents, and the average grain diameter of the solid solution is below 1.0 mu m.
Description
Technical Field
The invention belongs to the field of solid solution preparation, and particularly provides a preparation method of a tungsten carbide-titanium carbide solid solution.
Background
The tungsten carbide-titanium carbide solid solution belongs to (Ti, W) C compound carbide, has high melting point, high hardness, high wear resistance, excellent anti-bonding, anti-oxidation and wear resistance, and is widely applied to hard alloy products for machining. It has been found that when a mixture of carbides is added, it is generally added to cemented carbides in the form of a solid solution of carbides during the production of cemented carbides, because solid solution reactions occur during the sintering of the alloy, making control of the amount of carbon difficult. Researches show that raw materials used for preparing the solid solution, the adopted carbonization process and the like have obvious influence on the components, granularity, structure and performance of the (Ti, W) C solid solution and the alloy performance, and the alloy prepared from the (Ti, W) C with fine grains, large sub-crystal size and small microscopic strain has better performance. However, in the prior art, the ball mill is mostly used for ball milling the mixed raw materials, but the ball milling efficiency is low, the oxygen and nitrogen content of the product is high, the granularity is large, and the service performance of the product is influenced.
Disclosure of Invention
The invention provides a preparation method of a tungsten carbide-titanium carbide solid solution, which comprises the following steps:
(1) adding TiO into the mixture2Mixing the powder, WC powder, nano tungsten powder and carbon black, and performing jet milling to prepare superfine mixed powder;
(2) putting the superfine mixed powder obtained in the step (1) into a mixer, fully and uniformly stirring, putting into a graphite boat, introducing nitrogen into a carbon tube in the graphite boat, and heating and sintering to obtain a sintered product;
(3) and (3) carrying out airflow crushing on the sintered product obtained in the step (2), and sieving to obtain the tungsten carbide-titanium carbide solid solution.
According to the method of the present invention, in the step (1), the nano tungsten powder has an average particle diameter of 1 to 300nm, for example, 5 to 200 nm.
According to the method of the present invention, in the step (1) and the step (3), the carrier gas medium for jet milling is nitrogen. Preferably, the jet milling adopts multi-stage jet milling, for example, two-stage counter-jet milling, and preferably the jet milling has an air flow speed of 500-600 m/s.
According to the method of the present invention, in the step (1) and the step (3), the average particle diameter of the ultrafine mixed powder is 10 to 500nm, for example, 50 to 300 nm.
According to the process of the invention, in step (1), the TiO2The mass ratio of the powder, the WC powder, the nano tungsten powder and the carbon black is (10-35) to (10-15) to (7-15) to (1.5-3), such as (15-30) to (10-15) to (8-12) to 2.
According to the method of the invention, in the step (2), the flow rate of the nitrogen is 0.1-0.15m3/h。
According to the method of the invention, in the step (2), the heating sintering adopts temperature programming: raising the temperature from room temperature to 1000 ℃ within 40-50min, and keeping the temperature for 10-15 min; then the temperature is raised to 1800 plus 1860 ℃ within 15-20min, and the temperature is preserved for 50-60 min.
According to the method of the present invention, in the step (2), the sieving is 5000 mesh sieving.
The invention has the beneficial effects that:
the invention utilizes the high activity of the nano-grade tungsten powder, adopts a nitrogen gas jet milling method to prepare the raw material mixture of the superfine powder, so that the carbonization and solid solution reaction can be carried out more rapidly, the reaction temperature of the invention can be controlled at about 1800 ℃, the reaction temperature is greatly reduced, the energy is saved, and the tungsten carbide-titanium carbide solid solution with low oxygen and nitrogen contents can be produced through one-time reaction, thereby improving the production efficiency. The average particle size of the final product is below 1.0 μm, which is finer and more uniform than that produced by the traditional method, and the particle size distribution is better.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The preparation method of the tungsten carbide-titanium carbide solid solution comprises the following steps:
(1) adding TiO into the mixture2Mixing the powder, WC powder, nano tungsten powder (with average particle size of 20-40nm) and carbon black, and performing jet milling to obtain superfine mixed powder, wherein the average particle size of the superfine mixed powder is 30-100 nm;
TiO2the mass ratio of the powder, the WC powder, the nano tungsten powder and the carbon black is 30: 12: 11: 2;
(2) putting the superfine mixed powder obtained in the step (1) into a mixer, fully stirring the superfine mixed powder uniformly, putting the mixture into a graphite boat, and introducing nitrogen (the flow of the nitrogen is 0.15 m) into the carbon tubes in the graphite boat3And h), heating and sintering, wherein the heating and sintering adopts temperature programming: increasing the temperature from room temperature to 10 in 45minKeeping the temperature at 00 ℃ for 10 min; then heating to 1820 ℃ within 20min, and keeping the temperature for 60min to obtain a sintered product;
(3) and (3) performing jet milling on the sintered product obtained in the step (2), and sieving with a 5000-mesh sieve to obtain the tungsten carbide-titanium carbide solid solution.
The jet milling in the step (1) and the step (3) is two-stage jet milling, the carrier gas is nitrogen, the air flow speed is 550m/s, the raw material mixture passes through a charging hopper, enters a spray gun of a coarse milling bin through a feeding pipeline, is sprayed by high-speed air flow of the spray gun to carry out collision milling in the coarse milling bin, and is repeatedly and circularly collided through a circulating pipeline; when the particle size reaches about 1 μm, the particles enter the spray gun of the fine crushing bin through the discharge port, are sprayed by high-speed airflow of the spray gun to collide and crush again in the fine crushing bin, and are repeatedly and circularly collided through a circulating pipeline.
The tungsten carbide-titanium carbide solid solution obtained in this example had an average particle size of 1 μm, an oxygen element content of 0.10% by mass, and a nitrogen element content of 0.04% by mass.
Example 2
The preparation method of the tungsten carbide-titanium carbide solid solution comprises the following steps:
(1) adding TiO into the mixture2Mixing the powder, WC powder, nano tungsten powder (with the average particle size of 20-40nm) and carbon black, and performing jet milling to prepare superfine mixed powder, wherein the average particle size of the superfine mixed powder is 80-200 nm;
TiO2the mass ratio of the powder, the WC powder, the nano tungsten powder and the carbon black is 26: 13: 15: 2;
(2) putting the superfine mixed powder obtained in the step (1) into a mixer, fully stirring the superfine mixed powder evenly, putting the mixture into a graphite boat, and introducing nitrogen (the flow of the nitrogen is 0.1 m) into the carbon tubes in the graphite boat3And h), heating and sintering, wherein the heating and sintering adopts temperature programming: raising the temperature from room temperature to 1000 ℃ within 50min, and keeping the temperature for 15 min; then heating to 1850 ℃ within 15min, and preserving the heat for 60min to obtain a sintered product;
(3) and (3) performing jet milling on the sintered product obtained in the step (2), and sieving with a 5000-mesh sieve to obtain the tungsten carbide-titanium carbide solid solution.
The jet milling in the step (1) and the step (3) is two-stage jet milling, the carrier gas is nitrogen, the air flow speed is 600m/s, the raw material mixture passes through a charging hopper, enters a spray gun of a coarse milling bin through a feeding pipeline, is sprayed by high-speed air flow of the spray gun to carry out collision milling in the coarse milling bin, and is repeatedly and circularly collided through a circulating pipeline; when the particle size reaches about 1 μm, the particles enter the spray gun of the fine crushing bin through the discharge port, are sprayed by high-speed airflow of the spray gun to collide and crush again in the fine crushing bin, and are repeatedly and circularly collided through a circulating pipeline.
The tungsten carbide-titanium carbide solid solution obtained in this example had an average particle size of 900nm, an oxygen element content of 0.09% by mass, and a nitrogen element content of 0.042% by mass.
Example 3
The preparation method of the tungsten carbide-titanium carbide solid solution comprises the following steps:
(1) adding TiO into the mixture2Mixing the powder, WC powder, nano tungsten powder (with average particle size of 30-50nm) and carbon black, and performing jet milling with nitrogen as carrier gas and 550m/s of jet velocity to obtain superfine mixed powder with average particle size of 60-160 nm;
TiO2the mass ratio of the powder, the WC powder, the nano tungsten powder and the carbon black is 23: 11: 9: 1.7;
(2) putting the superfine mixed powder obtained in the step (1) into a mixer, fully stirring the mixture evenly, putting the mixture into a graphite boat, and introducing nitrogen (the flow of the nitrogen is 0.10 m) into the carbon tubes in the graphite boat3And h), heating and sintering, wherein the heating and sintering adopts temperature programming: heating from room temperature to 1000 deg.C within 45min, and maintaining for 15 min; then heating to 1860 ℃ within 20min, and preserving heat for 60min to obtain a sintered product;
(3) and (3) performing jet milling on the sintered product obtained in the step (2), and sieving with a 5000-mesh sieve to obtain the tungsten carbide-titanium carbide solid solution.
The jet milling in the step (1) and the step (3) is two-stage jet milling, the carrier gas is nitrogen, the air flow speed is 500m/s, the raw material mixture passes through a charging hopper, enters a spray gun of a coarse milling bin through a feeding pipeline, is sprayed by high-speed air flow of the spray gun to carry out collision milling in the coarse milling bin, and is repeatedly and circularly collided through a circulating pipeline; when the particle size reaches about 1 μm, the particles enter the spray gun of the fine crushing bin through the discharge port, are sprayed by high-speed airflow of the spray gun to collide and crush again in the fine crushing bin, and are repeatedly and circularly collided through a circulating pipeline.
The tungsten carbide-titanium carbide solid solution obtained in this example had an average particle size of 880nm, an oxygen element content of 0.088% by mass, and a nitrogen element content of 0.037% by mass.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of tungsten carbide-titanium carbide solid solution is characterized by comprising the following steps:
(1) adding TiO into the mixture2Mixing the powder, WC powder, nano tungsten powder and carbon black, and performing jet milling to prepare superfine mixed powder;
(2) putting the superfine mixed powder obtained in the step (1) into a mixer, fully and uniformly stirring, putting into a graphite boat, introducing nitrogen into a carbon tube in the graphite boat, and heating and sintering to obtain a sintered product;
(3) and (3) carrying out airflow crushing on the sintered product obtained in the step (2), and sieving to obtain the tungsten carbide-titanium carbide solid solution.
2. The preparation method according to claim 1, wherein in the step (1), the average particle diameter of the nano tungsten powder is 1 to 300 nm.
3. The production method according to claim 1, wherein in the step (1) and the step (3), the carrier gas medium for jet milling is nitrogen gas.
4. The method as claimed in claim 1, wherein the jet milling is performed in multiple stages, and the jet milling has an air velocity of 500-600 m/s.
5. The method of claim 4, wherein two-stage counter-jet air-jet milling is employed.
6. The method according to claim 1, wherein in the steps (1) and (3), the average particle diameter of the ultrafine mixed powder is 10 to 500 nm.
7. According to the process of the invention, in step (1), the TiO2The mass ratio of the powder, the WC powder, the nano tungsten powder and the carbon black is (10-35): (10-15): 7-15): 1.5-3.
8. The production method according to claim 1, wherein in the step (2), the flow rate of the nitrogen gas is 0.1 to 0.15m3/h。
9. The production method according to claim 1, wherein in the step (2), the heating sintering employs a temperature programming: raising the temperature from room temperature to 1000 ℃ within 40-50min, and keeping the temperature for 10-15 min; then the temperature is raised to 1800 plus 1860 ℃ within 15-20min, and the temperature is preserved for 50-60 min.
10. The method according to claim 1, wherein in the step (2), the sieving is 5000 mesh sieving.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114132927A (en) * | 2021-11-15 | 2022-03-04 | 赣州海盛钨钼集团有限公司 | Preparation system of tungsten carbide powder |
| CN114853487A (en) * | 2022-05-06 | 2022-08-05 | 苏州诺瑞达新材料科技有限公司 | Mullite castable based on titanium carbide and tungsten carbide composite |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174247A (en) * | 1997-06-14 | 1998-02-25 | 邓勇 | Tungsten carbide based hard alloy powder for spray welding (painting) and its production process |
| CN1196032A (en) * | 1995-09-12 | 1998-10-14 | 陶氏化学公司 | Method to produce transition metal carbide from partially reduced transition metal compound |
| CN1739894A (en) * | 2005-09-15 | 2006-03-01 | 自贡硬质合金有限责任公司 | Airflow crushing stepped tungsten carbide powder producing process |
| JP2008212904A (en) * | 2007-03-08 | 2008-09-18 | Kyoorin Food Kogyo Kk | Jet mill |
| CN102234729A (en) * | 2010-04-23 | 2011-11-09 | 河南省大地合金股份有限公司 | Preparation method for hard metal |
| CN102482739A (en) * | 2009-08-20 | 2012-05-30 | 住友电气工业株式会社 | Super hard alloy and cutting tool using same |
| JP2012117101A (en) * | 2010-11-30 | 2012-06-21 | Sumitomo Electric Ind Ltd | Method for manufacturing cemented carbide |
| CN102534277A (en) * | 2010-12-07 | 2012-07-04 | 北京有色金属研究总院 | New preparation method for coarse particles and super coarse particle hard alloy |
| CN103408015A (en) * | 2013-09-02 | 2013-11-27 | 株洲硬质合金集团有限公司 | Preparation method of ultrafine tungsten carbide powder |
| CN103484703A (en) * | 2013-10-15 | 2014-01-01 | 株洲硬质合金集团有限公司 | Preparation method of tungsten carbide-titanium carbide solid solution |
| CN105855556A (en) * | 2016-04-01 | 2016-08-17 | 厦门钨业股份有限公司 | Airflow mill pulverizer and airflow pulverization method |
| CN107475548A (en) * | 2017-06-28 | 2017-12-15 | 沈阳寰博磁电科技有限公司 | A kind of preparation method of nanometer of toughness reinforcing Ultra-fine Grained WC Co hard alloy |
-
2019
- 2019-12-25 CN CN201911361031.9A patent/CN111154993A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196032A (en) * | 1995-09-12 | 1998-10-14 | 陶氏化学公司 | Method to produce transition metal carbide from partially reduced transition metal compound |
| CN1174247A (en) * | 1997-06-14 | 1998-02-25 | 邓勇 | Tungsten carbide based hard alloy powder for spray welding (painting) and its production process |
| CN1739894A (en) * | 2005-09-15 | 2006-03-01 | 自贡硬质合金有限责任公司 | Airflow crushing stepped tungsten carbide powder producing process |
| JP2008212904A (en) * | 2007-03-08 | 2008-09-18 | Kyoorin Food Kogyo Kk | Jet mill |
| CN102482739A (en) * | 2009-08-20 | 2012-05-30 | 住友电气工业株式会社 | Super hard alloy and cutting tool using same |
| CN102234729A (en) * | 2010-04-23 | 2011-11-09 | 河南省大地合金股份有限公司 | Preparation method for hard metal |
| JP2012117101A (en) * | 2010-11-30 | 2012-06-21 | Sumitomo Electric Ind Ltd | Method for manufacturing cemented carbide |
| CN102534277A (en) * | 2010-12-07 | 2012-07-04 | 北京有色金属研究总院 | New preparation method for coarse particles and super coarse particle hard alloy |
| CN103408015A (en) * | 2013-09-02 | 2013-11-27 | 株洲硬质合金集团有限公司 | Preparation method of ultrafine tungsten carbide powder |
| CN103484703A (en) * | 2013-10-15 | 2014-01-01 | 株洲硬质合金集团有限公司 | Preparation method of tungsten carbide-titanium carbide solid solution |
| CN105855556A (en) * | 2016-04-01 | 2016-08-17 | 厦门钨业股份有限公司 | Airflow mill pulverizer and airflow pulverization method |
| CN107475548A (en) * | 2017-06-28 | 2017-12-15 | 沈阳寰博磁电科技有限公司 | A kind of preparation method of nanometer of toughness reinforcing Ultra-fine Grained WC Co hard alloy |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114132927A (en) * | 2021-11-15 | 2022-03-04 | 赣州海盛钨钼集团有限公司 | Preparation system of tungsten carbide powder |
| CN114132927B (en) * | 2021-11-15 | 2023-02-17 | 赣州海盛钨钼集团有限公司 | Preparation system of tungsten carbide powder |
| CN114853487A (en) * | 2022-05-06 | 2022-08-05 | 苏州诺瑞达新材料科技有限公司 | Mullite castable based on titanium carbide and tungsten carbide composite |
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Application publication date: 20200515 |