CN105537606A - Preparation method of ultra-fine tungsten carbide powder - Google Patents
Preparation method of ultra-fine tungsten carbide powder Download PDFInfo
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- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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Abstract
The invention discloses a preparation method of ultra-fine tungsten carbide powder and belongs to the technical field of powder metallurgy. The preparation method of the ultra-fine tungsten carbide powder comprises the technological steps that 100 mass parts of tungsten hexacarbonyl W(CO)6 and 3-5 mass parts of dicobalt octacarbonyl Co2(CO)8 are dissolved in diethyl ether in a three-opening bottle and stirred to be completely dissolved, and the diethyl ether is evaporated through vacuum distillation, so that a solid uniform mixture of the ungsten hexacarbonyl W(CO)6 and the dicobalt octacarbonyl Co2(CO)8 is obtained; the three-opening bottle is heated to the temperature of 50-90 DEG C, carrier gas is introduced to carry the gasified W(CO)6 mixture into a pyrolyzing furnace, methane gas preheated to the temperature of 300-450 DEG C is introduced into the pyrolyzing furnace at the same time, the temperature of the pyrolyzing furnace is kept being 300-450 DEG C, and the reaction time is 30-120 minutes; and the ultra-fine tungsten carbide powder which contains 1.0%-6.5% of cobalt by mass is finally obtained, and the granularity D50 of the powder is 50-600 nm. By the adoption of the method, the granularity of the tungsten carbide powder can be controlled; in addition, due to the fact that the tungsten carbide powder is doped with certain cobalt, abnormal growth of the tungsten carbide powder during high-temperature sintering can be restrained, and the excellent performance of the tungsten carbide powder is kept.
Description
Technical field
The invention belongs to powder metallurgical technology, particularly relate to a kind of preparation method of superfine tungsten carbide powder, prepared the superfine tungsten carbide powder of containing metal cobalt by carbonyl metal gas-phase deposition technique.
Background technology
Tungsten carbide (WC) is a kind of compound be made up of tungsten and carbon, for black hexagonal, there is metallic luster, for electricity, hot good conductor, there is very high hardness (hardness is close with diamond), good corrosion resistance and compression strength, there is the title of modern industry tooth, in the carbide alloy of more than 98%, all contain WC.In order to improve the mechanical property of WC carbide alloy further, best approach is by its grain size refinement, the grain size of alloy is thinner, its defect is less, when crystal grain is less than 0.1 μm, almost there is no defect, this carbide alloy had both had high hardness and wearability, there is again high intensity and toughness, current people pass through just tungsten carbide and composite powder crystallite dimension thereof and are reduced in nanometer range, to improve its hardness, toughness (the preparation of nanocrystalline WC hard alloys, structure and mechanical property [J], Tan Guolong, Wu Xijun etc., Materials Science and Engineering, 1998, 16 (1): 8).
Usually preparing tungsten-carbide powder is at high temperature reacted by tungsten powder or oxidation tungsten powder (being produced by wolframic acid or ammonium tungstate preparation) produce with carbon source (carbon black, graphite, carbon dioxide, organic high-carbon gas etc.), and powder size is usually at 1-10 μm.High-energy ball milling (interpolation grain inhibitor), programmed temperature method (TPR), precursor process etc. are generally then taked in the preparation of superfine tungsten carbide powder, the current preparation method of such tungsten-carbide powder is based on research, and the method realizing suitability for industrialized production is also rare.Because superfine tungsten carbide powder often uses high-sintering process in application process, cause the abnormal growth of crystal grain, make it lose original performance of Ultra-fine Grained, seriously constrain the performance application of Hardmetal materials.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of superfine tungsten carbide powder, prepared the superfine tungsten carbide powder of containing metal cobalt by gas-phase process, wherein to contain cobalt octacarbonyl Co
2(CO)
8tungsten carbonyl W (CO)
6for tungsten source, methane is carbon source.Superfine tungsten carbide powder is widely used in aspects such as producing carbide alloy, composite, special tool(s) material.
The concrete technology step of the preparation method of a kind of superfine tungsten carbide powder of the present invention is as follows:
Step 1: by 100 mass parts tungsten carbonyl W (CO)
6with the cobalt octacarbonyl Co of 3-5 mass parts
2(CO)
8in there-necked flask, be dissolved in ether, stir and make it dissolve completely, and remove by decompression distillation steaming the solid homogeneous mixture that ether obtains the two.
Step 2: heating there-necked flask to 50-90 DEG C, and passes into carrier gas by the W (CO) of gasification
6mixture is loaded in pyrolysis oven, the methane gas being preheated to 300-450 DEG C is also passed into pyrolysis oven simultaneously, keeps pyrolysis oven temperature 300-450 DEG C, reaction time 30-120min.So obtain the superfine tungsten carbide powder of containing metal cobalt, powder size D50 is 50-600nm.
Carrier gas in above-mentioned processing step is nitrogen or argon gas, and flow is 5-20ml/min.
Methane gas flow in above-mentioned processing step is 5-10ml/min.
As preferably, in above-mentioned processing step, the temperature of pyrolysis oven and the temperature of methane preheating all remain on 350-420 DEG C.
By above process, superfine tungsten carbide powder containing metal cobalt 1.0-6.5% (mass percent) prepared, tungsten-carbide powder granularity D50 is 50-600nm.
This process not only can control the granularity of tungsten-carbide powder, and due to containing the doping of certain metallic cobalt, can suppress the abnormal growth of crystal grain in superfine tungsten carbide powder high-temperature sintering process, keep the superhard ultra-tough energy that it is good.
Detailed description of the invention
Embodiment 1:
Get 10g tungsten carbonyl W (CO)
6with the cobalt octacarbonyl Co of 0.3g
2(CO)
8in there-necked flask, be dissolved in ether, stir and make it dissolve completely, and remove by decompression distillation steaming the solid homogeneous mixture that ether obtains the two.Then heat there-necked flask to 90 DEG C, nitrogen buffer gas, keep flow 15ml/min, by the W (CO) of gasification
6mixture is loaded in pyrolysis oven, simultaneously by being preheated to 300 DEG C, flow is that the methane gas of 5ml/min passes into pyrolysis oven, keeps pyrolysis oven temperature 300 DEG C, reaction 60min.Obtain the superfine tungsten carbide powder 2.2g of containing metal cobalt, powder size D50 is about 200nm, metallic cobalt content 2.1%.Embodiment 2:
Get 10g tungsten carbonyl W (CO)
6with the cobalt octacarbonyl Co of 0.5g
2(CO)
8in there-necked flask, be dissolved in ether, stir and make it dissolve completely, and remove by decompression distillation steaming the solid homogeneous mixture that ether obtains the two.Then heating there-necked flask to 50 DEG C, take argon gas as carrier gas, keeps flow 5ml/min, by the W (CO) of gasification
6mixture is loaded in pyrolysis oven, simultaneously by being preheated to 420 DEG C, flow is that the methane gas of 10ml/min passes into pyrolysis oven, keeps pyrolysis oven temperature 420 DEG C, reaction 120min.Obtain the superfine tungsten carbide powder 2.4g of containing metal cobalt, powder size D50 is about 550nm, metallic cobalt content 6.0%.Embodiment 3:
Get 10g tungsten carbonyl W (CO)
6with the cobalt octacarbonyl Co of 0.4g
2(CO)
8in there-necked flask, be dissolved in ether, stir and make it dissolve completely, and remove by decompression distillation steaming the solid homogeneous mixture that ether obtains the two.Then heating there-necked flask to 70 DEG C, take argon gas as carrier gas, keeps flow 10ml/min, by the W (CO) of gasification
6mixture is loaded in pyrolysis oven, simultaneously by being preheated to 380 DEG C, flow is that the methane gas of 10ml/min passes into pyrolysis oven, keeps pyrolysis oven temperature 380 DEG C, reaction 90min.Obtain the superfine tungsten carbide powder 2.5g of containing metal cobalt, powder size D50 is 80nm, metallic cobalt content 4.2%.
Claims (4)
1. a preparation method for superfine tungsten carbide powder, is characterized in that, processing step is as follows:
Step 1: by 100 mass parts tungsten carbonyl W (CO)
6with the cobalt octacarbonyl Co of 3-5 mass parts
2(CO)
8in there-necked flask, be dissolved in ether, stir and make it dissolve completely, and remove by decompression distillation steaming the solid homogeneous mixture that ether obtains the two;
Step 2: heating there-necked flask to 50-90 DEG C, and passes into carrier gas by the W (CO) of gasification
6mixture is loaded in pyrolysis oven, the methane gas being preheated to 300-450 DEG C is also passed into pyrolysis oven simultaneously, keeps pyrolysis oven temperature 300-450 DEG C, reaction time 30-120min; Finally obtain the superfine tungsten carbide powder of containing metal cobalt 1.0-6.5 quality % hundred, tungsten-carbide powder granularity D50 is 50-600nm.
2. superfine tungsten carbide powder preparation method according to claim 1, is characterized in that, carrier gas is nitrogen or argon gas, and flow is 5-20ml/min.
3. superfine tungsten carbide powder preparation method according to claim 1, is characterized in that, methane gas flow is 5-10ml/min.
4. superfine tungsten carbide powder preparation method according to claim 1, is characterized in that, the temperature of pyrolysis oven and the temperature of methane preheating all remain on 350-420 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352534A (en) * | 2017-06-28 | 2017-11-17 | 中国航发北京航空材料研究院 | The graphene oxide that a kind of nanometer tungsten carbide is modified |
| CN107915229A (en) * | 2017-11-14 | 2018-04-17 | 湖南大学 | A kind of 1-dimention nano carbonization tungsten and its preparation method and application |
| CN109867286A (en) * | 2019-04-15 | 2019-06-11 | 北京科技大学 | A kind of preparation method of ultrafine tungsten carbide |
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| CN1212191A (en) * | 1997-09-23 | 1999-03-31 | 上海华明高技术（集团）有限公司 | Method for manufacturing WC/CO composite nanometre powder |
| CN1590573A (en) * | 2003-08-25 | 2005-03-09 | 金益民 | Production technology of nano-grade tungsten cobalt mixed powder |
| CN101151114A (en) * | 2006-03-17 | 2008-03-26 | 纳诺泰克有限公司 | Manufacturing method for ultra fine composite powder of tungsten carbide and cobalt |
| KR20090123252A (en) * | 2008-05-27 | 2009-12-02 | 충남대학교산학협력단 | Fabrication method of ultra fine tungsten powders by self-propagating high-temperature synthesis induced molten salts |
| CN102078965A (en) * | 2010-12-10 | 2011-06-01 | 中国科学院上海硅酸盐研究所 | Method for preparing WC-Co (tungsten carbide-cobalt) nano-powder |
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2015
- 2015-12-30 CN CN201511022251.0A patent/CN105537606A/en active Pending
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| CN1212191A (en) * | 1997-09-23 | 1999-03-31 | 上海华明高技术（集团）有限公司 | Method for manufacturing WC/CO composite nanometre powder |
| CN1590573A (en) * | 2003-08-25 | 2005-03-09 | 金益民 | Production technology of nano-grade tungsten cobalt mixed powder |
| CN101151114A (en) * | 2006-03-17 | 2008-03-26 | 纳诺泰克有限公司 | Manufacturing method for ultra fine composite powder of tungsten carbide and cobalt |
| KR20090123252A (en) * | 2008-05-27 | 2009-12-02 | 충남대학교산학협력단 | Fabrication method of ultra fine tungsten powders by self-propagating high-temperature synthesis induced molten salts |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352534A (en) * | 2017-06-28 | 2017-11-17 | 中国航发北京航空材料研究院 | The graphene oxide that a kind of nanometer tungsten carbide is modified |
| CN107915229A (en) * | 2017-11-14 | 2018-04-17 | 湖南大学 | A kind of 1-dimention nano carbonization tungsten and its preparation method and application |
| CN109867286A (en) * | 2019-04-15 | 2019-06-11 | 北京科技大学 | A kind of preparation method of ultrafine tungsten carbide |
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