CN103183347A - Preparation method of crude tungsten carbide powder - Google Patents
Preparation method of crude tungsten carbide powder Download PDFInfo
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- CN103183347A CN103183347A CN2011104520961A CN201110452096A CN103183347A CN 103183347 A CN103183347 A CN 103183347A CN 2011104520961 A CN2011104520961 A CN 2011104520961A CN 201110452096 A CN201110452096 A CN 201110452096A CN 103183347 A CN103183347 A CN 103183347A
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Abstract
The invention relates to a preparation method of crude tungsten carbide powder, which comprises the following steps: (1) blending tungsten oxide powder and carbon black powder according to theoretic amounts for reaction, well mixing in a ball milling cylinder to obtain mixed powder; (2) weighing and loading the mixed powder into a boat of a high temperature carbide furnace, turning on a vacuum pump, introducing Ar and hydrogen under a vacuum negative pressure condition, stepwise increasing the temperature of the carbide furnace to 900-2650 DEG C, performing heat insulation, pushing in an empty material boat, pushing in the boat with the materials after seven empty material boat are pushed in, performing reduction and carbonization with reduction time of 1-3 hours and carbonization time of 15-20 hours, then pushing the materials into a cooling zone for cooling to obtain a tungsten carbide block; (3) breaking the tungsten carbide block, adding into a crushing ball milling cylinder for crushing to obtain the crude tungsten carbide powder. The crude WC particles prepared in the invention have a size of 20-100 microns, and have quite uniform particle sizes and few defects of the tungsten carbide powder.
Description
Technical field
The present invention relates to a kind of preparation method of thick tungsten carbide powder, particularly a kind of granularity is the preparation method of the tungsten carbide powder of 20～100 μ m, belongs to the metallurgy of rare metal field.
Background technology
The Wimet terminal use mainly is cutting tool and mining instrument, and mining instrument ratio has accounted for 25% of Wimet application respectively.Mining instrument aspect, Wimet plays a significant role at aspects such as mineral products, oil production, infrastructure constructions mainly as drilling tool, digging instrument, boring tool.Macrocrystalline tungsten carbide is used for mining instrument is improved the performance of cutter significantly, and the research of therefore carrying out the macrocrystalline tungsten carbide technology of preparing has become the research focus in Wimet field.The grain-size of WC has determined the performance of Wimet basically.Both at home and abroad Study of Cemented Carbide is mainly developed towards nanocrystalline and super coarse-grain both direction, and the Wimet grain size depends primarily on the grain fineness number of WC.The coarse grain wolfram varbide is because its crystal property is good, textural defect is few, the subgrain size is thick, microhardness is high, microdeformation is little, have certain series of advantages such as plasticity, for the production of Wimet, can significantly improve the anti-fracture toughness property of coarse-grain Wimet, improve work-ing life and be able to widespread use.
Preparing the comparatively traditional method of macrocrystalline tungsten carbide powder both at home and abroad is Tungsten oxide 99.999 high temperature reduction high temperature cabonization method, namely adopt Tungsten oxide 99.999 to produce varigrained tungsten powder through high temperature reduction, mix with solid carbon with tungsten powder again, through high temperature cabonization, produce wolfram varbide, this method for preparing wolfram varbide is the most extensive.This is a traditional classical way, still occupies dominant position at present at home.
But the super thick wolfram varbide of traditional method preparation exist crystal grain inadequately thick, granularity is inhomogeneous, fine particle is more, can occur problem such as particle bond in the high temperature cabonization process.Except traditional method, also have thermite process and alkali metal compound doped tungsten oxide high temperature reduction high temperature cabonization method.The size ratio of the coarse grain wolfram varbide of thermite process preparation is thicker, is that operation is longer but there is main drawback, and impurities is on the high side, and some impurity can't be removed fully and finally influence the over-all properties of alloy.Alkali metal compound doped tungsten oxide high temperature reduction high temperature cabonization legal system is equipped with the coarse grain tungsten-carbide powder and has following shortcoming: 1) coarse grain tungsten powder defective is many, and crystallization is bad, and distortion crystal grain is many; 2) be trapped in the carbonization process on the contrary can crystal grain thinning for basic metal, easily causes foreign matter content higher; 3) bad, the lack of homogeneity of grain morphology.
Summary of the invention
The object of the present invention is to provide a kind of new method prepared sizes is 20～100 μ m high purity carbonization tungsten powders, overcomes problems of the prior art.
The method that the present invention adopts high temperature reduction and high temperature cabonization to carry out continuously with stove prepares super thick tungsten carbide powder.
The preparation method of thick tungsten carbide powder of the present invention comprises the steps:
(1) Tungsten oxide 99.999 powder and carbon black powders are carried out proportioning according to the theoretical amount that generates the wolfram varbide reaction, mix in the threading ball milling cylindrical shell, cooling back blanking obtains mixed powder;
(2) adopt high temperature carbonization furnace, mixed powder is carried out weighing dress boat, open vacuum pump then, reach and send into Ar and hydrogen under the negative pressure of vacuum condition again, with carbide furnace temperature ladder rise to 900～2650 ℃ and be incubated, push empty material boat then, push the charging boat again when waiting to enter into the 7th sky material boat, reduce and carbonization, recovery time is 1～3 hour, carbonization time is 15～20h, then material is pushed cooling zone and cools off, and obtains tungsten carbide slug;
(3) tungsten carbide slug with step (2) gained smashes, and the cracker mill tube of packing into carries out fragmentation, obtains thick tungsten carbide powder.
During proportioning, the weight of carbon black powders accounts for 6.13%.
Preferably, the Fei Shi of described Tungsten oxide 99.999 powder (Fsss) granularity is 5～16 μ m.In the step (1), putting into the time of mixing in the ball milling cylindrical shell is 16～26h.
In the step (2), the temperature of described carbide furnace heats up by 5～10 ℃/minute speed.
In the step (3), the time of described fragmentation is 12～18h.
Preferably, after step (1) is finished, also comprise mixed powder is carried out the original step that carbon detects of joining.Mixed powder carries out the original carbon of joining and detects, and checks whether the degree of mixing of carbon reaches mix uniformly effect.By detecting, join carbon and reach fully and mix effect.
Advantage of the present invention:
The thick WC particle of the present invention's preparation is of a size of 20～100 μ m, and granularity is very even, and the tungsten carbide powder defective is few.The purity height of the tungsten carbide powder of the present invention's preparation, wolfram varbide purity is greater than 99.9%.Chemical combination carbon content height in the tungsten carbide powder, free carbon content are low.Different material is to preparing the influence of extraordinarily thick crystal grain tungsten carbide powder; Extraordinarily thick crystal grain tungsten carbide powder and carbon black hybrid technique and equipment; Extraordinarily thick crystal grain tungsten carbide powder carbonization technique; Extraordinarily thick crystal grain tungsten carbide powder crushing process and equipment; Develop extraordinarily thick crystal grain tungsten carbide powder Wimet, its mean grain size 〉=8 μ m uses total footage to surpass domestic similar leading product with ground miner's tool of its preparation.
The present invention will be further described below by the drawings and specific embodiments, but and do not mean that limiting the scope of the invention.
Description of drawings
Fig. 1 is the granule-morphology figure of the tungsten carbide powder of the embodiment of the invention 1 preparation.
Fig. 2 is the granule-morphology figure of the tungsten carbide powder of the embodiment of the invention 2 preparations.
Embodiment
Embodiment 1
Adopting the Fsss granularity is that the blue oxide tungsten powder of 5 μ m, natural high-quality carbon black (gross data by 6.13% (weight) is carried out proportioning) are raw material, carry out proportioning according to the gross data that generates wolfram varbide, add and put into the mixing of carrying out 16h in the experiment ball milling cylindrical shell, cooling back blanking, carry out the original carbon detection of joining after emitting material, check whether the degree of mixing of carbon reaches mix uniformly effect.By detecting, join carbon and reach fully and mix effect.Material unloaded out carry out weighing dress boat.The carbonizing apparatus that adopts is full-automatic high temperature carbonization furnace.Open vacuum pump then, reach and send into Ar and hydrogen under the negative pressure of vacuum condition again, the carbide furnace temperature is heated up by 5 ℃ of/minute ladder ground, push empty material boat then, push the charging boat again when waiting to enter into the 7th sky material boat, its reduction temperature is 900 ℃, and the recovery time is 1 hour; Carbonization temperature 2500 temperature, carbonization time are 15h, material is pushed cooling zone cool off, and when treating that material reaches near normal temperature, will expect to release discharging.After the discharging material is smashed, allow its tungsten carbide slug conveniently enter into experiment cracker mill tube and carry out fragmentation, the broken time is 12h.
Detect by sampling, it the results are shown in Table 1, and the fsss granularity of tungsten carbide powder is about 20～100um, total carbon 6.12% (weight), uncombined carbon 0.03% (weight), oxygen level 150ppm.The pattern of the extraordinarily thick brilliant tungsten carbide powder of gained as shown in Figure 1, as can be seen, the crystal grain of tungsten carbide powder particle is very thick, and is more even, fine powder is few, particle crystallization is good, carbonization is complete, does not have the phenomenon of ditungsten carbide.
Embodiment 2
Adopting the Fsss granularity is that the blue oxide tungsten powder of 16 μ m, natural high-quality carbon black (gross data by 6.13% (weight) is carried out proportioning) are raw material, carry out proportioning according to the gross data that generates wolfram varbide, add and put into the mixing of carrying out 26h in the experiment ball milling cylindrical shell, cooling back blanking, carry out the original carbon detection of joining after emitting material, check whether the degree of mixing of carbon reaches mix uniformly effect.By detecting, join carbon and reach fully and mix effect.Material unloaded out carry out weighing dress boat.The carbonizing apparatus that adopts is full-automatic high temperature carbonization furnace.Open vacuum pump then, reach and send into Ar and hydrogen under the negative pressure of vacuum condition again, the carbide furnace temperature is heated up by 5～10 ℃ of/minute ladder ground, push empty material boat then, push the charging boat again when waiting to enter into the 7th sky material boat, 1000 ℃ of its reduction temperatures, the recovery time is 3 hours; 2650 ℃ of carbonization temperatures, carbonization time are 20h, material is pushed cooling zone cool off, and when treating that material reaches near normal temperature, will expect to release discharging.After the discharging material is smashed, allow its tungsten carbide slug conveniently enter into experiment cracker mill tube and carry out fragmentation, the broken time is 15h.
Detect by sampling, the fsss granularity of tungsten carbide powder is about 20～100um, total carbon 6.12% (weight), uncombined carbon 0.03% (weight), oxygen level 150ppm.The pattern of the extraordinarily thick brilliant tungsten carbide powder of gained as shown in Figure 2, as can be seen, the crystal grain of tungsten carbide powder particle is very thick, and is more even, fine powder is few, particle crystallization is good, carbonization is complete, does not have the phenomenon of ditungsten carbide.
Embodiment 3
Adopting the Fsss granularity is that the blue oxide tungsten powder of 10 μ m, natural high-quality carbon black (gross data by 6.13% (weight) is carried out proportioning) are raw material, carry out proportioning according to the gross data that generates wolfram varbide, add and put into the mixing of carrying out 20h in the experiment ball milling cylindrical shell, cooling back blanking, carry out the original carbon detection of joining after emitting material, check whether the degree of mixing of carbon reaches mix uniformly effect.By detecting, join carbon and reach fully and mix effect.Material unloaded out carry out weighing dress boat.The carbonizing apparatus that adopts is full-automatic high temperature carbonization furnace.Open vacuum pump then, reach and send into Ar and hydrogen under the negative pressure of vacuum condition again, the carbide furnace temperature is heated up by 10 ℃ of/minute ladder ground, push empty material boat then, push the charging boat again when waiting to enter into the 7th sky material boat, 950 ℃ of its reduction temperatures, the recovery time is 1 hour; 2600 ℃ of carbonization temperatures, carbonization time are 20h, material is pushed cooling zone cool off, and when treating that material reaches near normal temperature, will expect to release discharging.After the discharging material is smashed, allow its tungsten carbide slug conveniently enter into experiment cracker mill tube and carry out fragmentation, the broken time is 18h.
Detect by sampling, the fsss granularity of tungsten carbide powder is about 20～100um, total carbon 6.12% (weight), uncombined carbon 0.03% (weight), oxygen level 150ppm.The crystal grain of tungsten carbide powder particle is very thick, and is more even, and fine powder is few, and particle crystallization is good, and carbonization is complete, do not have the phenomenon of ditungsten carbide.
The detected result of table 1 embodiment 1 preparation tungsten carbide powder
Claims (7)
1. the preparation method of a thick tungsten carbide powder comprises the steps:
(1) Tungsten oxide 99.999 powder and carbon black powders are carried out proportioning according to the theoretical amount of reaction, mix in the threading ball milling cylindrical shell, obtain mixed powder;
(2) adopt high temperature carbonization furnace, mixed powder is carried out weighing dress boat, open vacuum pump then, reach and send into Ar and hydrogen under the negative pressure of vacuum condition again, with carbide furnace temperature ladder rise to 900～2650 ℃ and be incubated, push empty material boat then, push the charging boat again when waiting to enter into the 7th sky material boat, reduce and carbonization, recovery time is 1～3 hour, carbonization time is 15～20h, then material is pushed cooling zone and cools off, and obtains tungsten carbide slug;
(3) tungsten carbide slug is smashed, the cracker mill tube of packing into carries out fragmentation, obtains thick tungsten carbide powder.
2. the preparation method of thick tungsten carbide powder according to claim 1, it is characterized in that: during proportioning, the weight of described carbon black powders accounts for 6.13%.
3. the preparation method of thick tungsten carbide powder according to claim 1, it is characterized in that: the Fisher particle size of described Tungsten oxide 99.999 powder is 5～16 μ m.
4. the preparation method of thick tungsten carbide powder according to claim 1 is characterized in that: the time of mixing in the described threading ball milling cylindrical shell is 16～26h.
5. the preparation method of thick tungsten carbide powder according to claim 1 is characterized in that: the temperature of described carbide furnace heats up by 5～10 ℃/minute speed.
6. the preparation method of thick tungsten carbide powder according to claim 1, it is characterized in that: the time of described fragmentation is 12～18h.
7. the preparation method of thick tungsten carbide powder according to claim 1 is characterized in that: after step (1) is finished, also comprise mixed powder is carried out the original step that carbon detects of joining.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030288A (en) * | 2014-06-12 | 2014-09-10 | 东北大学 | Method for producing tungsten carbide |
| CN107089662A (en) * | 2017-06-16 | 2017-08-25 | 重庆大学 | A kind of method that CH4 reduction and carbonizations WO3 prepares WC powders |
| CN108529628A (en) * | 2018-05-28 | 2018-09-14 | 株洲硬质合金集团有限公司 | A kind of preparation method of Coarse Tungsten Carbide Powder |
| CN109231212A (en) * | 2018-10-17 | 2019-01-18 | 东北大学 | A method of preparing superfine tungsten carbide powder |
| CN109319785A (en) * | 2018-10-17 | 2019-02-12 | 东北大学 | A kind of method that mechanochemical method prepares superfine tungsten carbide powder |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030288A (en) * | 2014-06-12 | 2014-09-10 | 东北大学 | Method for producing tungsten carbide |
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| CN107089662A (en) * | 2017-06-16 | 2017-08-25 | 重庆大学 | A kind of method that CH4 reduction and carbonizations WO3 prepares WC powders |
| CN107089662B (en) * | 2017-06-16 | 2019-05-31 | 重庆大学 | A kind of method that CH4 reduction and carbonization WO3 prepares WC powder |
| CN108529628A (en) * | 2018-05-28 | 2018-09-14 | 株洲硬质合金集团有限公司 | A kind of preparation method of Coarse Tungsten Carbide Powder |
| CN109231212A (en) * | 2018-10-17 | 2019-01-18 | 东北大学 | A method of preparing superfine tungsten carbide powder |
| CN109319785A (en) * | 2018-10-17 | 2019-02-12 | 东北大学 | A kind of method that mechanochemical method prepares superfine tungsten carbide powder |
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Application publication date: 20130703 |