CN100441347C - Method for producing high-pressure blank intensity tungsten powder by ammonium paratungstate direct reduction - Google Patents
Method for producing high-pressure blank intensity tungsten powder by ammonium paratungstate direct reduction Download PDFInfo
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- CN100441347C CN100441347C CNB2005100215254A CN200510021525A CN100441347C CN 100441347 C CN100441347 C CN 100441347C CN B2005100215254 A CNB2005100215254 A CN B2005100215254A CN 200510021525 A CN200510021525 A CN 200510021525A CN 100441347 C CN100441347 C CN 100441347C
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Abstract
The present invention belongs to a method for directly reducing and producing high-pressure cog strength tungsten by using ammonium paratungstate as a raw material in the field of powder metallurgy. The method comprises the following steps: reduction treatment, recovery and cyclic utilization of hydrogen gas and sieving for trash extraction under the temperature of 700 to 1000 DEG C and hydrogen atmpsphere. The present invention avoids the deposition of the tungsten to grow big in the process of reduction treatment so that granules are developed incompletely to form an unsystematic pattern and loose aggregation or bridging structure, and accordingly, the present invention is good for press forming. Therefore, the present invention has the characteristics of short production flow, simple, direct and advanced method, convenient and reliable operation control, high purity of the tungsten, large binding strength, stable quality; large density and good resistance to high temperature of sintered manufactured products, etc. The green strength is as high as 2.0 to 3.6MPa. The present invention can be widely used for manufacturing parts of flame projectors, rocket flight rudders, etc. in the fields of aviation and aerospace, and the present invention overcomes the disadvantages of the background art that the formability of the tungsten is bad, the green strength is at most 2.0mpa and can not be enhanced any longer, the background art can not satisfy the use in the fields of aviation and aerospace, etc.
Description
Technical field
The invention belongs to the production method of a kind of high-pressure blank intensity tungsten powder in the field of powder metallurgy, the straight reduction of particularly a kind of employing ammonium paratungstate (APT) is to produce the method for high-pressure blank intensity tungsten powder, and the tungsten powder that this method is produced is not for can adding the high-purity tungsten powder that forming agent can be pressed into the high strength pressed compact.This tungsten powder can be widely used in produces required product in the Aeronautics and Astronautics field.
Background technology
At present, being widely used in the method for producing high-pressure blank intensity tungsten powder is to be raw material with the ammonium paratungstate, makes it generate tungsten oxide (WO through calcination
3, WO
2.9) back, again tungsten oxide handle is generated tungsten powder through hydrogen reduction, after the screening removal of impurities promptly makes the object high-pressure blank intensity tungsten powder." Zhongnan Polytechnic Univ's journal " 1995,26 (5)-605-609 and disclosed this type of process that is of national science and technology achievement net " ammonium paratungstate is produced the research of blue tungsten, tungsten powder ".Though these class methods can reduce reduction process moisture, improve reduction reaction speed, make the tungsten powder particles zoon, the dispersiveness of powder, good fluidity, and size distribution is concentrated and is formed higher peak value, and the tungsten powder of being produced can be used for making the characteristics such as high-quality hard metal article of uniform crystal particles; But adopt this method just because of the tungsten powder particles zoon, surface texture is regular, powder is dispersed and good fluidity, if being used for the pure tungsten powder is that raw material compression moulding manufacturing tungsten base high-density and high-temperature-resistant material then exists defectives such as processability is poor, compact strength is low, its compact strength value only is 1.3～2.0Mpa and can't improves again; And, reduce, will reduce again the density and the resistance to elevated temperatures of end article because of its purity of infiltration of impurity if add forming agent to improve compact strength.Thereby this type of technology exist the tungsten powder produced in its follow-up production insufficient formability, compact strength is low when not adding forming agent, not being suitable for the pure tungsten powder is that defectives such as tungsten base high density, resistant to elevated temperatures goods are produced in raw material compression moulding.
Summary of the invention
The objective of the invention is a kind of method that adopts producing high-pressure blank intensity tungsten powder by ammonium paratungstate direct reduction of research and design.Production procedure is short, technology is simple and direct to reach, advanced, steady quality, tungsten powder purity and compact strength height thereof, purpose such as, resistance to elevated temperatures big in order to sintered article density is good.
Solution of the present invention is to save at first ammonium paratungstate to be calcined in the background technology to make it generate the operation of tungsten oxide, and directly the raw material ammonium paratungstate is placed reduce under nitrogen atmosphere and the reduction temperature processing, make and contain assorted tungsten powder, promptly obtain the object of the invention object height through the screening removal of impurities again and suppress the base tungsten powder.Therefore, the inventive method comprises:
A, hydrogen reducing handle: with purity is that ammonium paratungstate more than the technical pure places high temperature resistant boat anti-oxidant and that do not react with hydrogen and tungsten, thick 10～the 40mm of the bed of material, send into then in the reduction furnace under nitrogen atmosphere and 700～1000 ℃ of temperature, divide 3～5 temperature bands to handle 6～12 hours, contain assorted tungsten powder with promptly getting after the stove cooling with the boat speed that the pushes away reduction that 10～35mm/ divides; Hydrogen flowing quantity 5～20m
3/ hour;
B, screening removal of impurities: will be after reduction be handled the gained tungsten powder send into the multi-deck screen of 75～150 μ m or vibratory sieve to remove bulky grain and field trash, promptly getting Fei Shi (FSSS) granularity is the object high-pressure blank intensity tungsten powder of 1.8～3.5 μ m.
Above-mentioned purity is the above ammonium paratungstate of technical pure, and its apparent density is 2.0～3.0g/cm
3, Fei Shi (FSSS) granularity 25～45 μ m.Described anti-oxidant and high temperature resistant boat that do not react with hydrogen and tungsten is heat-resistance stainless steel boat or nickel boat, molybdenum boat.And 3～5 temperature bands of described branch, each temperature band is respectively 700～860 ℃, 820～900 ℃, 850～1000 ℃ when adopting 3 temperature bands, then be respectively 700～800 ℃, 780～880 ℃, 820～920 ℃, 870～1000 ℃ when adopting 4 temperature bands, each temperature band then is respectively 700～800 ℃, 750～850 ℃, 800～900 ℃, 850～950 ℃ and 900～1000 ℃ when adopting 5 temperature bands.Described hydrogen is the hydrogen below the dew-point temperature-40 ℃, hydrogen drives in the wrong direction and imports in reduction treatment process, input hydrogen is preheated in the material of cooling after reduction is handled, and the hydrogen of tail end (feed end) after reduction is handled filters, imports in the reduction furnace after dry the processing again recycling by retracting device.
The present invention is owing to adopt directly reduction processing under nitrogen atmosphere of ammonium paratungstate, and the first temperature band in the reduction reaction primary stage mainly forms a large amount of volatile WO
3Or WO
2.9And cause both to deposit back bonding, loose aggregated structure and the bridging structure of formation mutually, the tungsten powder that the tungsten oxide of these structures forms when the fast restore of high-temperature region destroyed tungsten oxide in conjunction with dynamics, still keep original loose gathering or bridging structure, avoided the deposition of tungsten powder to grow up, made the particle ateliosis, helped compression moulding thereby form irregular granule-morphology.Thereby the present invention to have a production procedure short, simple and direct, advanced, convenient operation and control, reliable, tungsten powder purity height, big, the steady quality of bond strength; Characteristics such as powder Fisher particle size 1.8～3.5 μ m, compact strength be up to 2.0～3.6Mpa, and, resistance to elevated temperatures big in order to the extrudate density that sinters into is good can be widely used in the Aeronautics and Astronautics field and make parts such as flame thrower, rocket flight rudder.
The specific embodiment 1
A, hydrogen reduction: with purity is chemical pure, apparent density 2.8g/cm
3, Fisher particle size 40 μ m ammonium paratungstate, pack in the heat-resistance stainless steel boat by the thick 35mm of the bed of material, boat charge 800g/ boat, and send into to reduce in 3 temperature band heating furnaces of 15 pipes and handled 8 hours; Each temperature band temperature is respectively 800 ℃, 880 ℃ and 950 ℃, pushes away boat speed 20mm/ branch, and below the dew point of hydrogen temperature-40 ℃, flow is 8m
3/ hour, reverse entering in the boiler tube, material contains assorted tungsten powder with promptly getting after the stove cooling; Follow also after the retracting device of the hydrogen input tape screen pack after reduction is handled and drying are handled and use;
B, screening removal of impurities: it is that revolving of 120 μ m shaken and sieved in the sieve that the tungsten powder after above-mentioned reduction handled is sent into sieve diameter, with after removing field trashes such as bulky grain and boat skin, particle mean size be the high-pressure blank intensity tungsten powder of 3.05 μ m.This tungsten powder under the condition of not adding any forming agent, its compact strength reaches 2.32Mpa.
The specific embodiment 2
Present embodiment adopts purity for analyzing pure, apparent density 2.4g/cm
3, Fisher particle size 30 μ m ammonium paratungstate be raw material, its method is:
A, hydrogen reduction: the above-mentioned raw materials ammonium paratungstate is pressed the thick 20mm of the bed of material, and boat charge 400g/ boat is packed in the pure nickel boat, adopts double-deck boat to send in 15 pipes, the 5 temperature band natural gas Heating Reduction Furnace for Tungsten, is 12m at hydrogen flowing quantity
3/ hour, each temperature band is respectively under the condition of 750 ℃, 800 ℃, 840 ℃, 890 ℃ and 920 ℃ reduction and handled 10 hours, material promptly gets after with the stove cooling and contains assorted tungsten powder; The hydrogen recycle and reuse is with embodiment 1;
B, screening removal of impurities: will send into the aperture through the tungsten powder after the A reduction is that revolving of 100 μ m shaken and sieved in the sieve to remove impurity such as bulky grain and boat skin, promptly to get the high-pressure blank intensity tungsten powder that particle mean size is 2.25 μ m.This tungsten powder is suppressed under the condition of not adding any forming agent, and its compact strength reaches 3.20Mpa.
Claims (5)
1, the method for producing high-pressure blank intensity tungsten powder by ammonium paratungstate direct reduction, its method comprises:
A, hydrogen reducing handle: with purity is that ammonium paratungstate more than the technical pure places high temperature resistant boat anti-oxidant and that do not react with hydrogen and tungsten, thick 10～the 40mm of the bed of material, send into then in the reduction furnace under nitrogen atmosphere and 700～1000 ℃ of temperature, divide 3～5 temperature bands to handle 6～12 hours, contain assorted tungsten powder with promptly getting after the stove cooling with the boat speed that the pushes away reduction that 10～35mm/ divides; Hydrogen flowing quantity 5～20m
3/ hour;
B, screening removal of impurities: will be after reduction be handled the gained tungsten powder send into the multi-deck screen of 75～150 μ m or vibratory sieve to remove bulky grain and field trash, promptly getting Fisher particle size is the object high-pressure blank intensity tungsten powder of 1.8～3.5 μ m.
2, by the method for the described production high-pressure blank intensity tungsten powder of claim 1, it is characterized in that described purity is the above ammonium paratungstate of technical pure, its apparent density is 2.0～3.0g/cm
3, Fisher particle size 25～45 μ m.
3, by the method for the described production high-pressure blank intensity tungsten powder of claim 1, it is characterized in that described high temperature resistant boat is heat-resistance stainless steel boat, nickel boat or molybdenum boat.
4, press the method for the described production high-pressure blank intensity tungsten powder of claim 1, it is characterized in that 3～5 temperature bands of described branch, each temperature band is respectively 700～860 ℃, 820～900 ℃, 850～1000 ℃ when adopting 3 temperature bands, then be respectively 700～800 ℃, 780～880 ℃, 820～920 ℃, 870～1000 ℃ when adopting 4 temperature bands, each temperature band then is respectively 700～800 ℃, 750～850 ℃, 800～900 ℃, 850～950 ℃ and 900～1000 ℃ when adopting 5 temperature bands.
5, press the method for the described production high-pressure blank intensity tungsten powder of claim 1, it is characterized in that described hydrogen is the hydrogen below the dew-point temperature-40 ℃, hydrogen drives in the wrong direction and imports in reduction treatment process, input hydrogen is preheated in the material of cooling after reduction is handled, and the hydrogen of tail end after reduction is handled filters, imports in the reduction furnace after dry the processing again recycling by retracting device.
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| CNB2005100215254A CN100441347C (en) | 2005-08-25 | 2005-08-25 | Method for producing high-pressure blank intensity tungsten powder by ammonium paratungstate direct reduction |
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Families Citing this family (13)
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| JP4797099B2 (en) * | 2009-10-01 | 2011-10-19 | Ｊｘ日鉱日石金属株式会社 | Manufacturing method of high purity tungsten powder |
| CN102198507B (en) * | 2011-05-16 | 2012-10-24 | 赣州虹飞钨钼材料有限公司 | Method for producing tungsten bar serving as halogen tungsten lamp tungsten filament |
| CN102161101B (en) * | 2011-05-31 | 2012-08-01 | 赣州虹飞钨钼材料有限公司 | A method of preparing high purity tungsten material used for very large scale integrated circuits |
| CN102672175B (en) * | 2012-05-15 | 2013-12-25 | 赣州海盛钨钼集团有限公司 | Preparation method of potassium-containing round-tungsten-doped aluminum strip |
| CN103240421B (en) * | 2013-05-27 | 2015-12-23 | 江西稀有稀土金属钨业集团有限公司 | A kind of production method of high-pressure blank intensity tungsten powder and system |
| CN104399997A (en) * | 2014-11-26 | 2015-03-11 | 北京矿冶研究总院 | Preparation method of tungsten powder |
| CN106141198A (en) * | 2015-04-02 | 2016-11-23 | 上海六晶科技股份有限公司 | The method of ultrafine tungsten powder is prepared in a kind of direct-reduction |
| CN106077696B (en) * | 2016-08-24 | 2018-04-24 | 洛阳金鹭硬质合金工具有限公司 | A kind of preparation method of spherical single crystal tungsten powder used for hot spraying |
| CN108746657B (en) * | 2018-06-20 | 2021-07-23 | 广东翔鹭钨业股份有限公司 | Preparation method of high-pressure billet strength tungsten powder |
| CN109261980B (en) * | 2018-07-31 | 2022-01-18 | 自贡硬质合金有限责任公司 | Preparation method of tungsten powder for high-density alloy |
| CN111283211A (en) * | 2020-02-26 | 2020-06-16 | 厦门虹鹭钨钼工业有限公司 | Preparation method of high-purity tungsten powder |
| CN111872409B (en) * | 2020-07-29 | 2024-01-16 | 铜陵铜冠优创特种材料有限公司 | Production process of high-purity aviation-grade rhenium particles |
| CN114472913B (en) * | 2022-02-14 | 2023-10-03 | 崇义章源钨业股份有限公司 | Preparation method of high-pressure blank strength tungsten powder |
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