CN109014232B - Method for preparing superfine tungsten-copper composite powder - Google Patents
Method for preparing superfine tungsten-copper composite powder Download PDFInfo
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- CN109014232B CN109014232B CN201810995928.6A CN201810995928A CN109014232B CN 109014232 B CN109014232 B CN 109014232B CN 201810995928 A CN201810995928 A CN 201810995928A CN 109014232 B CN109014232 B CN 109014232B
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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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
Abstract
A method for preparing superfine tungsten-copper alloy powder belongs to the field of alloy materials. Mixing ammonium tungstate and copper nitrate according to the required copper content, grinding and mixing to obtain a uniformly mixed powder raw material; roasting the powder raw material in air atmosphere, preserving heat for a period of time at a certain temperature, cooling after heat preservation,obtaining corresponding oxide powder, then mixing the oxide powder with carbon black less than the theoretical proportion according to a certain molar ratio, and carrying out carbothermic prereduction in an argon atmosphere to obtain the product containing a small amount of WO2Most of the powder is W and Cu powder; and in a hydrogen atmosphere, carrying out deep deoxidation on the powder obtained after the carbothermic reduction to obtain the superfine tungsten-copper composite powder. The tungsten-copper composite powder with crystal grains less than 200nm and uniform size distribution can be obtained by using the process. The method is simple to operate, low in cost and easy for industrial implementation and operation. The scheme can be also used for preparing the ultra-fine molybdenum-copper composite powder.
Description
Technical Field
The invention belongs to the field of alloy materials, discloses a method for preparing superfine tungsten-copper composite powder, and particularly relates to a method for preparing tungsten-copper composite powder by using two-stage reduction combining carbon black and hydrogen.
Background
The tungsten-copper alloy has both high hardness and high melting point of tungsten and high electrical and thermal conductivity of copper. Wherein tungsten has high melting point (3410 deg.C), and high density (19.34 g/cm)3) (ii) a The copper has excellent electric and heat conducting performance, and the tungsten-copper alloy (with the general component range of WCu7-WCu50) has uniform microstructure, high temperature resistance, high strength, electric arc ablation resistance and high density; the conductive and heat-conducting properties are moderate, and the material can be widely applied to military high-temperature-resistant materials, electric alloys for high-voltage switches, electric processing electrodes and microelectronic materials, and can be widely applied to industries such as aerospace, aviation, electronics, electric power, metallurgy, machinery, sports equipment and the like as parts and components.
The main methods for preparing the tungsten-copper alloy at present are a direct mixing method of tungsten powder and copper powder, an infiltration method and the like. The tungsten copper prepared by directly mixing tungsten powder and copper powder by the method has poor uniformity, more closed gaps and density generally lower than 98%. The infiltration method has complex production process, higher production cost and higher difficulty in preparing the low-copper alloy. The tungsten-copper alloy prepared by sintering the superfine tungsten-copper composite powder serving as a raw material has great advantages. At present, tungsten-copper composite powder is mainly prepared by reducing tungsten-copper oxide with hydrogen, but for preparing superfine tungsten-copper composite powder, special pretreatment needs to be carried out on raw materials, such as obtaining composite oxide in a sol-gel mode or high-energy ball milling, and the processes are complex, high in cost and easy to introduce impurities.
Disclosure of Invention
The invention aims to prepare the superfine tungsten-copper composite powder by using ammonium tungstate and copper nitrate as raw materials and using carbon black and hydrogen as reducing agents to carry out two-stage reduction, thereby simplifying the operation process, reducing the cost and refining crystal grains.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method for preparing superfine tungsten-copper alloy powder is characterized by comprising the following steps: preparing superfine tungsten-copper composite powder by adopting a carbon-hydrogen two-stage reduction method, specifically, mixing ammonium tungstate and copper nitrate according to the required copper content, grinding and mixing to obtain a uniformly mixed powder raw material; roasting the powder raw material in the air atmosphere, preserving heat for a period of time at a certain temperature, finishing the heat preservation, cooling to obtain corresponding oxide powder, then mixing with carbon black less than the theoretical proportion according to a certain molar ratio, and carrying out carbothermic prereduction in the argon atmosphere to obtain the product containing a small amount of WO2Most of the powder is W and Cu powder; and in a hydrogen atmosphere, carrying out deep deoxidation on the powder obtained after the carbothermic reduction to obtain the superfine tungsten-copper composite powder.
Further, ammonium tungstate and copper nitrate are used as raw materials, and are mixed according to the required mass ratio of W to Cu and then are roasted for 1-4 hours at the temperature of 400-600 ℃.
Further, the product obtained after roasting ammonium tungstate and copper nitrate is subjected to carbon-deficiency pre-reduction, and the carbon distribution is calculated according to the following rule: WO in the roasted product3And for reduction of WO3According to a molar ratio of 1: 0.5-1: 2.5; CuO and carbon black for reducing CuO are mixed in a molar ratio of 1: 0.5-1: 1, mixing materials. The total carbon content is reduced WO3And the amount of carbon black used to reduce CuO.
Further, under the argon atmosphere, the uniformly mixed raw materials are subjected to heat preservation for 2-4 hours at the temperature of 400-2Most of W and Cu powderAnd (3) a body.
Further, the product of carbothermic reduction is subjected to deep deoxidation at the temperature of 600-900 ℃ for 1-4 hours, and then is cooled in a hydrogen atmosphere, so that the ultrafine tungsten-copper composite powder with the size less than 200nm is obtained.
Furthermore, the carbon-hydrogen two-stage reduction method is also suitable for preparing the ultrafine molybdenum-copper composite powder, and all technical routes and process parameters adopt the method for preparing the tungsten-copper composite powder, and the only difference is that ammonium molybdate and copper nitrate are adopted as raw materials.
The method can obtain the tungsten-copper composite powder with the crystal grain less than 200nm and uniform size distribution. The method is simple to operate, low in cost and easy for industrial implementation and operation. The scheme can be also used for preparing the ultra-fine molybdenum-copper composite powder.
Detailed Description
Example one: preparing a W-30% Cu alloy, wherein the mass ratio of tungsten to copper in ammonium tungstate and copper nitrate is (7): 3, uniformly mixing. Then the raw materials are put into a high-temperature furnace, the temperature is raised to 400 ℃ along with the furnace in the air atmosphere, the temperature is preserved for 4 hours, and then the raw materials are cooled in the air atmosphere. Carbon blending is carried out according to the following rules: WO3And for reduction of WO3In a molar ratio of 1: 2; molar ratio of CuO to carbon black for reducing CuO was in the range of 1: 0.5, uniformly mixing, reacting at 600 ℃ for 2 hours under the argon atmosphere, then reacting at 1000 ℃ for 2 hours, and cooling under the argon atmosphere to obtain W, Cu and a small amount of WO2A mixture of (a). Then preserving the heat of the product after the carbon thermal pre-reduction for 4 hours at 800 ℃ in a hydrogen atmosphere, cooling the product to room temperature in the hydrogen atmosphere to obtain tungsten-copper composite powder with the grain diameter of less than 200nm,
example two: preparing a W-10% Cu alloy, wherein the mass ratio of tungsten to copper in ammonium tungstate and copper nitrate is 90: 10 are mixed homogeneously. Then the raw materials are put into a high-temperature furnace to be heated to 500 ℃ along with the furnace in the air atmosphere, the temperature is kept for 4 hours, and then the raw materials are cooled in the air atmosphere. Carbon blending is carried out according to the following rules: WO3And for reduction of WO3In a molar ratio of 1: 2.1; CuO and for reductionThe molar ratio of carbon black of CuO is 1: 0.5, uniformly mixing, reacting at 600 ℃ for 2 hours under the argon atmosphere, then reacting at 1000 ℃ for 2 hours, and cooling under the argon atmosphere to obtain W, Cu and a small amount of WO2A mixture of (a). And then preserving the heat of the product of the carbon thermal pre-reduction for 2 hours at 850 ℃ in a hydrogen atmosphere, and cooling the product in the hydrogen atmosphere to obtain the tungsten-copper composite powder with the particle size of less than 200 nm.
Claims (1)
1. A method for preparing superfine tungsten-copper composite powder is characterized by comprising the following steps: preparing superfine tungsten-copper composite powder by adopting a carbon-hydrogen two-stage reduction method, specifically, mixing ammonium tungstate and copper nitrate according to the required copper content, grinding and mixing to obtain a uniformly mixed powder raw material; roasting the powder raw material in an air atmosphere, preserving heat for 1-4 hours at the temperature of 400-600 ℃, finishing the heat preservation, cooling to obtain corresponding oxide powder, then carrying out carbon deficiency pre-reduction on the product obtained after roasting ammonium tungstate and copper nitrate, and calculating the carbon distribution according to the following rules: WO in the roasted product3And for reduction of WO3According to a molar ratio of 1: 0.5-1: 2.5; CuO and carbon black for reducing CuO are mixed in a molar ratio of 1: 0.5-1: 1 mixing materials, carrying out carbon thermal pre-reduction in argon atmosphere, preserving the uniformly mixed raw materials at the temperature of 400-2Most of the powder is W and Cu powder; and then, under a hydrogen atmosphere, preserving the heat of the carbothermic reduction product at the temperature of 600-900 ℃ for 1-4 hours for deep deoxidation, and then, cooling under the hydrogen atmosphere to obtain the ultrafine tungsten-copper composite powder with the size less than 200 nm.
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| CN112974814A (en) * | 2021-04-25 | 2021-06-18 | 陕西斯瑞新材料股份有限公司 | Method for preparing regenerated copper-tungsten alloy powder |
| CN114029496B (en) * | 2021-10-12 | 2022-11-08 | 南昌大学 | Preparation method of novel superfine molybdenum-rhenium alloy powder |
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