CN102909389B - Method for reducing and preparing nano molybdenum-copper composite powder with low temperature - Google Patents
Method for reducing and preparing nano molybdenum-copper composite powder with low temperature Download PDFInfo
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- CN102909389B CN102909389B CN201210453461.5A CN201210453461A CN102909389B CN 102909389 B CN102909389 B CN 102909389B CN 201210453461 A CN201210453461 A CN 201210453461A CN 102909389 B CN102909389 B CN 102909389B
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Abstract
A method for reducing and preparing nano molybdenum-copper composite powder with low temperature comprises two steps: step 1, preparing molybdenum-copper oxide precursor, and step 2, preparing nano molybdenum-copper composite powder. In step 1, a water solution of molybdenum salt and an ammonia water solution of copper salt are mixed, the mixed solution is heated through micro-wave heating for fast concentration, and resolvents are removed to obtain molybdenum-copper oxide precursor powder; and in step 2, molybdenum-copper oxide precursor powder is heated to be 325 to 400 DEG C, calcined, taken out of a stove, cooled by air, and then heated to 525 to 625 DEG C for reducing after being placed in an H2 atmosphere, so as to obtain nano molybdenum-copper composite powder. The nano molybdenum-copper composite powder prepared according to the method has the advantages that the specific surface area is large; the crystal grains are fine and the purity is high. As molybdenum-copper oxide precursor powder is prepared by combining a simple and effective liquid phase chemical method with micro-wave heating, and nano molybdenum-copper composite powder is prepared through calcining and reducing, the method provided by the invention is simple and fast; the process is easy to control; the powder yield is large; the efficiency is high; the reducing temperature of powder is greatly reduced; and suitability for industrialized mass production is realized.
Description
Technical field
The invention discloses a kind of low-temperature reduction and prepare the method for molybdenum-copper composite nano-powder, belong to powder metallurgy preparing technical field.
Background technology
Composite material of molybdenum and copper is a kind of pseudo-alloy, combines high-ductility, the high-conductivity of high-melting-point, high strength and the copper of molybdenum, has good combination property.Molybdenum copper product was applied mainly as the electrical contact of high-voltage switch gear in the past, was used widely in recent years in Aero-Space and weapon industry.
By melting infiltration sintering and simple liquid-phase sintering preparation, all there is the shortcomings such as component segregation, relative density are not high in tradition molybdenum copper product, has a strong impact on the advantage of molybdenum copper product.Utilize powder metallurgy sintered molybdenum-copper composite nano-powder to prepare composite material of molybdenum and copper and can effectively avoid above shortcoming.Prepare at present nanometer molybdenum cuprum powder and be mainly divided into Mechanical Method and chemical method, Mechanical Method, by ball milling molybdenum Cu oxide, reaches the object of refinement particle, and reduction obtains molybdenum-copper compound powder, but ball milling has been introduced Fe impurity for a long time, has a strong impact on the performance of molybdenum copper product; Chemical method has been avoided introducing impurity, by producing micro-nano molybdenum copper precursor, makes molybdenum-copper compound powder by calcining reduction.But there is corresponding shortcoming, existing chemical method has sol-gal process, atomization conversion method, electroless plating method, liquid phase reduction etc., these methods are high to equipment requirement, or technique relative complex, wherein also need individually multistage reduction, reduction temperature is generally 700 ~ 900 ℃, or chronic, difficulty has an equipment, technique simple, the method that the time is short.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art and provide simple, the easy to operate low-temperature reduction of a kind of process to prepare the method for molybdenum-copper composite nano-powder.The nanometer molybdenum cuprum composite powder preparing, powder mean particle sizes can be less than 100nm, and grain size is less than 30nm.
A kind of low-temperature reduction of the present invention is prepared the method for molybdenum-copper composite nano-powder, comprises the steps:
The first step: the preparation of molybdenum Cu oxide presoma
Get the aqueous solution of molybdenum salt, the ammonia spirit of mantoquita mixes, and obtains mixed solution, by concentrated mixed solution heating, removes solvent, obtains molybdenum Cu oxide precursor powder; Wherein, in the ammonia spirit of mantoquita, NH
3consumption be that in mantoquita, copper ion all generates
theoretical consumption 2-4 doubly;
Second step: the preparation of molybdenum-copper composite nano-powder
The molybdenum Cu oxide precursor powder that the first step is obtained is heated to 325～400 ℃ of calcinings, and the air cooling of coming out of the stove, then, is placed in H by powder
2in atmosphere, be heated to 525～625 ℃ and reduce, obtain molybdenum-copper composite nano-powder.
A kind of low-temperature reduction of the present invention is prepared the method for molybdenum-copper composite nano-powder, and described molybdenum salt is ammonium dimolybdate or ammonium paramolybdate.
A kind of low-temperature reduction of the present invention is prepared the method for molybdenum-copper composite nano-powder, and described mantoquita is copper chloride or copper nitrate.
A kind of low-temperature reduction of the present invention is prepared the method for molybdenum-copper composite nano-powder, in the first step, in described mixed solution, the molar concentration of copper atom is 0.05～0.4mol/L, the molar concentration of molybdenum atom is 0.05～0.75mol/L, and molybdenum atom concentration is more than or equal to copper atom concentration.
A kind of low-temperature reduction of the present invention is prepared the method for molybdenum-copper composite nano-powder, and the concentrated employing of mixed solution heating micro-wave oven is thermal source, and concentration time is less than or equal to 40min.
A kind of low-temperature reduction of the present invention is prepared the method for molybdenum-copper composite nano-powder, and in second step, molybdenum Cu oxide precursor powder calcination time is 0.5～1.5h, and the recovery time after calcining in hydrogen is 1.5～2.5h.
A kind of low-temperature reduction of the present invention is prepared the method for molybdenum-copper composite nano-powder, and the particle mean size of described molybdenum-copper composite nano-powder is 100nm; Molybdenum copper powder mean grain size is 30nm.
Advantage of the present invention and good effect, be embodied in:
The present invention is owing to adopting above-mentioned process, the present invention adopts microwave concentrated, in concentration process, forming core is even, nucleated time is short, and the molybdenum copper powders crystallite dimension of reduction preparation is very little, is less than 30nm, particle mean size can be less than 100nm, purity is high, can reach more than 99.5%, and oxygen content is less than 0.2wt%; In adjusting mixed solution, the ratio of molybdenum salt and mantoquita, can obtain the nanometer molybdenum cuprum composite powder that Mo content is greater than the arbitrary proportion of 60wt%.The nanometer molybdenum cuprum composite powder that the present invention prepares has specific area prosperity, and crystal grain is tiny, purity advantages of higher.Owing to adopting, microwave is concentrated, and forming core is more even, and nucleated time is short, and precursor crystal grain is tiny, even, powder 525 ~ 625 ℃ reducible, reduction temperature of the present invention is low compared with existing method, is that temperature is prepared in molybdenum-copper compound powder in existing reduction minimum.Compared with the method for reporting, the inventive method simple and fast, technique is easy to control, and powder output is large, and efficiency is high, is applicable to industrialization volume production.
Accompanying drawing explanation:
The Mo-Cu powder XRD figure that accompanying drawing 1 makes for the embodiment of the present invention 1.
Accompanying drawing 2 is the worth Mo-Cu powder TEM figure of the embodiment of the present invention 1.
From Fig. 1, can go out, in powder prepared by embodiment 1, be formed by molybdenum and two kinds of materials of copper.
As can be seen from Figure 2 in powder, assemble the second particle forming, specific area prosperity by very little primary particle.
The specific embodiment
Embodiment 1:
(1) take 12.36g ammonium paramolybdate, 10.95g copper nitrate, measure 150ml concentrated ammonia liquor (25 ~ 28%), be configured to the aqueous solution of ammonium paramolybdate, the ammonia spirit of copper nitrate, mixes and adds H
2o is configured to 1L mixed solution.
(2) four parts of the solution deciles (1) configuration being obtained, gradation is placed in micro-wave oven (700W), concentrates fast, obtains molybdenum Cu oxide precursor powder.
(3) precursor powder (2) being made is calcined in air, and calcining heat is 350 ℃, and calcination time is 0.75h, obtains molybdenum Cu oxide composite powder.
(4) composite powder (3) being made is at H
2in in 575 ℃ of insulation 2h, obtain the nanometer molybdenum cuprum composite powder of 70Mo-30Cu.Referring to accompanying drawing 1, the data that obtained by Fig. 1, are analyzed and are obtained half-peak breadth by Jade, and utilizing Scherrer formula to calculate average grain size by half-peak breadth is 19nm.
Embodiment 2:
(1) take 12.36g ammonium paramolybdate, 6.39g copper nitrate, measure 100ml concentrated ammonia liquor (25 ~ 28%), be configured to the aqueous solution of ammonium paramolybdate, the ammonia spirit of copper nitrate, mixes and adds H
2o is configured to 1L mixed solution.
(2) five parts of the solution deciles (1) configuration being obtained, gradation is placed in micro-wave oven (700W), concentrates fast, obtains molybdenum Cu oxide precursor powder.
(3) precursor powder (2) being made is calcined in air, and calcining heat is 350 ℃, and calcination time is 0.75h, obtains molybdenum Cu oxide composite powder.
(4) composite powder (3) being made is at H
2in in 575 ℃ of insulation 2h, obtain the nanometer molybdenum cuprum composite powder of 80Mo-20Cu.
Embodiment 3:
(1) take 17.96g ammonium paramolybdate, 20g copper nitrate, measure 500ml concentrated ammonia liquor (25 ~ 28%), be configured to the aqueous solution of ammonium paramolybdate, the ammonia spirit of copper nitrate, mixes and adds H
2o is configured to 1L mixed solution.
(2) four parts of the solution deciles (1) configuration being obtained, gradation is placed in micro-wave oven (700W), concentrates fast, obtains molybdenum Cu oxide precursor powder.
(3) precursor powder (2) being made is calcined in air, and calcining heat is 400 ℃, and calcination time is 0.5h, obtains molybdenum Cu oxide composite powder.
(4) composite powder (3) being made is at H
2in in 600 ℃ of insulation 2h, obtain the nanometer molybdenum cuprum composite powder of 65Mo-35Cu.
Claims (6)
1. low-temperature reduction is prepared a method for molybdenum-copper composite nano-powder, comprises the steps:
The first step: the preparation of molybdenum Cu oxide presoma
Get the aqueous solution of molybdenum salt, the ammonia spirit of mantoquita mixes, and obtains mixed solution, by concentrated mixed solution heating, removes solvent, obtains molybdenum Cu oxide precursor powder; Wherein, in the ammonia spirit of mantoquita, NH
3consumption be that in mantoquita, copper ion all generates Cu(NH
3)
4 2+theoretical consumption 2-4 doubly; The concentrated employing of mixed solution heating micro-wave oven is thermal source, and concentration time is less than or equal to 40 min;
Second step: the preparation of molybdenum-copper composite nano-powder
The molybdenum Cu oxide precursor powder that the first step is obtained is heated to 325 ~ 400 ℃ of calcinings, and the air cooling of coming out of the stove, then, is placed in H by powder
2in atmosphere, be heated to 525 ~ 625 ℃ and reduce, obtain molybdenum-copper composite nano-powder.
2. a kind of low-temperature reduction according to claim 1 is prepared the method for molybdenum-copper composite nano-powder, it is characterized in that: described molybdenum salt is ammonium dimolybdate or ammonium paramolybdate.
3. a kind of low-temperature reduction according to claim 1 and 2 is prepared the method for molybdenum-copper composite nano-powder, it is characterized in that: described mantoquita is copper chloride or copper nitrate.
4. a kind of low-temperature reduction according to claim 3 is prepared the method for molybdenum-copper composite nano-powder, it is characterized in that: in the first step, in described mixed solution, the molar concentration of copper atom is 0.05 ~ 0.4mol/L, the molar concentration of molybdenum atom is 0.05 ~ 0.75 mol/L, and molybdenum atom concentration is more than or equal to copper atom concentration.
5. a kind of low-temperature reduction according to claim 4 is prepared the method for molybdenum-copper composite nano-powder, it is characterized in that: in second step, molybdenum Cu oxide precursor powder calcination time is 0. 5 ~ 1.5 h, and the recovery time after calcining in hydrogen is 1.5 ~ 2.5 h.
6. a kind of low-temperature reduction according to claim 5 is prepared the method for molybdenum-copper composite nano-powder, it is characterized in that: molybdenum copper powder mean grain size is less than or equal to 30nm.
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| CN104475759A (en) * | 2015-01-04 | 2015-04-01 | 湖南科技大学 | Preparation method for high-dispersion superfine nanometer Mo-Cu compound powder |
| CN104722769A (en) * | 2015-04-16 | 2015-06-24 | 柳州豪祥特科技有限公司 | Copper molybdenum powder preparation process |
| CN108515179B (en) * | 2018-04-16 | 2021-06-29 | 湖南工业大学 | Method for preventing copper loss in liquid-phase sintering process of tungsten-copper material |
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| KR100462274B1 (en) * | 2001-12-27 | 2004-12-17 | 주식회사 나노테크 | A method of manufacturing tungsten- copper based composite powder and sintered alloy for heat sink using the same |
| CN100589902C (en) * | 2007-09-26 | 2010-02-17 | 中南大学 | Ultra-fine or nanometer molybdenum cuprum composite powder and method of producing the alloy thereof |
| CN101234430A (en) * | 2008-02-22 | 2008-08-06 | 中南大学 | Method for preparing ultrafine molybdenum powder and ultrafine molybdenum powder doped with rare earth |
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