CN1392012A - Process for preparing super fine tunsten-copper composite powder - Google Patents
Process for preparing super fine tunsten-copper composite powder Download PDFInfo
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- CN1392012A CN1392012A CN 02114601 CN02114601A CN1392012A CN 1392012 A CN1392012 A CN 1392012A CN 02114601 CN02114601 CN 02114601 CN 02114601 A CN02114601 A CN 02114601A CN 1392012 A CN1392012 A CN 1392012A
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Abstract
The present invention prepares superfine composite tungsten-copper powder through liquid phase chemical deposition process. Inside one reactor, copper compound solution is mixed with dispersant to elimiante electrostatic attraction between solid particles and copper phase is deposited homogeneously onto the surface of superfine tungsten partical to obtain copper phase coated tungsten phase particle and thus superfine composite tungsten-copper powder. The process has the features of low power consumption, short production period, high purity and low oxygen content of composite tungsten-copper powder, etc. The composite tungsten-copper powder may be further produced into pseudo tungsten-copper alloy and high-density, high-heat conductivity, high-conductivity and low-expansion coefficient composite material with wide application.
Description
(1) technical field:
The present invention relates to the preparation method of ultra-fine tungsten-copper composite powder in the metal material field.
(2) background technology:
Tungsten-copper pseudo-alloy is with high temperature resistant, the high rigidity of tungsten and copper, low-expansion coefficient, high heat-conductivity conducting, good characteristics such as plasticity, and is with a wide range of applications.Main manufacture methods by tungsten-device that the copper pseudo-alloy is formed comprises: cellular tungsten is to infiltrate liquid copper in the skeleton, and the hot compression composite W-Cu powder comprises liquid-phase sintering, recompression, various technology such as blast compression.The method of utilizing mould to annotate composite W-Cu powder can be made complicated section bar.The energy employing is in or makes device near tungsten-copper pseudo-alloy of solid density is optimal.Except mechanical property improvement, improve pseudo-alloy density and also can improve thermal conductivity, be crucial for the tungsten-copper pseudo-alloy of the electronic device material that is used for high-performance, high integration, high reliability in the electronics industry.
Since in tungsten-copper system between different component intersolubility very little, therefore, more than 1083 ℃ and when having liquid copper, density effect completely appears in tungsten-copper pseudo-alloy.Because liquid copper moulding and the compressibility capillary pressure that is produced when sprawling, liquid copper is tungsten reason such as oligodynamical in copper to the lubrication of tungsten particle and when being higher than 1200 ℃, tungsten particle produces relative displacement during sintering, tungsten particle might be replaced by copper, the local density effect and the rearrangement of tungsten structure, to cause tungsten phase and the copper distributional difference mutually and the leakage of copper in the sintering device, and cause the hot property of sintering device and mechanical performance to descend.
At present, the preparation method of tungsten-copper composite powder mainly contains high temperature reduction method and mechanical alloying method.The high temperature reduction method is that first oxide or hydroxide reaction generation with wolframic acid ammonium salt and copper contains copper tungstate (CuWO
4) and tungstic acid (WO
3) tungsten-copper composite oxide power, again this composite powder is reduced with hydrogen continuously 300～00 ℃ of scopes, make the tungsten-copper composite powder that a kind of tungsten coats the copper phase mutually.Mechanical alloying method is that tungsten and copper are mixed by a certain percentage, makes tungsten-copper composite powder by mechanical ball milling.Because tungsten and aspects such as copper particle size, proportion and hardness is different, so be difficult to make tungsten phase and the mutually equally distributed tungsten-copper composite powder of copper with mechanical alloying method, and the ratio of tungsten and copper is difficult to accurate control in the composite powder, in making the device process, easily produce copper leakage, make this functional composite material combination property descend.
(3) summary of the invention:
For overcome the tungsten that exists in the prior art mutually with copper mutually in skewness, the composite powder ratio of tungsten and copper be difficult to accurate control, in making the device process, easily produce copper leakage, temperature height, time are long, and material combination property decline weak point, the present invention proposes a kind of method for preparing ultra-fine tungsten-copper composite powder.
The present invention adopts liquid-phase chemistry deposition technique to prepare ultra-fine tungsten-copper composite powder.
This preparation method produces the liquid phase chemical deposition copper solution in reactor, in liquid phase chemical deposition copper solution deposition process, added dispersant, eliminated the electrostatic attraction between solid particle, make copper deposit to superfine metal tungsten particle sub-surface mutually uniformly, obtain coating the ultra-fine tungsten-copper composite powder body that the monodisperse particles of tungsten phase is formed mutually substantially by copper.In preparation process, should make copper deposition solution be in dynamical state.
Concrete method is:
(1) respectively with deionized water with quantitative copper sulphate (CuSO
45H
2O), complexing agent, stabilizing agent and dispersant are mixed with solution.Above-mentioned various solution are added to one are equipped with in the reactor of agitator and mix, regulating pH with NaOH solution is 0～14, adds formaldehyde, transfers to finite concentration with deionized water at last, is the liquid phase chemical deposition copper solution;
(2) under the copper solution dynamic condition, quantitative ultrafine tungsten powder is added in the copper solution, after 0.5～5 hour, leaves standstill cooling,, solids 60～160 ℃ of vacuum dehydration dryings, is got ultra-fine tungsten-copper composite powder through separating 30～70 ℃ of continuous stirring reactions.
Dispersant can singlely be selected anion surfactant or non-ionic surface active agent for use, also can be with anion and the compound use of non-ionic surface active agent.The total concentration of dispersant is 0～10g/L.When being the complexing agent of anion surfactant and non-ionic surface active agent as dispersant, the percentage by weight of non-ionic surface active agent and anion surfactant is 0～100, and the gained tungsten-copper composite powder does not produce agglomeration, for monodisperse particles is formed.
The present invention compared with prior art owing to be in solution, to carry out chemical deposition, Cu in the solution
2+Ion can be reduced to metallic copper fully substantially and be coated on the tungsten particle surface, according to adding Cu in the solution
2+Ion concentration and tungsten powder amount make tungsten-copper ratio easy to control.Owing in solution, carry out having added dispersant in the chemical deposition process, eliminated the electrostatic adsorption between particle and the particle, metallic copper and matrix tungsten powder particles to deposition have peptizaiton, thereby make copper deposit to the surface of individual tungsten powder particle uniformly, form by copper and coat the tungsten-copper composite powder that the individuality of tungsten phase is formed mutually substantially.Simultaneously, this product have that energy consumption is little, with short production cycle, the characteristics of tungsten-copper composite powder purity height, little, the no copper leakage phenomenon of oxygen content and even tissue.
(4) specific embodiment:
Embodiment 1:
Preparation copper content is 4% class composite W-Cu powder 93.7g.
With copper sulphate (CuSO
4H
2O) 15.0g and complexing agent (sodium potassium tartrate tetrahydrate 8.0g, disodium EDTA 36.0g) are used 500mL deionized water dissolving (filtering and impurity removing in case of necessity) respectively, again copper-bath and enveloping agent solution are added to simultaneously that being equipped with of 2500mL stirred and the reactor of heater in mix, regulating its pH value with NaOH solution is 12.(potassium ferrocyanide 0.015g, α, α-Lian Biding 0.03g) also uses deionized water dissolving with stabilizing agent, and dispersant is added in the solution, and adding to overall solution volume with deionized water again is 2000mL, gets copper sulphate (CuSO
4H
2O) concentration is the solution of 7.5g/L; Open agitating device, and be warming up to 40 ℃, add formaldehyde (37%) 16mL, tungsten powder (about 1 micron of particle size) 90.0g in stirring, 40 ℃ of control solution temperatures were with the mixing speed stirring reaction of 100r/min 3 hours; Leave standstill cooling, isolated by filtration; Spend the acquired solids of deionised water more than 3 times, under vacuum condition dry 1 hour, its temperature was controlled at 100 ℃, got final product to such an extent that required copper content is 4% class composite W-Cu powder.Product is through scanning electron microscope analysis, and particle size maintains the original state substantially, and is the monodisperse particles composition; X-ray diffraction is analyzed it and is tungsten phase and copper phase composition.
Used dispersant is the complexing agent of anion surfactant and non-ionic surface active agent in the present embodiment, and its match ratio is APES 1g, sodium alkyl benzene sulfonate 1g.
Embodiment 2:
With copper sulphate (CuSO
45H
2O) 40.0g and complexing agent (sodium potassium tartrate tetrahydrate 24.0g, disodium EDTA 40.0g) are used 800mL deionized water dissolving (filtering and impurity removing in case of necessity) respectively, again copper-bath and enveloping agent solution are added to simultaneously that being equipped with of 2500mL stirred and the reactor of heater in mix, regulating its pH value with NaOH solution is 13.Stabilizing agent (potassium ferrocyanide 0.04g, α, α-Lian Biding 0.03g) is dissolved with appropriate amount of deionized water, and dispersant is added in the above-mentioned solution, adding to overall solution volume with deionized water again is 2000mL, gets copper sulphate (CuSO
4H
2O) concentration is the solution of 20.0g/L; Open agitating device, and be warming up to 60 ℃, under agitation add formaldehyde (37%) 20mL, slowly add tungsten powder (about 1 micron of particle size) 40.0g, 60 ℃ of control solution temperatures were with the mixing speed stirring reaction of 140r/min 1 hour; Leave standstill cooling, isolated by filtration, spend the acquired solids of deionised water more than 3 times, under vacuum condition dry 1 hour, its temperature was controlled at 90 ℃, got final product to such an extent that copper content is 20% class composite W-Cu powder 50g.Product is through scanning electron microscope analysis, and particle size maintains the original state substantially, and is the monodisperse particles composition; X-ray diffraction is analyzed it and is tungsten phase and copper phase composition.
Used dispersant is the complexing agent of anion surfactant and non-ionic surface active agent in the present embodiment, and its match ratio is AEO 2g, fatty alcohol polyoxyethylene ether sulfate 4g.
Embodiment 3:
With copper sulphate (CuSO
45H
2O) 20.0g and complexing agent (sodium potassium tartrate tetrahydrate 14.0g, disodium EDTA 25.0g) are used 500mL deionized water dissolving (filtering and impurity removing in case of necessity) respectively, again copper-bath and enveloping agent solution are added to simultaneously that being equipped with of 2500mL stirred and the reactor of heater in mix, regulating its pH value with NaOH solution is 12.5.Stabilizing agent (potassium ferrocyanide 0.02g, α, α-Lian Biding 0.01g) is dissolved with appropriate amount of deionized water, and dispersant is added in the above-mentioned solution, adding to overall solution volume with deionized water again is 2000mL, gets copper sulphate (CuSO
4H
2O) concentration is the solution of 10.0g/L; Open agitating device, and be warming up to 50 ℃, under agitation add formaldehyde (37%) 15mL, slowly add tungsten powder (about 1 micron of particle size) 45.0g, 50 ℃ of control solution temperatures were with the mixing speed stirring reaction of 160r/min 2 hours; Leave standstill cooling, isolated by filtration, spend the acquired solids of deionised water more than 3 times, under vacuum condition dry 1 hour, its temperature was controlled at 100 ℃, got final product to such an extent that copper content is 10% class composite W-Cu powder 50g.Product is through scanning electron microscope analysis, and particle size maintains the original state substantially, but part particle agglomeration phenomenon is arranged; X-ray diffraction is analyzed it and is tungsten phase and copper phase composition.
Used dispersant is an anion surfactant in the present embodiment, i.e. alkylbenzenesulfonate 3g.
Embodiment 4:
With copper sulphate (CuSO
45H
2O) 20.0g and complexing agent (sodium potassium tartrate tetrahydrate 14.0g, disodium EDTA 25.0g) are used 500mL deionized water dissolving (filtering and impurity removing in case of necessity) respectively, again copper-bath and enveloping agent solution are added to simultaneously that being equipped with of 2500mL stirred and the reactor of heater in mix, regulating its pH value with NaOH solution is 12.5.Stabilizing agent (potassium ferrocyanide 0.02g, α, α-Lian Biding 0.01g) is dissolved with appropriate amount of deionized water, and dispersant is added in the above-mentioned solution, adding to overall solution volume with deionized water again is 2000mL, gets copper sulphate (CuSO
4H
2O) concentration is the solution of 10.0g/L; Open agitating device, and be warming up to 50 ℃, under agitation add formaldehyde (37%) 15mL, slowly add tungsten powder (about 1 micron of particle size) 45.0g, 50 ℃ of control solution temperatures were with the mixing speed stirring reaction of 160r/min 2 hours; Leave standstill cooling, isolated by filtration, spend the acquired solids of deionised water more than 3 times, under vacuum condition dry 1 hour, its temperature was controlled at 100 ℃, got final product to such an extent that copper content is 10% class composite W-Cu powder 50g.Product is through scanning electron microscope analysis, and particle size maintains the original state substantially, but part particle agglomeration phenomenon is arranged; X-ray diffraction is analyzed it and is tungsten phase and copper phase composition.
Used dispersant is a non-ionic surface active agent in the present embodiment, i.e. AEO 3g.
Claims (4)
1. the preparation method of a ultra-fine tungsten-copper composite powder body is characterized in that adopting liquid-phase chemistry deposition technique, and has added dispersant in the liquid phase chemical deposition copper solution of preparation, and concrete grammar is:
A. with copper sulphate (CuSO
45H
2O), complexing agent, dispersant, stabilizing agent be mixed with certain concentration solution with deionized water in proportion, regulates pH with alkaline solution, becomes the liquid phase chemical deposition copper solution;
B. solution is stirred, and heat, when stirring, add formaldehyde and ultrafine tungsten powder, carry out the copper deposition;
C. will deposit the cooling of tungsten-copper composite powder solution left standstill, separate;
D. spend the tungsten-copper composite powder of deionised water gained;
E. the tungsten-copper composite powder vacuum dehydration drying after will washing.
2. the preparation method of ultra-fine tungsten-copper composite powder body as claimed in claim 1 is characterized in that mixing speed is 30～300r/min.
3. the preparation method of ultra-fine tungsten-copper composite powder body as claimed in claim 1, its feature is 40～180 ℃ with the vacuum dehydration baking temperature of separating obtained tungsten-copper composite powder.
4. the preparation method of ultra-fine tungsten-copper composite powder body as claimed in claim 2, it is characterized in that dispersant can singlely select anion surfactant or non-ionic surface active agent for use, also can be the compound of non-ionic surface active agent and anion surfactant, and the percentage by weight of nonionic and anion surfactant be 0～100.
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| CN1254340C CN1254340C (en) | 2006-05-03 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411779C (en) * | 2006-10-13 | 2008-08-20 | 武汉理工大学 | Prepn process of composite W-Cu powder for preparing high density alloy |
| CN100446899C (en) * | 2005-04-14 | 2008-12-31 | 中南大学 | Prepn process of superfine W-Cu composite powder |
| CN101428345B (en) * | 2007-11-09 | 2010-08-11 | 北京有色金属研究总院 | Method of manufacturing ultrafine molybdenum powder or ultrafine tungsten powder surface clad metal copper |
| CN101987359A (en) * | 2010-11-16 | 2011-03-23 | 蒋剑秋 | Preparation method of reduced copper coated iron composite powder by using wet method |
| CN102554218A (en) * | 2011-11-23 | 2012-07-11 | 西安理工大学 | Method for preparing tungsten-copper composite powder by means of electroless copper plating |
| CN101780541B (en) * | 2009-01-16 | 2012-07-25 | 蒋剑秋 | Bronze-coated iron composite powder and manufacturing method thereof |
| CN104174854A (en) * | 2014-07-14 | 2014-12-03 | 昆山安泰美科金属材料有限公司 | Method for manufacturing miniature tungsten-based alloy part |
| CN104550943A (en) * | 2015-01-28 | 2015-04-29 | 中国科学院过程工程研究所 | Spherical copper coating tungsten composite powder, preparation method and application thereof |
| CN115609000A (en) * | 2020-12-24 | 2023-01-17 | 赵伟 | Preparation method of high-dispersion nickel nano dispersion liquid |
-
2002
- 2002-05-30 CN CN 02114601 patent/CN1254340C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446899C (en) * | 2005-04-14 | 2008-12-31 | 中南大学 | Prepn process of superfine W-Cu composite powder |
| CN100411779C (en) * | 2006-10-13 | 2008-08-20 | 武汉理工大学 | Prepn process of composite W-Cu powder for preparing high density alloy |
| CN101428345B (en) * | 2007-11-09 | 2010-08-11 | 北京有色金属研究总院 | Method of manufacturing ultrafine molybdenum powder or ultrafine tungsten powder surface clad metal copper |
| CN101780541B (en) * | 2009-01-16 | 2012-07-25 | 蒋剑秋 | Bronze-coated iron composite powder and manufacturing method thereof |
| CN101987359A (en) * | 2010-11-16 | 2011-03-23 | 蒋剑秋 | Preparation method of reduced copper coated iron composite powder by using wet method |
| CN101987359B (en) * | 2010-11-16 | 2012-10-03 | 蒋剑秋 | Preparation method of reduced copper coated iron composite powder by using wet method |
| CN102554218A (en) * | 2011-11-23 | 2012-07-11 | 西安理工大学 | Method for preparing tungsten-copper composite powder by means of electroless copper plating |
| CN104174854A (en) * | 2014-07-14 | 2014-12-03 | 昆山安泰美科金属材料有限公司 | Method for manufacturing miniature tungsten-based alloy part |
| CN104174854B (en) * | 2014-07-14 | 2016-08-24 | 昆山安泰美科金属材料有限公司 | A kind of method preparing miniature tungsten-bast alloy part |
| CN104550943A (en) * | 2015-01-28 | 2015-04-29 | 中国科学院过程工程研究所 | Spherical copper coating tungsten composite powder, preparation method and application thereof |
| CN115609000A (en) * | 2020-12-24 | 2023-01-17 | 赵伟 | Preparation method of high-dispersion nickel nano dispersion liquid |
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|---|---|
| CN1254340C (en) | 2006-05-03 |
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