CN100446899C - Prepn process of superfine W-Cu composite powder - Google Patents
Prepn process of superfine W-Cu composite powder Download PDFInfo
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- CN100446899C CN100446899C CNB2005100314461A CN200510031446A CN100446899C CN 100446899 C CN100446899 C CN 100446899C CN B2005100314461 A CNB2005100314461 A CN B2005100314461A CN 200510031446 A CN200510031446 A CN 200510031446A CN 100446899 C CN100446899 C CN 100446899C
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Abstract
The present invention relates to a method for preparing ultrafine tungsten copper composite powder. In the method, prepared soluble tungsten copper salt collosol is treated by spray drying by the collosol and spray drying techniques, ultrafine or nanon powder with adjustable tungsten copper component proportion is prepared by calcination and two-step reduction, raw materials are prepared into 10 to 35 wt% of a solution according to needed copper and tungsten, a surface active agent is added, acid or alkali is added to control the pH value of the solution or collosol to be 3 or 4, the collosol is then treated by spray drying to obtain tungsten-copper salt or oxide composite powder precursors, and the precursor powder is calcined to obtain the tungsten copper composite powder. The composite powder has the advantages of high heat conductivity, electric conductivity and tensibility and greatly increased intensity.
Description
Technical field:
The present invention relates to nano-powder material field and field of powder metallurgy, particularly adopt nanometer technology to prepare superfine W-Cu composite powder.
Background technology:
Tungsten-copper composite material has the advantage of tungsten and copper, its density height, thermal coefficient of expansion are low, electric conductivity and thermal conductivity are good, are widely used as in contact material, electrode material and the modern microelectronics information industry and are used as electronic package material and heat sink materials such as microwave power device substrate, connector, radiating subassembly.Militarily this material can be used as the guide material of magnetic artillery and the broken first property of medicine cover of high explosive anti-tank cartridge.Traditional preparation process tungsten-copper composite material method is generally high-temperature liquid-phase sintering process and infiltration method.The high-temperature liquid-phase sintering is that tungsten powder and copper powder are mixed the back at sintering more than 1500 ℃, because tungsten and copper are immiscible, temperature is too high, and copper oozes out easily, and prepared alloy density has only about 94-95%; Adopt the activating solution phase sintering though add activators such as nickel, cobalt, but make density reach 98-99%, but the electric conductivity and the thermal conductivity of alloy all had adverse effect.Infiltration method is to prepare W skeleton earlier, then with infiltration of copper in the W skeleton hole, can make the alloy density reach 99%, alloy density height, electrical and thermal conductivity than the preparation of high-temperature liquid-phase sintering process are good, but infiltration method has limited size, the shape of the composition and the parts of alloy, coarse microstructure simultaneously, and skewness influences the electrical and thermal conductivity and the distortion of materials processing characteristics of alloy.Nanometer powder is owing to have nanometer size effect, can make immiscible tungsten and copper produce solid solution, and the nano-class composite W-Cu powder body presents strong densified effect when sintering, can one the step sintering near complete fine and close, overcome by adding the problem that activating agent improves material density and causes material property decline.
The existing abroad report of the preparation method of relevant W-Cu composite powder.United States Patent (USP) 5,956,560 adopt chemical coating method that tungsten powder surface is evenly coated one deck copper powder.But chemical coating method just coats one deck copper powder at tungsten powder surface, not have the original position of powder element of realization atomic scale truly compound, can not really solve the solubility of tungsten in copper.P/M Science﹠amp; Technology (1999, No.1,9-14) reported that employing sodium tungstate crystal and Schweinfurt green crystal are raw material in " Synthesis and Evaluation of advancednano-crystalline tungsten based materials ", it is mixed with mixed solution, obtain W-Cu solid solution colloid, the gauge that the W particle surface is coated with Cu is 25-75nm.But this coating layer thickness differs, and technical process is more complicated also, is unsuitable for prepared in batches nano-class composite W-Cu powder end.Domestic also have research to W-Cu composite powder, but sintering temperature is difficult to control, and copper is easy to ooze out mutually, and chemistry is easy to introduce when coating and is mingled with.Chinese invention patent Zl03143145.3 adopts mechanical alloying method to prepare the thin brilliant tungsten-copper alloy with higher-strength, this invention is passed through the mechanical alloying method process lowest optimization, add surfactant and process control agent, W-Cu composite powder is evenly distributed and extremely refinement of crystal grain, even forming nanocrystallinely, mechanical alloying W-Cu composite powder direct sintering can reach densified fully.Its shortcoming be the time long, be not suitable for producing in batches, powder is sheet, insufficient formability, and the increase that brought impurity iron content of long-time ball milling, reduces the electrical and thermal conductivity performance of the tungsten-copper composite material behind the sintering.Coprecipitation is that CuWO is produced in elder generation's co-precipitation in solution
4, carry out hydrogen reduction again, though can obtain tungsten, copper is evenly distributed and tungsten particle is tiny composite powder, this powder compacting poor performance, sintered alloy density is lower, and wet processing is tediously long, and technological parameter is wayward.Oxide mixing and ball milling-spray-drying-co-reducing process is the oxide mixing with cupric oxide and tungsten, long-time ball milling, again that ball milling is good slip spray-drying is prepared spray-dired powder reduction the superfine W-Cu composite powder that tungsten is evenly distributed mutually with copper mutually in reducing atmosphere.This technology is fit to large-scale industrial production, but technology controlling and process is difficult, repeatability and poor stability, and equally also introduce impurity element in the mechanical milling process easily, influence the performance of material.
Summary of the invention:
The present invention fully utilizes the strong point of existing process, adopting chemical colloidal sol-spray-drying-calcining-(low temperature+high temperature) two step hydrogen reduction technology to prepare the tungsten copper composition can be with the superfine W-Cu composite powder of arbitrary proportion to satisfy occasions different to Tungsten-copper Composites conduction, heat conduction and mechanical property requirements under the different condition, powder size is less than 1 μ m, powder shape spherical in shape, oxygen content in power is low, this method is suitable for large-scale industrial production, and technology controlling and process is simple.For achieving the above object, the scheme that the present invention adopts is:
(1) material composition is tungsten and copper, and wherein copper is 1-99wt%, and all the other content are tungsten.
(2) adopting a kind of in a kind of and copper nitrate in metatungstate, paratungstate, the wolframic acid, copper chloride, the copper sulfate crystal is raw material.
(3) raw material in (2) is mixed in required tungsten, copper component ratio, be mixed with the solution that concentration is 10-35wt%.
(4) adding small amount of acid or alkali adjusting pH is 3～4 in solution.
(5) add surfactant polyethylene (PEG), stearic acid (or stearate), N in (4) solution, dinethylformamide after stirring, obtains colloid.
(6) colloid in (5) is carried out spray pyrolysis on spray dryer, make ultra-fine mixed-powder presoma.
(7) the ultra-fine mixed-powder presoma that (6) are made is calcined 0.5-3h between 150～500 ℃, obtains tungsten copper oxide composite end.
(8) the superfines presoma that (7) are made is at reducing atmosphere H
2In, behind 120～400 ℃ and 500-900 ℃ reduction 30-150min, obtain superfine W-Cu composite powder respectively.
Advantage of the present invention and good effect are embodied in:
(1) powder size of the present invention's preparation is thin, can be less than 200nm, and the purity height reaches more than 99.5%, and oxygen content can be according to the W-Cu composite powder of operating position under the different condition according to performance requirement design and preparation heterogeneity less than 0.4wt% in the powder.
(2) the superfine W-Cu composite powder particle spherical in shape of the present invention's preparation has good flowability and mouldability, can be at the complex-shaped parts of 100-500MPa forming under the pressure.
(3) W-Cu composite powder of the present invention's preparation has realized that the original position of tungsten and copper is compound, and component distributing is very even.
(4) W-Cu composite powder of the present invention's preparation has good sintering characteristic, can be directly once sintered near complete fine and close, and powder is insensitive to sintering temperature in full densification temperature scope, can control material property preferably.
(5) alloy has high thermal conductivity and high ductility behind the prepared W-Cu composite powder sintering of the present invention, with the alloy phase ratio of using high-temperature liquid-phase sintering, infiltration or prepared by mechanical alloy under the identical component condition, its thermal conductivity, electric conductivity and ductility, intensity improve greatly.
(6) compare with reported method, technology of the present invention is simple, and process is easy to control, and powder output is big, is fit to suitability for industrialized production.
The specific embodiment
Be described further below in conjunction with example:
Example 1:
(1) takes by weighing 97g Cu (NO
3)
23H
2O and 128gAMT are dissolved in 774gH
2O is configured to the solution that concentration is 20wt%.
(2) in (1), add salpeter solution and regulate pH value to 3～4.
(3) in (2), add 0.5wt% polyethylene glycol PEG, evenly stir 10min.
(4) colloid in (3) is carried out spray pyrolysis, obtain tungsten copper oxide mixed-powder presoma.
(5) tungsten copper oxide mixed-powder presoma in (4) is calcined in air, calcining heat is 250 ℃, and calcination time is 90min, obtains the superfine W-Cu oxide mixed-powder of W-20Cu.
(6) to (5) powder at H
2Respectively through two step reducing process of 200 ℃ and 750 ℃, obtain the superfine W-Cu composite powder of W-20Cu under the atmosphere.
(7), and become thin brilliant W-20Cu composite at 1200 ℃ of following high temperature sinterings with the W-20Cu composite powder compression moulding under the pressure of 250Mpa for preparing.
Example 2:
(1) takes by weighing 185gCu (NO
3)
23H
2O and 58gAPT are dissolved in 756gH
2O is configured to the solution that concentration is 20wt%.
(2) in (1), add oxalic acid solution and regulate pH value to 3～4.
(3) add 0.5wt%N in (2), dinethylformamide evenly stirs 30min.
(4) colloid in (3) is carried out spray pyrolysis, obtain tungsten copper oxide mixed-powder presoma.
(5) tungsten copper oxide mixed-powder presoma in (4) is calcined in air, calcining heat is 300 ℃, and calcination time is 90min, obtains W-50Cu superfine W-Cu composite powder.
(6) to (5) powder at H
2Respectively through the two step reducing process of 300 ℃ of reduction 120min and 750 ℃ of reduction 150min, obtain the superfine W-Cu composite powder of W-50Cu under the atmosphere.
(7), and become thin brilliant W-50Cu composite at 1300 ℃ of following high temperature sinterings with the W-50Cu composite powder compression moulding under the pressure of 250Mpa for preparing.
Example 3:
(1) takes by weighing 303gCu (NO
3)
23H
2O and 27.4gAMT are dissolved in 544gH
2O is configured to the solution that concentration is 30wt%.
(2) in (1), add oxalic acid solution and regulate pH value to 3～4.
(3) in (2), add the 0.5wt% stearic acid, evenly stir 40min.
(4) colloid in (3) is carried out spray pyrolysis, obtain tungsten copper oxide mixed-powder presoma.
(5) tungsten copper oxide mixed-powder presoma in (4) is calcined in air, calcining heat is 400 ℃, and calcination time is 150min, obtains the superfine W-Cu oxide mixed-powder of W-80Cu.
(6) with (5) powder at H
2Respectively through the two step reducing process of 400 ℃ of reduction 120min and 850 ℃ of reduction 150min, obtain the superfine W-Cu composite powder of W-80Cu under the atmosphere.
(7), and become thin brilliant W-80Cu composite at 1100 ℃ of following high temperature sinterings with the W-80Cu composite powder compression moulding under the pressure of 400Mpa for preparing.
Claims (1)
1. the preparation method of a superfine W-Cu composite powder adopts colloidal sol and the spray drying technology tungsten copper soluble-salt colloidal sol spray-drying with preparation, goes on foot the powder that the reduction preparation is ultra-fine or the fine/nano tungsten-copper component ratio is adjustable through calcining and two, it is characterized in that:
(1) material composition is tungsten and copper, and wherein copper is 1-99wt%, and all the other content are tungsten;
(2) adopting a kind of in a kind of and copper nitrate in metatungstate, paratungstate, the wolframic acid, copper chloride, the copper sulfate crystal is raw material;
(3) raw material is mixed in required tungsten, copper component ratio, be mixed with the solution that concentration is 10-35wt%;
(4) adding small amount of acid or alkali adjusting pH is 3～4 in solution;
(5) add surfactant polyethylene, stearic acid or N, dinethylformamide stirs, and obtains colloid;
(6) colloid is carried out spray pyrolysis on spray dryer, make ultra-fine mixed-powder presoma;
(7) ultra-fine mixed-powder presoma is calcined 0.5-3h between 250～400 ℃, obtain superfine W-Cu oxide composite end;
(8) superfine W-Cu oxide composite end is at reducing atmosphere H
2In, behind 120～400 ℃ and 500-900 ℃ reduction 30-150min, obtain superfine W-Cu composite powder respectively.
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041421B (en) * | 2011-01-13 | 2012-11-07 | 中南大学 | High-tungsten content high-compactness fine-grain tungsten-copper material and preparation method thereof |
| CN102161097A (en) * | 2011-01-29 | 2011-08-24 | 中南大学 | Preparation method of novel fine grained tungsten copper electrode material |
| CN102601378A (en) * | 2011-07-18 | 2012-07-25 | 厦门虹鹭钨钼工业有限公司 | Method for preparing ultrafine tungsten copper composite powder by low-temperature combustion method |
| CN103223494B (en) * | 2013-03-27 | 2015-05-13 | 河南科技大学 | Preparation method of tungsten copper oxide composite powder through hydro-thermal synthesis |
| CN103521763A (en) * | 2013-11-01 | 2014-01-22 | 赣州中瑞材料科技有限公司 | Process for preparing superfine tungsten-base alloy powder by microwave-assisted ball-milling |
| CN103600087B (en) * | 2013-11-18 | 2016-01-20 | 厦门理工学院 | A kind of aerosol spray-reducing process prepares the method at ultrafine tungsten argentum composite powder end |
| CN103935961B (en) * | 2014-04-21 | 2017-01-25 | 华侨大学 | Metallic oxide nano-powder preparation method capable of achieving large-scale production |
| CN105734318A (en) * | 2016-04-21 | 2016-07-06 | 长沙微纳坤宸新材料有限公司 | Method for preparing nano-gradient composite W-Cu material |
| CN106077695B (en) * | 2016-08-11 | 2019-03-01 | 河南科技大学 | A kind of preparation method of high-copper tungsten copper nano composite powder |
| CN108620600B (en) * | 2017-12-18 | 2021-10-22 | 贵研铂业股份有限公司 | High-purity platinum black with large specific surface area and preparation method thereof |
| CN108251685B (en) * | 2018-01-22 | 2020-04-07 | 北京科技大学 | Tungsten dispersion strengthening copper-based composite material and preparation method thereof |
| CN110961656B (en) * | 2019-11-18 | 2021-07-09 | 昆明理工大学 | Preparation method of copper-nickel alloy powder |
| CN112958778B (en) * | 2021-02-02 | 2021-12-03 | 长沙微纳坤宸新材料有限公司 | Superplastic nano in-situ composite W-Cu material and preparation method thereof |
| CN113714506A (en) * | 2021-09-03 | 2021-11-30 | 天津大学 | Freeze-drying preparation method of molybdenum-doped superfine tungsten-copper alloy |
| CN114015920B (en) * | 2021-11-04 | 2022-11-08 | 中南大学 | Nano-carbide reinforced fine-grain high-temperature W-Cu material and preparation method thereof |
| CN114535589B (en) * | 2022-01-07 | 2024-02-13 | 西安理工大学 | Preparation method of tungsten copper heat sink component for optical module |
| CN114959333B (en) * | 2022-05-31 | 2022-11-11 | 河源市凯源硬质合金股份有限公司 | Tungsten-copper alloy and preparation method thereof |
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