CN101168197A - Method for preparing ultra-fine/nano tungsten-copper-nickel composite powder - Google Patents
Method for preparing ultra-fine/nano tungsten-copper-nickel composite powder Download PDFInfo
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- CN101168197A CN101168197A CNA2006100324557A CN200610032455A CN101168197A CN 101168197 A CN101168197 A CN 101168197A CN A2006100324557 A CNA2006100324557 A CN A2006100324557A CN 200610032455 A CN200610032455 A CN 200610032455A CN 101168197 A CN101168197 A CN 101168197A
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Abstract
Provided is a process for preparing an ultra-fine/nanometer W-Cu-Ni composite powder. Firstly according to the proportion of W-Cu-Ni ingredients, relative metal salt is prepared to mixed salt solution with a concentration of 10-30wt% percents, a small amount of acids are added to control the pH, and surfactant gels are added to control particles in solution to reunite, thereby obtaining a mixed salt sol colloid of a homogeneous system. The mixed salt sol colloid is sprayed, dried, burned, and two-stage or multi-stage reduction is applied between 150 and 900 DEG C and under H2 atmosphere, and the ultra-fine/nanometer W-Cu-Ni composite powder is obtained. By adopting the ultra-fine/nanometer W-Cu-Ni composite powder prepared by the invention, the proportion of ingredients can be adjusted, and the proportion of ingredients of each element in powder is capable of being adjusted according to the requirement of alloys property. The powder has good coking characteristic, the density of alloys is high, and the characteristic that inhomogeneous organization when the content of CU is high in W-Cu alloys system is overcome.
Description
Technical field:
The present invention relates to a kind of ultra-fine/nano-scale W-Cu-Ni composite powder that adopts nanometer technology prepared composition adjustable ratio, belong to nano-powder material field and field of powder metallurgy.
Background technology:
The W-Cu composite all has purposes very widely in electrical industry, electronic information and war industry, as, being used as the mesohigh electrical contact material, Electronic Packaging, heat sink material etc. are a kind of purposes materials very widely.But because W and Cu are immiscible, Cu is to the non-constant of the wellability of W, and the fusing point of W and Cu differs greatly, and the uniformity in alloy property, material composition and institutional framework when sintering prepares the W-Cu composite is difficult to meet the demands.Tradition W-Cu composite generally adopts high-temperature liquid-phase sintering, Cu melting infiltration sintering, and these two kinds of methods all have very big shortcoming.
Chinese patent 03143145.3 discloses a kind of preparation method of thin brilliant tungsten-copper composite material, this patent adopts the mechanical alloying method preparation to have the thin brilliant W-20Cu alloy of higher-strength, this invention is passed through the mechanical alloying method process lowest optimization, add surfactant and process control agent, the tungsten copper mixed powder is evenly distributed and extremely refinement, even forming nanocrystallinely, mechanical alloying W-Cu composite powder direct sintering can reach densified fully.Chinese patent 200510031446.1 discloses a kind of method that adopts colloidal sol-spray-drying-two step hydrogen reduction method to prepare ultra-fine W-Cu composite powder, utilize the prepared powder sphericity height of this method, good fluidity, powder size is tiny, can reach below the 100nm, the sintering character of powder is good, sintering temperature reduces greatly, can adopt a step low-temperature sintering directly to reach density more than 99%, and adopt this method can realize that the component ratio of powder is adjustable, satisfy the occasion of the high ductility of material high density.
But when the Cu phase constituent height in the powder (surpass more than 40%), adopt said method to be easy to generate the segregation of Cu, make the sintering process difficulty of all even alloy densification of control institutional framework strengthen, to improve and the performance of stable alloy unfavorable.
Summary of the invention
In order to overcome the deficiency of existing W-Cu powder preparation method, the present invention proposes a kind of method that adopts colloidal sol-spray-drying-multistep reduction technique to prepare the adjustable ultra-fine/fine/nano tungsten-copper-nickel composite powder of W-Cu-Ni component ratio, and prepared powder particle is less than 100nm.
For achieving the above object, the scheme that the present invention adopts is:
A kind of ultra-fine/preparation method of fine/nano tungsten-copper-nickel composite powder, comprise batching, spray pyrolysis, calcining, hydrogen reducing, detailed process is as follows: adopt tungstate crystal, the mantoquita crystal, the nickel salt crystal is a raw material, raw material is mixed by required tungsten copper nickel component ratio, be mixed with the mixed-salt aqueous solution that concentration is 10～35wt%, adding acid for adjusting pH in solution is 2～3, adding mass percent and be 0.1～0.5% surfactant in solution stirs, obtain transparent colloid, colloid is carried out spray pyrolysis on spray dryer, make ultra-fine mixed-powder presoma, the ultra-fine mixed-powder presoma that makes is calcined 0.5～3h at 180～500 ℃, obtain tungsten copper nickel oxide mixed-powder, with the superfines presoma of gained at reducing atmosphere H
2In, through 120～300 ℃ and 600～900 ℃ of two step reduction, obtain ultra-fine/nano-scale W-Cu-Ni composite powder respectively.Or at 120～300 ℃, 400～600 ℃ and 650～900 ℃ of multistep reduction obtain ultra-fine/nano-scale W-Cu-Ni composite powder.
Described tungstate crystal comprises metatungstate crystal or paratungstate crystal;
Described mantoquita crystal comprises copper nitrate crystal or copper sulphate or copper chloride crystal;
Described nickel salt crystal comprises nickel nitrate crystal or nickelous sulfate or nickel chloride crystal;
Surfactant is poly-hexylene glycol (PEG) or poly-hexylene glycol or stearic acid (or stearate) or N, dinethylformamide.
Compare with existing method, adding element Ni further improves the adjustability of powder sintered performance and alloying component, can be adjustable to the powder composition in any range, the alloy organizing structure is very even, do not produce phase segregation, the ductility of alloy further improves, and sintering process is simplified, and is suitable for suitability for industrialized production.Adopt the powder size of the present invention's preparation tiny, can be less than 100nm, even less than 50nm, and purity height, reach more than 99.5%, oxygen content is less than 0.4wt% in the powder, and tungsten copper nickel component ratio can be regulated arbitrarily in the composite powder, can require design and prepare the tungsten copper nickel composite powder of various component ratios according to performance design; The pattern of the ultra-fine/nano-scale W-Cu-Ni composite powder of the present invention's preparation is spherical in shape or class is spherical, the flowability of powder and formability are good, can satisfy the requirement of powder injection forming well to mobile and apparent density, also can be used for press forming, powder has good sintering property, and density can be near complete fine and close behind the sintering; With the W-Cu-Ni composite powder of the method preparation, its sintering character is mixed with W-Cu-Ni alloy phase ratio with conventional element powders, and sintering temperature reduces more than 100 ℃, and the grain structure of alloy can refine to below the 3 μ m, and the mechanical property of alloy is improved.
Be described further below in conjunction with example:
The specific embodiment
Embodiment 1:
1. be the W-40Cu-10Ni batching by final powder component ratio, 142.6g copper nitrate crystal, 45.6g nickel nitrate crystal and 62.4g ammonium metatungstate crystal are dissolved in 750g H
2O is configured to the 20wt% mixed solution;
2. add dilute nitric acid solution and regulate pH value to 2～3;
3. add the 0.5wt% polyethylene glycol, evenly stir 10min;
4. colloid in (3) is carried out spray pyrolysis, obtain tungsten copper nickel oxide mixed-powder presoma;
5. powder presoma in (4) is calcined in air, calcining heat is 300 ℃, and calcination time is 90min, obtains ultra-fine/fine/nano tungsten-copper nickel oxide mixed-powder;
With tungsten copper nickel oxide mixed-powder at H
2Under the atmosphere respectively through two step reducing process of 150 ℃ and 790 ℃, obtain ultra-fine/fine/nano tungsten-copper-nickel composite powder of W-40Cu-10Ni, the granularity of powder is less than 100nm, powder agglomerates is the hollow ball shelly, form less than the nano particle of 100nm by several granularities, powder has good sintering characteristic at sintering below 1200 ℃, and institutional framework is very even, and sintered density reaches more than 99%.
Embodiment 2:
1. be that 90W-4Cu-6Ni calculates in final powder composition quality ratio, 21.9g copper chloride crystal, 49.8g nickel chloride crystal and 271.9g order of ammoniumparatungstate crystal are dissolved in 655.4gH
2Among the O, be configured to the 30wt% mixed solution;
2. add dilute nitric acid solution and regulate pH value to 2～3;
3. add polyethylene glycol 1g, evenly stir 10min;
4. colloid in (3) is carried out spray pyrolysis, obtain tungsten copper nickel oxide mixed-powder presoma;
5. powder presoma in (4) is calcined in air, calcining heat is 500 ℃, and calcination time is 120min, obtains ultra-fine/fine/nano tungsten-copper nickel oxide mixed-powder.
6. the tungsten copper nickel oxide mixed-powder that (5) are prepared is at H
2Under the atmosphere respectively through 120 ℃, three step reducing process of 600 ℃ and 800 ℃, obtain ultra-fine/nanoscale tungsten copper nickel composite powder of 90W-4Cu-6Ni, the granularity of powder is less than 100nm, powder agglomerates is the hollow ball shelly, is made up of less than the nano particle of 100nm several granularities, and powder has good sintering characteristic at sintering below 1300 ℃, institutional framework is very even, and sintered density reaches more than 99%.
Claims (2)
1. the preparation method of ultra-fine/fine/nano tungsten-copper-nickel composite powder, it is characterized in that: comprise batching, spray pyrolysis, calcining, hydrogen reducing, detailed process is as follows: adopt tungstate crystal, the mantoquita crystal, the nickel salt crystal is a raw material, raw material is mixed by required tungsten copper nickel component ratio, be mixed with the mixed-salt aqueous solution that concentration is 10～35wt%, adding acid for adjusting pH in solution is 2～3, adding mass percent and be 0.1～0.5% surfactant in solution stirs, obtain transparent colloid, colloid is carried out spray pyrolysis on spray dryer, make ultra-fine mixed-powder presoma, the ultra-fine mixed-powder presoma that makes is calcined 0.5～3h at 180～500 ℃, obtain tungsten copper nickel oxide mixed-powder, with the superfines presoma of gained at reducing atmosphere H
2In, through 120～300 ℃ and 600～900 ℃ of two step reduction, obtain ultra-fine/nano-scale W-Cu-Ni composite powder respectively;
Described tungstate crystal comprises metatungstate crystal or paratungstate crystal;
Described mantoquita crystal comprises copper nitrate crystal or copper sulphate or copper chloride crystal;
Described nickel salt crystal comprises nickel nitrate crystal or nickelous sulfate or nickel chloride crystal;
Described surfactant is poly-hexylene glycol or poly-hexylene glycol or stearic acid or stearate or N, dinethylformamide.
2. method according to claim 1 is characterized in that: described reduction can also be at 120～300 ℃, and 400～600 ℃ and 650～900 ℃ of three step reduction obtain ultra-fine/nano-scale W-Cu-Ni composite powder.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145386A (en) * | 2011-05-06 | 2011-08-10 | 河南煤业化工集团研究院有限责任公司 | Method for preparing metal with surface coated with nano nickel |
| 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 |
| CN104759632A (en) * | 2015-03-23 | 2015-07-08 | 北京科技大学 | Method of preparing nano-crystalline powdered alloy powder |
| CN105057681A (en) * | 2015-07-29 | 2015-11-18 | 昆山德泰新材料科技有限公司 | Preparation method for tungsten copper nickel alloy powder |
| CN105268983A (en) * | 2015-10-21 | 2016-01-27 | 陕西理工学院 | Preparation method of W-Ni-Cu prealloyed powder |
| CN107988543A (en) * | 2017-11-30 | 2018-05-04 | 西北有色金属研究院 | A kind of high-copper W-Ni-Cu alloy materials and preparation method thereof |
| CN108202145A (en) * | 2018-01-10 | 2018-06-26 | 昆明理工大学 | A kind of preparation method of nano aluminium oxide/copper composite strengthening phase |
| CN108889943A (en) * | 2018-09-05 | 2018-11-27 | 河北工业大学 | A kind of preparation of copper iron compound powder body material and its forming method |
| CN110961656A (en) * | 2019-11-18 | 2020-04-07 | 昆明理工大学 | Preparation method of copper-nickel alloy powder |
| CN110961653A (en) * | 2018-09-28 | 2020-04-07 | 荆门市格林美新材料有限公司 | Preparation method of copper-doped superfine nickel powder |
| CN111069618A (en) * | 2020-01-02 | 2020-04-28 | 崇义章源钨业股份有限公司 | WC-Co composite powder and preparation method and application thereof |
| CN114535589A (en) * | 2022-01-07 | 2022-05-27 | 西安理工大学 | Preparation method of tungsten-copper heat sink component for optical module |
| CN115401208A (en) * | 2022-09-02 | 2022-11-29 | 江苏大学 | Preparation method of nickel-based nano powder with controllable morphology |
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- 2006-10-25 CN CNA2006100324557A patent/CN101168197A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145386A (en) * | 2011-05-06 | 2011-08-10 | 河南煤业化工集团研究院有限责任公司 | Method for preparing metal with surface coated with nano nickel |
| 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 |
| CN104759632A (en) * | 2015-03-23 | 2015-07-08 | 北京科技大学 | Method of preparing nano-crystalline powdered alloy powder |
| CN105057681A (en) * | 2015-07-29 | 2015-11-18 | 昆山德泰新材料科技有限公司 | Preparation method for tungsten copper nickel alloy powder |
| CN105268983A (en) * | 2015-10-21 | 2016-01-27 | 陕西理工学院 | Preparation method of W-Ni-Cu prealloyed powder |
| CN105268983B (en) * | 2015-10-21 | 2017-09-22 | 陕西理工学院 | The preparation method of W Ni Cu pre-alloyed powders |
| CN107988543A (en) * | 2017-11-30 | 2018-05-04 | 西北有色金属研究院 | A kind of high-copper W-Ni-Cu alloy materials and preparation method thereof |
| CN108202145B (en) * | 2018-01-10 | 2021-12-17 | 昆明理工大学 | Preparation method of nano aluminum oxide/copper composite reinforced phase |
| CN108202145A (en) * | 2018-01-10 | 2018-06-26 | 昆明理工大学 | A kind of preparation method of nano aluminium oxide/copper composite strengthening phase |
| CN108889943A (en) * | 2018-09-05 | 2018-11-27 | 河北工业大学 | A kind of preparation of copper iron compound powder body material and its forming method |
| CN110961653A (en) * | 2018-09-28 | 2020-04-07 | 荆门市格林美新材料有限公司 | Preparation method of copper-doped superfine nickel powder |
| CN110961656B (en) * | 2019-11-18 | 2021-07-09 | 昆明理工大学 | Preparation method of copper-nickel alloy powder |
| CN110961656A (en) * | 2019-11-18 | 2020-04-07 | 昆明理工大学 | Preparation method of copper-nickel alloy powder |
| CN111069618A (en) * | 2020-01-02 | 2020-04-28 | 崇义章源钨业股份有限公司 | WC-Co composite powder and preparation method and application thereof |
| CN111069618B (en) * | 2020-01-02 | 2022-10-25 | 崇义章源钨业股份有限公司 | WC-Co composite powder and preparation method and application thereof |
| CN114535589A (en) * | 2022-01-07 | 2022-05-27 | 西安理工大学 | Preparation method of tungsten-copper heat sink component for optical module |
| 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 |
| CN115401208A (en) * | 2022-09-02 | 2022-11-29 | 江苏大学 | Preparation method of nickel-based nano powder with controllable morphology |
| CN115401208B (en) * | 2022-09-02 | 2024-02-27 | 江苏大学 | Preparation method of nickel-based nano powder with controllable morphology |
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