CN102389971B - Preparation method of La-doped W-Cu composite powder - Google Patents
Preparation method of La-doped W-Cu composite powder Download PDFInfo
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Abstract
The invention discloses a preparation method of La-doped W-Cu composite powder, which comprises the preparation of activated tungsten powder and the preparation of composite powder, wherein the preparation of the activated tungsten powder comprises the following steps: carrying out ultrasonic activation on tungsten powder in an activation liquid for 30-40 minutes, washing with de-ionized water after the activation is completed, and drying to obtain the activated tungsten powder. The preparation of the composite powder comprises the following steps: adding the activated tungsten powder into a chemical deposition solution, wherein the dosage of the tungsten powder is 30-50g/L; regulating with sodium hydroxide until the pH value is 12.0-13.0; carrying out ultrasonic deposition and coating at normal temperature for 40-80 minutes; and standing for 2-3 hours, filtering, washing, and drying to obtain the composite powder. The obtained powder has high component homogenizing degree, avoids the tungsten and copper oxide reduction process of the conventional preparation method, and has the advantages of simple treatment process and low preparation cost. Besides, the invention greatly improves the flowability of the composite powder in the sintering process, and carries out direct sintering at low temperature; and the relative density of sintering samples can be up to 98.7% or above.
Description
One, technical field
The present invention relates to the powder body material preparation field, specifically a kind of preparation method of La doping W-Cu composite powder.
Two, background technology
Powder metallurgy W-Cu composite is because having good Physical and mechanical properties, stronger Burning corrosion resistance, thermal shock resistance, and excellent thermal control and microwave absorbing property etc., be widely used in fields such as national defense industry, Aero-Space, electronic information and machinings, in national economy, occupy an important position, therefore, tungsten-bast alloy has been subject to the great attention of countries in the world all the time, has become one of comparatively active research field of material supply section educational circles.In these are used, often require the W-Cu material to have higher densification degree to improve its performance level.Just from present main direction of studying, ultra-fine/nanometer and gradient-structure functional material are the main directions of W-Cu composite research, and full densification, high performance aplitic texture W-Cu composite manufacture key are obtaining of ultra-fine/nanostructured W-Cu composite granule.At present, research both at home and abroad reports that the technology of preparing of more ultra-fine W-Cu powder has mechanical alloying, spray-drying method, colloidal sol-spray-drying-co-reducing process, freeze-dried method, sol-gel process, homogeneous precipitation method, mechanical thermal chemical method, oxide co-reducing process etc.For example, Central South University adopts colloidal sol-spray-drying-co-reducing process to prepare ultra-fine/nanometer W-10%Cu composite powder, and its alloy can obtain good combination property reason, and to be to obtain higher density and institutional framework behind sintering evenly tiny.HeFei University of Technology adopts homogeneous precipitation method, obtains Cu
2WO
4(OH)
2/ CuWO
42H
2The O predecessor after calcining, reduction, finally obtains copper content and is 30% ultra-fine W-Cu composite powder.The human sol-gel processes such as Raghunathan have prepared the nanocrystalline W base composite powder of sizes at 10～30nm, such as composite powders such as W-Mo, W-Cu, W-Ni and WC-Co.Said method partly exists cost higher, and the processing time is longer, is difficult to batch production, and there is easy introducing impurity in part preparation method, oxygen content is higher and the easy phenomenon such as agglomerating of powder.
Three, summary of the invention
The present invention aims to provide a kind of preparation method of La doping W-Cu composite powder, and technical problem to be solved is to make composite powder sintering under lower temperature reach higher sintered density, and reduces the agglomerating phenomenon of composite powder.
Technical solution problem of the present invention adopts following technical scheme:
The preparation method's of La doping W-Cu composite powder of the present invention characteristics are: comprise the preparation that activates tungsten powder and the preparation of composite powder;
The preparation of described activation tungsten powder is that tungsten powder was placed the activating solution ultrasonic activation 30-40 minute, obtains activating tungsten powder after activation is finished with deionized water washing and in 180-200 ℃ of dry 1-3 hour; The particle diameter of described tungsten powder is not more than 1 micron;
Described activating solution is the aqueous solution of hydrofluoric acid, ammonium fluoride and nitric acid, and the concentration of hydrofluoric acid is 30-60ml/L in the described activating solution, in the hydrofluoric acid solution of mass concentration 40%; The concentration of ammonium fluoride is 8-10g/L; The concentration of nitric acid is 50-80ml/L, in the salpeter solution of mass concentration 65%;
The preparation of described composite powder is that the activation tungsten powder is added in the chemical deposition solution, the addition of tungsten powder is 30-50g/L, with NaOH adjust pH 12.0-13.0, ultrasonic deposition coats 40-80 minute under the normal temperature, leaves standstill filtration after 2-3 hour, washing and drying and obtains composite powder;
Described chemical deposition solution is the aqueous solution of copper sulphate, lanthanum chloride, formaldehyde, disodium ethylene diamine tetraacetate and natrium citricum, the concentration of copper sulphate is 6-25g/L in the described chemical deposition solution, the concentration of lanthanum chloride is 0.8-2.6g/L, the concentration of formaldehyde is 5-20mL/L, the concentration of disodium ethylene diamine tetraacetate is 10-20g/L, and the concentration of natrium citricum is 20-30g/L.
The supersonic frequency of described ultrasonic activation is 40KHz, and power is 300-400W.
The supersonic frequency that described ultrasonic deposition coats is 40KHz, and power is 300-400W.
Described drying is prior to 120-160 ℃ of dry 0.5-1, again in 160-200 ℃ of dry 3-6 hour.
The composite powder of preparation is obtained pressed compact with the compacting of the unit pressure of 100MPa, described pressed compact is placed tube type resistance furnace, at H
2Protection is lower, and 1150-1300 ℃ of sintering 90-120min namely gets La doping W-Cu composite.
Then the present invention passes through normal temperature ultrasonic wave assistant chemical sedimentation at tungsten powder surface Coated Doping with Rare Earth Lanthanum Cu layer by tungsten powder being carried out the auxiliary activation processing of normal temperature ultrasonic wave, finally obtains the La doping W-Cu composite powder that homogeneous chemical composition distributes.Prepared powder has good sintering activity, direct lower temperature sintering, and sintering sample relative density reaches more than 98.7%, has namely reached very high densification degree.
Compared with the prior art, beneficial effect of the present invention is embodied in:
Compare with the preparation method of present ultra-fine W-Cu composite granule, normal temperature ultrasonic wave assistant chemical sedimentation prepares superfine rare-earth La doping W-Cu composite powder, and its copper tungsten composition is controlled, to satisfy the performance requirement of W-Cu sill under the different condition; The homogenising degree of gained powder composition of the present invention is high; Particularly need not conventional preparation method's tungsten copper Reduction of Oxide process, treatment process is simpler, and preparation cost is lower; The prepared Doping with Rare Earth Lanthanum Cu of the present invention coats W surface recombination powder, Cu and La reach respectively 15-25% and 0.5-2% at whole composite granule Atom ratio content, greatly improved the flowability of composite granule sintering process, direct lower temperature sintering, sintering sample relative density reaches more than 98.7%.
Four, the specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1:
1, the preparation of activation tungsten powder
Particle diameter was placed the activating solution ultrasonic activation 30 minutes less than 1 micron tungsten powder, and supersonic frequency is 40KHz, and power is 300-400W, obtains activating tungsten powder in 1 hour with deionized water washing three times and in 200 ℃ of dryings after activation is finished;
Described activating solution is the aqueous solution of hydrofluoric acid, ammonium fluoride and nitric acid, and the concentration of hydrofluoric acid is 60ml/L in the described activating solution, in the hydrofluoric acid solution of mass concentration 40%; The concentration of ammonium fluoride is 9g/L; The concentration of nitric acid is 60ml/L, in the salpeter solution of mass concentration 65%;
2, the preparation of composite powder
To activate tungsten powder adds in the chemical deposition solution, the addition of tungsten powder is 30g/L, with sodium hydroxide solution adjust pH 13.0, ultrasonic deposition coats 60 minutes under the normal temperature, supersonic frequency is 40KHz, and power is 300-400W, leaves standstill after 2 hours to filter, wash, prior to 120 ℃ of dryings 1 hour, obtained composite powder in 3 hours in 200 ℃ of dryings again;
Described chemical deposition solution is the aqueous solution of copper sulphate, lanthanum chloride, formaldehyde, disodium ethylene diamine tetraacetate and natrium citricum, the concentration of copper sulphate is 6g/L in the described chemical deposition solution, the concentration of lanthanum chloride is 2g/L, the concentration of formaldehyde is 10mL/L, the concentration of disodium ethylene diamine tetraacetate is 10g/L, and the concentration of natrium citricum is 20g/L;
3, compacting sintering
The composite powder of the present embodiment preparation with the compressing pressed compact that obtains of the unit pressure of 100MPa, is then placed tube type resistance furnace, at H
2Protection is sintering 90min under 1300 ℃ of temperature down, obtains La doping W-Cu Composite Sintering body.
La doping W-Cu composite powder homogenization of composition, the powder purity of the present embodiment preparation are high, the powder lumping phenomenon do not occur.Prepared Doping with Rare Earth Lanthanum Cu coats W surface recombination powder, and Cu and La reach respectively 15% and 1% at whole composite granule Atom ratio content, and prepared pressed compact is under sintering 90min condition under 1300 ℃ of temperature, and sintering sample relative density reaches 99.1%.
Embodiment 2:
1, the preparation of activation tungsten powder
Particle diameter was placed the activating solution ultrasonic activation 40 minutes less than 1 micron tungsten powder, and supersonic frequency is 40KHz, and power is 300-400W, obtains activating tungsten powder in 3 hours with deionized water washing three times and in 180 ℃ of dryings after activation is finished;
Described activating solution is the aqueous solution of hydrofluoric acid, ammonium fluoride and nitric acid, and the concentration of hydrofluoric acid is 30ml/L in the described activating solution, in the hydrofluoric acid solution of mass concentration 40%; The concentration of ammonium fluoride is 8g/L; The concentration of nitric acid is 80ml/L, in the salpeter solution of mass concentration 65%;
2, the preparation of composite powder
To activate tungsten powder adds in the chemical deposition solution, the addition of tungsten powder is 50g/L, with sodium hydroxide solution adjust pH 13.0, ultrasonic deposition coats 40 minutes under the normal temperature, supersonic frequency is 40KHz, and power is 300-400W, leaves standstill after 3 hours to filter, wash, prior to 160 ℃ of dryings 0.5 hour, obtained composite powder in 6 hours in 160 ℃ of dryings again;
Described chemical deposition solution is the aqueous solution of copper sulphate, lanthanum chloride, formaldehyde, disodium ethylene diamine tetraacetate and natrium citricum, the concentration of copper sulphate is 25g/L in the described chemical deposition solution, the concentration of lanthanum chloride is 0.8g/L, the concentration of formaldehyde is 20mL/L, the concentration of disodium ethylene diamine tetraacetate is 15g/L, and the concentration of natrium citricum is 30g/L;
3, compacting sintering
The composite powder of the present embodiment preparation with the compressing pressed compact that obtains of the unit pressure of 100MPa, is then placed tube type resistance furnace, at H
2Protection is sintering 120min under 1150 ℃ of temperature down, obtains La doping W-Cu Composite Sintering body.
La doping W-Cu composite powder homogenization of composition, the powder purity of the present embodiment preparation are high, the powder lumping phenomenon do not occur.Prepared Doping with Rare Earth Lanthanum Cu coats W surface recombination powder, and Cu and La reach respectively 25% and 0.5% at whole composite granule Atom ratio content, and prepared pressed compact is under sintering 120min condition under 1150 ℃ of temperature, and sintering sample relative density reaches 98.7%.
Embodiment 3:
1, the preparation of activation tungsten powder
Particle diameter was placed the activating solution ultrasonic activation 35 minutes less than 1 micron tungsten powder, and supersonic frequency is 40KHz, and power is 300-400W, obtains activating tungsten powder in 2 hours with deionized water washing three times and in 190 ℃ of dryings after activation is finished;
Described activating solution is the aqueous solution of hydrofluoric acid, ammonium fluoride and nitric acid, and the concentration of hydrofluoric acid is 50ml/L in the described activating solution, in the hydrofluoric acid solution of mass concentration 40%; The concentration of ammonium fluoride is 10g/L; The concentration of nitric acid is 50ml/L, in the salpeter solution of mass concentration 65%;
2, the preparation of composite powder
To activate tungsten powder adds in the chemical deposition solution, the addition of tungsten powder is 40g/L, with sodium hydroxide solution adjust pH 12.0, ultrasonic deposition coats 80 minutes under the normal temperature, supersonic frequency is 40KHz, and power is 300-400W, leaves standstill after 2 hours to filter, wash, prior to 160 ℃ of dryings 0.5 hour, obtained composite powder in 5 hours in 180 ℃ of dryings again;
Described chemical deposition solution is the aqueous solution of copper sulphate, lanthanum chloride, formaldehyde, disodium ethylene diamine tetraacetate and natrium citricum, the concentration of copper sulphate is 15g/L in the described chemical deposition solution, the concentration of lanthanum chloride is 2.6g/L, the concentration of formaldehyde is 5mL/L, the concentration of disodium ethylene diamine tetraacetate is 20g/L, and the concentration of natrium citricum is 25g/L;
3, compacting sintering
The composite powder of the present embodiment preparation with the compressing pressed compact that obtains of the unit pressure of 100MPa, is then placed tube type resistance furnace, at H
2Protection is sintering 110min under 1250 ℃ of temperature down, obtains La doping W-Cu Composite Sintering body.
La doping W-Cu composite powder homogenization of composition, the powder purity of the present embodiment preparation are high, the powder lumping phenomenon do not occur.Prepared Doping with Rare Earth Lanthanum Cu coats W surface recombination powder, and Cu and La reach respectively 19% and 2% at whole composite granule Atom ratio content, and prepared pressed compact is under sintering 110min condition under 1250 ℃ of temperature, and sintering sample relative density reaches 99.2%.
Claims (3)
1. the preparation method of a La doping W-Cu composite powder is characterized in that: comprise the preparation that activates tungsten powder and the preparation of composite powder;
The preparation of described activation tungsten powder is that tungsten powder was placed the activating solution ultrasonic activation 30-40 minute, obtains activating tungsten powder after activation is finished with deionized water washing and in 180-200 ℃ of dry 1-3 hour; The particle diameter of described tungsten powder is not more than 1 micron;
Described activating solution is the aqueous solution of hydrofluoric acid, ammonium fluoride and nitric acid, and the concentration of hydrofluoric acid is 30-60ml/L in the described activating solution, in the hydrofluoric acid solution of mass concentration 40%; The concentration of ammonium fluoride is 8-10g/L; The concentration of nitric acid is 50-80ml/L, in the salpeter solution of mass concentration 65%;
The preparation of described composite powder is that the activation tungsten powder is added in the chemical deposition solution, the addition of tungsten powder is 30-50g/L, with NaOH adjust pH 12.0-13.0, ultrasonic deposition coats 40-80 minute under the normal temperature, leaves standstill filtration after 2-3 hour, washing and drying and obtains composite powder; Described drying is prior to 120-160 ℃ of dry 0.5-1 hour, again in 160-200 ℃ of dry 3-6 hour;
Described chemical deposition solution is the aqueous solution of copper sulphate, lanthanum chloride, formaldehyde, disodium ethylene diamine tetraacetate and natrium citricum, the concentration of copper sulphate is 6-25g/L in the described chemical deposition solution, the concentration of lanthanum chloride is 0.8-2.6g/L, the concentration of formaldehyde is 5-20ml/L, the concentration of disodium ethylene diamine tetraacetate is 10-20g/L, and the concentration of natrium citricum is 20-30g/L.
2. preparation method according to claim 1, it is characterized in that: the supersonic frequency of described ultrasonic activation is 40KHz, power is 300-400W.
3. preparation method according to claim 1 is characterized in that: the supersonic frequency that described ultrasonic deposition coats is 40KHz, and power is 300-400W.
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| CN103736992A (en) * | 2013-11-22 | 2014-04-23 | 合肥工业大学 | Preparation method of nano TiC/W composite powder of core-shell structure |
| CN103894600B (en) * | 2014-04-22 | 2016-06-29 | 合肥工业大学 | A kind of high-strength highly-conductive W-Cu/Lu2O3Composite and preparation method thereof |
| CN110605385B (en) * | 2019-10-29 | 2021-08-24 | 广东银纳科技有限公司 | Preparation method of tungsten-based micro-nano composite powder and tungsten-based micro-nano composite powder |
| CN112570724B (en) * | 2020-12-11 | 2022-11-25 | 江西理工大学 | Preparation method of rare earth tungsten copper composite powder |
| CN115178740B (en) * | 2022-08-22 | 2024-01-16 | 合肥工业大学 | Tungsten-copper functionally graded material and preparation method thereof |
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| CN1160773A (en) * | 1995-11-17 | 1997-10-01 | 奥斯兰姆施尔凡尼亚公司 | Tungsten-copper composite powder |
| CN101428345A (en) * | 2007-11-09 | 2009-05-13 | 北京有色金属研究总院 | Method of manufacturing ultrafine molybdenum powder or ultrafine tungsten powder surface clad metal copper |
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| JPH04202602A (en) * | 1990-11-30 | 1992-07-23 | Mitsubishi Petrochem Co Ltd | Manufacture of metal magnetic powder |
| US6955703B2 (en) * | 2002-12-26 | 2005-10-18 | Millennium Inorganic Chemicals, Inc. | Process for the production of elemental material and alloys |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1160773A (en) * | 1995-11-17 | 1997-10-01 | 奥斯兰姆施尔凡尼亚公司 | Tungsten-copper composite powder |
| CN101428345A (en) * | 2007-11-09 | 2009-05-13 | 北京有色金属研究总院 | Method of manufacturing ultrafine molybdenum powder or ultrafine tungsten powder surface clad metal copper |
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| JP平4-202602A 1992.07.23 |
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