CN113414399A - Tungsten-copper powder with high copper content and preparation method thereof - Google Patents
Tungsten-copper powder with high copper content and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
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- C—CHEMISTRY; METALLURGY
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- C01F17/00—Compounds of rare earth metals
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/218—Yttrium oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
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- C—CHEMISTRY; METALLURGY
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/229—Lanthanum oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
The invention discloses tungsten-copper powder with high copper content and a preparation method thereof, wherein the tungsten-copper powder comprises the following components in percentage by mass: 0-4% of rare earth metal oxide, 40-90% of copper and 10-60% of tungsten. The preparation method comprises the steps of firstly preparing a soluble metal salt solution, mixing the metal salt solution with a urea solution, then carrying out hydrothermal reaction to prepare oxide powder, then carrying out ball milling and mixing on the metal oxide powder and the tungsten salt powder uniformly, and finally carrying out two-stage reduction reaction on the mixed powder in a reducing atmosphere to obtain the tungsten-copper powder with high copper content. The tungsten-copper powder with high copper content prepared by the invention has uniform and fine grains, the grain size range is 80-120nm, the sintering performance of the tungsten-copper alloy can be effectively improved, and the tungsten-copper alloy with higher density and excellent heat conduction and electric conductivity can be prepared.
Description
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to tungsten-copper powder with high copper content and a preparation method thereof.
Background
The tungsten-copper alloy has the advantages of high density, high melting point, high strength, low expansion coefficient of tungsten, good ductility and high heat and electricity conductivity of copper and the like, and the properties (such as electrical, thermal and mechanical properties and the like) of the alloy can be designed and regulated by adjusting the proportion of tungsten and copper elements, so that the tungsten-copper alloy is widely applied to the industries such as electric power, railways, electronic and electric appliances, metallurgy and the like.
Because W and Cu are not dissolved mutually, a nearly fully compact product is difficult to obtain no matter liquid phase sintering or solid phase sintering. In recent years, the preparation of high-density tungsten-copper alloy by using superfine tungsten-copper composite powder is greatly concerned. The sintering activity of the tungsten-copper powder can be improved by the nanocrystallization and the homogenization of the components, so that the tungsten-copper alloy with good physical properties and high density can be obtained. The existing powder preparation methods comprise a chemical coprecipitation method, a spray drying method, a sol-gel method and the like, but the methods have complicated processes and are difficult to operate, and the prepared composite powder has low dispersibility and uniformity; impurities are easily introduced into the raw material powder prepared by the mechanical mixing method, and the defects influence the subsequent preparation process and reduce the performance of the alloy.
In the preparation process of the high-copper-content tungsten-copper powder, the alloy powder needs to be reduced in hydrogen, and if the reduction temperature is low, tungsten oxides in the powder cannot be completely reduced, and tungsten oxides can remain in the powder; the reduction temperature is high, a large amount of nano copper powder exists in the powder, the fusion and the bonding are easy to occur, and the sintering of the copper powder occurs in severe cases. Therefore, in the process of reducing the tungsten-copper powder with high copper content, how to ensure the complete reduction of the tungsten oxide and reduce the fusion bonding of the nano-copper powder to the maximum extent is a difficult problem to be solved urgently.
Disclosure of Invention
In view of the above problems, the present invention provides a high copper content tungsten-copper powder and a method for preparing the same, which can prepare a nano-sized tungsten-copper powder with high copper content and good dispersibility uniformity.
The method comprises the steps of firstly preparing a soluble metal salt solution, mixing the metal salt solution with a urea solution, then carrying out hydrothermal reaction to prepare oxide powder, then carrying out ball milling and uniform mixing on the metal oxide powder and the tungsten salt powder, and finally carrying out two-stage reduction reaction on the mixed powder in a reducing atmosphere to obtain the tungsten-copper powder with high copper content.
The preparation method of the tungsten-copper powder with high copper content comprises the following specific steps:
1) respectively preparing a soluble copper salt solution, a soluble rare earth metal salt solution and a urea solution by taking water as a solvent, and uniformly stirring and mixing the above solutions to obtain a mixed solution; wherein, the proportion of the soluble copper salt and the soluble rare earth metal salt is calculated according to the content of the target product, and the molar ratio of metal ions (copper ions and rare earth metal ions) to urea is 1: (1-1.1).
2) Placing the mixed solution obtained in the step 1) into a hydrothermal reaction kettle for hydrothermal reaction, and filtering, washing and drying a reaction product to obtain the copper oxide and rare earth oxide composite powder.
In the process of hydrothermal reaction, urea is firstly hydrolyzed, the hydrolysis product reacts with copper ions to generate basic copper carbonate, the basic copper carbonate is decomposed to generate nano-level copper oxide, and the generation principle of rare earth oxide is similar to that of the copper oxide.
3) Ball-milling the composite powder obtained in the step 2) and the tungsten salt powder by taking absolute ethyl alcohol as a medium, and drying the powder after ball-milling to obtain mixed powder; the tungsten salt is ammonium paratungstate or ammonium tungstate; the proportion of the composite powder to the tungsten salt powder is calculated according to the content of the target product.
The ball milling process enables the copper oxide and the tungsten salt powder to be uniformly mixed, and the particle size of the powder is smaller; meanwhile, the ball milling process improves the stress, strain and defects of the powder, and causes a large amount of nano crystal boundaries and phase boundaries to be generated, thereby increasing the energy storage of the system, greatly improving the activity of the powder and promoting the subsequent hydrogen reduction reaction process.
4) Placing the mixed powder in the step 3) in a hydrogen reducing atmosphere, and carrying out two-stage reduction reaction to obtain high-copper-content tungsten-copper powder; wherein the temperature of the first-stage reduction reaction is 400-600 ℃, and the temperature of the second-stage reduction reaction is 700-800 ℃.
In the first reduction process, the copper oxide powder is reduced into metal copper powder, ammonium paratungstate or ammonium tungstate is subjected to physical adsorption water and chemical adsorption water removal, and then NH is decomposed and released3And H2O, continues to decompose with increasing temperature to form WO3(ii) a Generated WO3Reducing the tungsten by hydrogen to generate a series of tungsten suboxides; and finally obtaining the tungsten-copper powder with high copper content through a two-stage hydrogen reduction process.
The preparation method of the tungsten-copper powder with high copper content can be further implemented under the following conditions:
the water in the step 1) is deionized water or distilled water.
The soluble copper salt in the step 1) is preferably one of copper nitrate, copper chloride and copper sulfate; the concentration of the copper salt solution is 0.3-2.0 mol/L.
The concentration of the rare earth metal salt solution in the step 1) is 0.2-1.0mol/L, and the rare earth metal is one or a mixture of lanthanum, yttrium, cerium and gadolinium.
The concentration of the urea solution in the step 1) is 0.5-1.5 mol/L.
The hydrothermal reaction pressure in the step 2) is 8-18Mpa, the temperature is 180-.
The ball milling speed in the step 3) is 800-.
In the step 4), the first-stage reduction heat preservation time is 0.5-3h, and the second-stage reduction heat preservation time is 1-4 h.
The tungsten-copper powder with high copper content prepared by the preparation method comprises the following components in percentage by mass: 0-4% of rare earth metal oxide, 40-90% of copper and 10-60% of tungsten; wherein the rare earth oxide is one or a mixture of more of lanthanum oxide, yttrium oxide, cerium oxide and gadolinium oxide.
The invention has the beneficial effects that:
1) the invention prepares the copper oxide and rare earth oxide composite powder in one step in the reaction kettle without thermal decomposition, and adopts ammonium paratungstate or ammonium tungstate as a tungsten source, thereby reducing the processes of precursor solution atomization, drying, calcination decomposition and the like in the prior method. The calcination of the tungsten source powder is completed in the hydrogen reduction process, so that the production process can be shortened, the production cost can be saved, and the tungsten-copper composite powder with good performance can be obtained.
2) According to the invention, the oxide powder and the tungsten salt are subjected to ball milling, so that the powder is uniformly mixed, the stress, strain and defects of the powder are improved, a large amount of nano crystal boundaries and phase boundaries are generated, the energy storage of a system is increased, the activity of the powder is greatly improved, the subsequent hydrogen reduction process is accelerated, and the reaction temperature is reduced; in the first-stage reduction process, the ball-milled ammonium paratungstate or ammonium tungstate powder is gradually decomposed to generate tungsten oxides, and the tungsten oxides are quickly reduced into low-valence oxides in short time, so that conditions are provided for obtaining the tungsten powder with fine grains through the second-stage reduction. The tungsten powder with uniform dispersion and fine grains simultaneously reduces the fusion bonding of the nano copper powder, so the tungsten-copper powder prepared by the method has more uniform and fine granularity, and the grain size range of the powder is between 80 and 120 nm.
3) The preparation method can also dope the rare earth oxide on the tungsten-copper powder, and the rare earth oxide is dispersed among the powder as a hard phase and plays a role in inhibiting the growth of crystal grains in the sintering process of preparing the tungsten-copper alloy; the rare earth oxide can also improve the properties of the tungsten-copper alloy such as strength, toughness and the like.
4) The invention can fully utilize the existing tungsten powder reduction process and equipment to prepare the tungsten-copper powder with wide component distribution range, superfine particles and uniform tissue and high copper content and the rare earth oxide powder doped with the tungsten-copper powder. The process is simple, the operation is easy, the energy is saved, the obtained powder can effectively improve the sintering performance of the tungsten-copper alloy, and the preparation of the tungsten-copper alloy with higher density and excellent heat and electric conductivity is facilitated.
Drawings
FIG. 1 SEM image of a sample of example 1;
FIG. 2 SEM image of example 2 sample;
FIG. 3 SEM image of example 3 sample;
FIG. 4 SEM image of example 4 sample;
FIG. 5 TEM image of example 4 sample;
figure 6 XRD diffractogram of the sample of example 4.
Detailed Description
The invention will be further described with reference to the following examples for better understanding, but the scope of the invention is not limited to the examples.
Example 1
The embodiment is a preparation method of W-90Cu composite powder, which comprises the following specific steps:
1) respectively preparing 1.0mol/L copper nitrate solution and 0.5mol/L urea solution, and uniformly stirring and mixing the two solutions to obtain mixed solution, namely Cu2+The molar ratio to urea was 1: 1.1.
2) And (2) placing the mixed solution obtained in the step 1) into a high-pressure reaction kettle, reacting for 20 hours under the conditions of 10Mpa and 180 ℃, filtering, washing and drying a reaction product to obtain copper oxide powder.
3) Weighing ammonium tungstate according to the tungsten-copper mass ratio of 1:9, ball-milling the copper oxide powder and the ammonium tungstate obtained in the step 2) for 1h at 1500rpm by using ethanol as a medium, and drying to obtain mixed powder.
4) Placing the mixed powder in the step 3) in a hydrogen reducing atmosphere to carry out two-stage reduction reaction, wherein the temperature of the first stage reduction is 500 ℃, and keeping the temperature for 1.5 h; the second-stage reduction temperature is 730 ℃, the temperature is kept for 2h, and the W-90Cu composite powder is obtained after natural cooling.
After X-ray diffraction analysis, the composite powder prepared in this example consisted of copper and tungsten, and had no other impurities, and the morphology of the powder was as shown in fig. 1.
Example 2
This example is W-70Cu-1.0La2O3The preparation method of the composite powder comprises the following specific steps:
1) respectively preparing 0.5mol/L copper nitrate solution, 1.0mol/L lanthanum nitrate solution and 0.8mol/L urea solution, stirring and mixing the three solutions uniformly to obtain mixed solution, and metal ions (Cu)2++La2+) The molar ratio to urea was 1: 1.05.
2) And (2) placing the mixed solution obtained in the step 1) into a high-pressure reaction kettle, reacting for 16 hours at the temperature of 200 ℃ under the pressure of 8Mpa, and filtering, washing and drying a reaction product to obtain the composite powder of copper oxide and lanthanum oxide.
3) Weighing ammonium tungstate according to the tungsten-copper mass ratio of 2.9:7, ball-milling the composite powder obtained in the step 2) for 1h at 1500rpm by using ethanol as a medium, and drying to obtain mixed powder.
4) Placing the mixed powder in the step 3) in a hydrogen reducing atmosphere to carry out two-stage reduction reaction, wherein the temperature of the first stage reduction is 450 ℃, and keeping the temperature for 2 h; the temperature of the second-stage reduction is 800 ℃, the temperature is kept for 1.5h, and the W-70Cu-1.0La is obtained after natural cooling2O3And (3) composite powder.
The composite powder prepared in this example was analyzed by X-ray diffraction to be composed of Cu, W and La2O3The composition is free of other impurities, and the morphology of the powder is shown in figure 2.
Example 3
The embodiment is a preparation method of W-50Cu composite powder, which comprises the following specific steps:
1) respectively preparing 1.5mol/L copper nitrate solution and 1.5mol/L urea solution, and uniformly stirring and mixing the two solutions to obtain mixed solution, namely Cu2+The molar ratio to urea was 1:1.
2) And (2) placing the mixed solution obtained in the step 1) into a high-pressure reaction kettle, reacting for 24 hours under the conditions of 10Mpa and 180 ℃, filtering, washing and drying a reaction product to obtain the copper oxide powder.
3) Weighing ammonium paratungstate according to the tungsten-copper mass ratio of 1:1, ball-milling the copper oxide powder obtained in the step 2) for 0.8h under the condition of 1200rpm by taking ethanol as a medium, and drying to obtain mixed powder.
4) Placing the mixed powder in the step 3) in a hydrogen reducing atmosphere to carry out two-stage reduction reaction, wherein the temperature of the first stage reduction is 500 ℃, and keeping the temperature for 1.5 h; the second-stage reduction temperature is 800 ℃, the temperature is kept for 2h, and the W-50Cu composite powder is obtained after natural cooling.
After X-ray diffraction analysis, the composite powder prepared in this example consisted of copper and tungsten, and had no other impurities, and the morphology of the powder was as shown in fig. 3.
Example 4
The embodiment is a preparation method of W-80Cu composite powder, which comprises the following specific steps:
1) respectively preparing 0.4mol/L copper nitrate solution and 0.8mol/L urea solution, and uniformly stirring and mixing the two solutions to obtain mixed solution, namely Cu2+The molar ratio to urea was 1: 1.1.
2) And (2) placing the mixed solution obtained in the step 1) into a high-pressure reaction kettle, reacting for 16 hours under the conditions of 12Mpa and 200 ℃, filtering, washing and drying a reaction product to obtain the copper oxide powder.
3) Weighing ammonium paratungstate according to the tungsten-copper mass ratio of 1:4, ball-milling the copper oxide powder obtained in the step 2) for 0.5h under the condition of 1600rpm by taking ethanol as a medium, and drying to obtain mixed powder.
4) Placing the mixed powder in the step 3) in a hydrogen reducing atmosphere to carry out two-stage reduction reaction, wherein the temperature of the first stage reduction is 400 ℃, and keeping the temperature for 2 hours; the second-stage reduction temperature is 750 ℃, the temperature is kept for 2.0h, and the W-80Cu composite powder is obtained after natural cooling.
The morphology of the W-80Cu composite powder prepared by the embodiment is shown in FIG. 4, and the powder is uniformly dispersed and has fine grains; the transmission electron microscope is shown in FIG. 5, and the particle size of the composite powder is between 80 and 120 nm; the X-ray diffraction analysis is shown in fig. 6, and the composite powder is composed of copper and tungsten, and has no other impurities.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The tungsten-copper powder with high copper content is characterized by comprising the following components in percentage by mass: 10-60% of tungsten, 40-90% of copper and 0-4% of rare earth metal oxide; the particle size of the powder is 80-120 nm.
2. The tungsten-copper powder with high copper content according to claim 1, wherein the rare earth oxide is one or a mixture of lanthanum oxide, yttrium oxide, cerium oxide and gadolinium oxide.
3. The method for preparing the tungsten-copper powder with high copper content according to claim 1, comprising the following steps:
1) respectively preparing a soluble copper salt solution, a soluble rare earth metal salt solution and a urea solution by taking water as a solvent, and uniformly stirring and mixing the above solutions to obtain a mixed solution;
2) placing the mixed solution obtained in the step 1) into a hydrothermal reaction kettle for hydrothermal reaction, and filtering, washing and drying a reaction product to obtain copper oxide and rare earth oxide composite powder;
3) ball-milling the composite powder obtained in the step 2) and the tungsten salt powder by taking absolute ethyl alcohol as a medium, and drying the powder after ball-milling to obtain mixed powder;
4) putting the mixed powder in the step 3) in a hydrogen reducing atmosphere, and carrying out two-stage reduction reaction to obtain the high-copper-content tungsten-copper powder.
4. The method for preparing the high-copper-content tungsten-copper powder according to claim 3, wherein the water in the step 1) is deionized water or distilled water.
5. The method for preparing the high copper content tungsten-copper powder of claim 3, wherein the soluble copper salt in step 1) is one of copper nitrate, copper chloride and copper sulfate; the concentration of the soluble copper salt solution is 0.3-2.0 mol/L.
6. The method for preparing the high-copper-content tungsten-copper powder according to claim 3, wherein the concentration of the soluble rare earth metal salt solution in the step 1) is 0.2-1.0mol/L, and the concentration of the urea solution is 0.5-1.5 mol/L.
7. The method for preparing the tungsten-copper powder with high copper content as claimed in claim 3, wherein the hydrothermal reaction pressure in the step 2) is 8-18MPa, the temperature is 180-.
8. The method for preparing the tungsten-copper powder with high copper content as claimed in claim 3, wherein the ball milling speed in step 3) is 800-.
9. The method according to claim 3, wherein the tungsten salt is ammonium paratungstate or ammonium tungstate.
10. The method for preparing the tungsten-copper powder with high copper content as claimed in claim 3, wherein the temperature of the first stage reduction reaction in the step 4) is 400-; the temperature of the second-stage reduction reaction is 700-800 ℃, and the heat preservation time is 1-4 h.
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