Preparation process of high-copper-content tungsten-copper alloy

Abstract

The application relates to a preparation process of a high-copper-content tungsten-copper alloy. An anionic surfactant is dispersed into n-nonyl alcohol as solution I, a tungsten salt aqueous solution is prepared as solution II, a copper salt aqueous solution is prepared as solution III, solution II is added into solution I to obtain a mixed solution S1 by stirring, solution III is added into the mixed solution S1 to obtain a mixed solution S2 by stirring, the pH of the mixed solution S2 is controlled to be 5-6.4 by using an ethanolamine solution, oil bath heating and stirring reaction is carried out, the obtained product is filtered, washed, dried and calcined, hydrogen reduction is carried out, the reduced powder is cold isostatic pressing, then the powder is sleeved and hot isostatic pressing treatment is carried out, and the high-copper-content tungsten-copper alloy is obtained. The process is simple, controllable and operable, no impurities are introduced, the mass ratio of copper and tungsten can be accurately controlled, the process has wide applicability, the tungsten-copper alloy with fine grains, high density and uniform structure can be prepared, and the alloy performance can meet the application of contact materials and high-voltage switches.

Description

Technical Field

[0001] This invention belongs to the field of alloy material preparation technology, specifically a preparation process for a high copper content tungsten-copper alloy. Background Technology

[0002] Metallic copper possesses excellent electrical and thermal conductivity, high ductility, and good processing properties. However, its low melting point and hardness, coupled with softening and deformation at higher temperatures, limit its applications. Tungsten-copper alloys combine the advantages of both tungsten and copper, such as tungsten's high melting point, high strength, and high wear resistance, and copper's high ductility and high thermal and electrical conductivity. With rapid technological advancements, the applications of tungsten-copper alloys are becoming increasingly widespread, placing higher demands on their microstructure and properties. For example, ultra-high-voltage power transmission networks require electrical contact materials with higher mechanical properties, and high-voltage switch contacts require materials with high wear resistance. Because tungsten-copper alloys are not solid-solid, densification during sintering is difficult, leading to a decline in alloy performance.

[0003] Currently, the industrial-scale preparation processes for tungsten-copper alloys include: melt infiltration, high-temperature liquid-phase sintering, and activated liquid-phase sintering. In melt infiltration and high-temperature liquid-phase sintering, the sintering temperature is higher than the melting point of copper, and densification is mainly achieved by the flow of liquid copper to fill the gaps between particles. The sintering temperature of these processes is higher than the melting point of copper, making them unsuitable for the preparation of high-copper-content tungsten-copper alloys with copper as the matrix. Activated sintering improves the tungsten-copper interface and increases sintering density by adding activating elements such as Co and Ni, but this leads to a decrease in the material's electrical and thermal conductivity. For high-copper-content tungsten-copper alloys with copper as the matrix, how to significantly improve the alloy's mechanical properties and deformation resistance while maintaining high conductivity and density is one of the urgent problems to be solved. Summary of the Invention

[0004] To overcome the problems of existing technologies, this invention provides a preparation process for a high-copper-content tungsten-copper alloy. This invention utilizes a water-oil two-phase "nanoreactor" to construct the process. Tungsten salts and copper salts react in the water-oil two-phase environment under oil bath conditions. Subsequent calcination and hydrogen reduction yield tungsten-copper composite powder with controllable particle size. Then, a cold-pressing-hot isostatic pressing process is employed, with controlled process parameters, to prepare a fine-grained, high-density, and uniformly structured high-copper-content tungsten-copper alloy. This high-copper-content tungsten-copper alloy has a uniform and dense structure, with tungsten particles evenly distributed in the copper matrix. Its density can reach over 98.6%. The alloy has a uniform structure and fine grains (less than 2 μm), which can meet the requirements for contact materials, high-voltage switches, and other applications, and has a very broad application prospect and promotional value.

[0005] This invention is specifically achieved through the following technical solution: a preparation process for a high-copper-content tungsten-copper alloy proposed in this invention includes the following steps: 1) Disperse the anionic surfactant in nonanol as solution I, prepare a soluble tungsten salt aqueous solution as solution II, and prepare a soluble copper salt aqueous solution as solution III. Add solution II dropwise to solution I and stir until homogeneous to obtain mixture S1 (that is, tungsten ions and the aqueous medium are coated by the organic phase and surfactant to form a "nanoreactor"). Then add solution III to mixture S1 and stir until homogeneous to obtain mixture S2. Preferably, the concentration of the anionic surfactant in solution I is 0.5~2 mol / L; the concentration of the tungsten salt in solution II is 0.01~2 mol / L; the concentration of the copper salt in solution III is 0.5~2.0 mol / L; and the copper-tungsten mass ratio is (60~99):(1~40). 2) Add the ethanolamine solution dropwise to the mixture S2, stir until homogeneous, control the pH of the mixture to 5-6.4, then heat and stir in an oil bath, filter the precursor obtained from the reaction, wash the filtrate with distilled water until neutral, then wash with ethanol 2-3 times, and dry to obtain the precursor. 3) The precursor obtained in step 2) is calcined in air at a heating rate of 10~20 ℃ / min, a calcination temperature of 500~650℃, and a calcination time of 1~5 h; then it is reduced in a hydrogen atmosphere to obtain tungsten-copper composite powder with controllable particle size; wherein, the particle size of the tungsten-copper composite powder can be controlled by controlling the hydrogen flow rate, powder thickness, reduction time and temperature during the reduction process. 4) The tungsten-copper composite powder is loaded into a rubber mold and subjected to cold isostatic pressing to produce a green blank; 5) Vacuum the obtained green billet, and then put the vacuum-sealed green billet into a hot isostatic pressing (HIP) equipment for HIP treatment. The HIP temperature is 850~1000℃, the pressure is 90~150 MPa, and the treatment time is 2~6 h. After removing the cladding, a high copper content tungsten-copper alloy is obtained.

[0006] In the aforementioned preparation process of high copper content tungsten-copper alloy, the anionic surfactant in step 1) is preferably fatty alcohol polyoxyethylene ether sulfate, alkyl alcohol amide, or alkylphenol sulfonate; the soluble tungsten salt is preferably one or more of ammonium metatungstate, sodium tungstate, ammonium paratungstate, and potassium tungstate; and the soluble copper salt is preferably one or more of copper nitrate, copper chloride, copper sulfate, and copper oxalate.

[0007] In the aforementioned preparation process of high copper content tungsten-copper alloy, the preferred volume ratio of nonanol to solution III in step 1) is 1:4.

[0008] Preferably, in step 2), the concentration of the ethanolamine solution is 0.1~1.5 mol / L; the oil bath heating and stirring reaction temperature is 75~110℃, the time is 2~12 h, and the stirring rate is 50~500 r / min.

[0009] Preferably, the reduction in step 3) is a two-stage hydrogen reduction, wherein the first stage hydrogen reduction is carried out at a temperature of 400~550℃ for 1~3 h, and the hydrogen flow rate is 10 m³ / h. 3 / h~20 m 3 / h, powder spreading height ≤2 / 3; second-stage hydrogen reduction temperature 750~800℃, time 1~4 h, hydrogen flow rate 15 m³ / h. 3 / h~25 m 3 / h, powder spreading height ≤2 / 3.

[0010] Preferably, the pressure for cold isostatic pressing is 110~200 MPa and the time is 20~60 min.

[0011] Preferably, the sheath can be made of carbon steel or similar material, achieving a vacuum level of 1×10⁻⁶ during evacuation. -5 Pa ~ 1×10 -2 Pa.

[0012] The high copper content tungsten-copper alloy prepared according to the aforementioned method has a copper content of 60-99% and a tungsten content of 1-40%. The high copper content tungsten-copper alloy has an electrical conductivity of 70.5-92% IACS, a hardness of 75-209 HV, and a density of 98.6-99.5%.

[0013] The present invention also provides a high copper content tungsten-copper alloy prepared according to the above method, which can be used in contact materials, electrical switches and other fields.

[0014] Compared with existing technologies, this invention has significant advantages and beneficial effects. Through the above technical solution, this invention achieves considerable technological advancement and practicality, and has broad application value, possessing at least the following advantages: (1) This invention utilizes a water-oil two-phase "nanoreactor" to construct a tungsten salt and copper salt in an oil bath under water-oil two-phase conditions. After subsequent calcination and hydrogen reduction, a tungsten-copper composite powder with controllable particle size is obtained. This tungsten-copper composite powder is nearly spherical, with uniform particle size of 35-50 nm. The particle size of the tungsten-copper composite powder can be controlled by adjusting the hydrogen flow rate, powder thickness, reduction time, and temperature during the reduction process. By using a cold pressing-hot isostatic pressing process and controlling reasonable process parameters, a high-copper-content tungsten-copper alloy with fine grains, high density, and uniform microstructure was prepared. This high-copper-content tungsten-copper alloy has a uniform and dense microstructure, with tungsten particles uniformly distributed in the copper matrix. The tungsten particle size is less than 2 μm, and no voids are observed. Its density can reach over 98.6%, oxygen content is less than 40 ppm, the alloy structure is uniform, the grains are fine (less than 2 μm), and the density and conductivity increase with the increase of copper content, with conductivity exceeding 70.5%. It can meet the application requirements of contact materials, high voltage switches, etc., and has a very broad application prospect and promotion value.

[0015] (2) The process of this invention is simple and controllable, highly operable, does not introduce impurities, and the ratio of the two phase components can be precisely controlled, making the process widely applicable. It can also be applied to the preparation of second-phase doped tungsten-copper alloys, molybdenum-copper alloys, etc. Attached Figure Description

[0016] Figure 1 This is a TEM image of the tungsten-copper composite powder prepared in Example 2.

[0017] Figure 2 This is a BSEM image of the high-copper-content tungsten-copper alloy prepared in Example 2.

[0018] Figure 3 This is a BSEM image of the high-copper-content tungsten-copper alloy prepared in Example 3.

[0019] Figure 4 This is a SEM image of the tungsten-copper composite powder prepared in Example 4.

[0020] Figure 5 This is a BSEM image of the high-copper-content tungsten-copper alloy prepared in Example 4. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Example 1 (1) Disperse fatty alcohol polyoxyethylene ether sulfate in 50 mL of n-nonanol to make the concentration of fatty alcohol polyoxyethylene ether sulfate 0.8 mol / L, to obtain solution I; prepare 0.5 mol / L potassium tungstate aqueous solution as solution II and 200 mL of 0.4 mol / L copper sulfate solution as solution III according to the copper-tungsten mass ratio of 6:4. (2) Add solution II dropwise to solution I and stir until homogeneous to obtain mixture S1. Add solution III to mixture S1 and stir until homogeneous to obtain mixture S2. (3) The prepared 0.2 mol / L ethanolamine solution was added dropwise to the mixture S2, stirred evenly, and the pH value was adjusted to 5.5. The reaction was carried out by heating and stirring in an oil bath at 100℃ for 3 h and stirring at 200 r / min. The precursor obtained from the reaction was filtered, and the filtrate was first washed with distilled water until neutral, then washed with ethanol 2-3 times, and finally dried at 120℃ for 16 h to obtain the precursor. (4) The precursor obtained in step (3) is calcined in air at a heating rate of 20℃ / min and a calcination temperature of 600℃ for 2 h. After calcination, a two-stage reduction is carried out in a hydrogen atmosphere. The first stage of hydrogen reduction is performed at a temperature of 500℃ for 2 h and a hydrogen flow rate of 15 m³ / min. 3 / h, powder spreading height ≤2 / 3; second-stage hydrogen reduction temperature is 800℃, time is 3 h, hydrogen flow rate is 20 m³ / h. 3 / h, with a powder spreading height ≤2 / 3, tungsten-copper composite powder with controllable particle size is obtained; the particle size of tungsten-copper powder can be controlled by adjusting the hydrogen flow rate, powder spreading thickness, reduction time and temperature during the reduction process; (5) The tungsten copper powder was loaded into a rubber mold and subjected to cold isostatic pressing at 180 MPa for 30 min to prepare a green blank; the obtained green blank was then encased in a vacuum chamber and the vacuum degree reached 2.0 × 10⁻⁶. -4 After Pa, the alloy is sealed and then placed in a hot isostatic pressing (HIP) equipment for HIP treatment. The HIP treatment temperature is 1000℃ and 180 MPa for 3 h. After removing the cladding, a high copper content tungsten-copper alloy is obtained.

[0023] Example 2 (1) Disperse alkylphenol sulfonate in 50 mL of n-nonanol to make the concentration of alkylphenol sulfonate 1.2 mol / L to obtain solution I; prepare 0.3 mol / L ammonium metatungstate aqueous solution as solution II and 200 mL of 0.6 mol / L copper nitrate solution as solution III according to the copper-tungsten mass ratio of 7:3; (2) Add solution II dropwise to solution I and stir until homogeneous to obtain mixture S1. Add solution III to mixture S1 and stir until homogeneous to obtain mixture S2. (3) The prepared 0.5 mol / L ethanolamine solution was added dropwise to the mixture S2, the pH was adjusted to 5.8, and the reaction was carried out by oil bath heating and stirring at 90℃ for 4 h and stirring rate of 300 r / min. The precursor obtained from the reaction was filtered, the filtrate was first washed with distilled water until neutral, then washed with ethanol 2-3 times, and finally dried at 100℃ for 26 h to obtain the precursor. (4) The precursor obtained in step (3) is calcined in air at a heating rate of 15℃ / min and a calcination temperature of 500℃ for 4 h. After calcination, a two-stage reduction is carried out in a hydrogen atmosphere. The first stage hydrogen reduction is performed at a temperature of 450℃ for 4 h and a hydrogen flow rate of 15 m³ / min. 3 / h, powder spreading height ≤2 / 3; second-stage hydrogen reduction temperature is 800℃, time is 3 h, hydrogen flow rate is 18 m³ / h. 3 / h, with a powder spreading height ≤2 / 3, tungsten-copper composite powder with controllable particle size is obtained; the particle size of tungsten-copper powder can be controlled by adjusting the hydrogen flow rate, powder spreading thickness, reduction time and temperature during the reduction process; (5) The tungsten copper powder was loaded into a rubber mold and subjected to cold isostatic pressing at 110 MPa for 60 min to prepare a green blank; the obtained green blank was then encased in a vacuum chamber and the vacuum degree reached 2.0 × 10⁻⁶. -4 After Pa, the alloy is sealed and then placed in a hot isostatic pressing (HIP) equipment for HIP treatment. The HIP treatment is carried out at 980℃ and 150 MPa for 4 h. After removing the cladding, a high copper content tungsten-copper alloy is obtained.

[0024] Example 3 (1) Disperse the alkylolamide in 50 mL of n-nonanol to make the concentration of the alkylolamide 1.5 mol / L to obtain solution I; prepare 0.7 mol / L sodium tungstate aqueous solution as solution II and 200 mL of 1.0 mol / L copper chloride solution as solution III according to the copper-tungsten mass ratio of 8:2. (2) Add solution II dropwise to solution I and stir until homogeneous to obtain mixture S1. Add solution III to mixture S1 and stir until homogeneous to obtain mixture S2. (3) The prepared 0.8 mol / L ethanolamine solution was added dropwise to the mixture S2, the pH was adjusted to 5.2, and the reaction was carried out by oil bath heating and stirring at 80℃ for 6 h and stirring rate of 200 r / min. The precursor obtained from the reaction was filtered, the filtrate was first washed with distilled water until neutral, then washed with ethanol 2-3 times, and finally dried at 110℃ for 20 h to obtain the precursor. (4) The precursor obtained in step (3) is calcined in air at a heating rate of 15℃ / min and a calcination temperature of 550℃ for 3 h. After calcination, a two-stage reduction is carried out in a hydrogen atmosphere. The first stage of hydrogen reduction is carried out at a temperature of 400℃ for 4 h and a hydrogen flow rate of 20 m³ / min. 3 / h, powder spreading height ≤2 / 3; second-stage hydrogen reduction temperature is 750℃, time is 3 h, hydrogen flow rate is 18 m³ / h. 3 / h, with a powder spreading height ≤2 / 3, tungsten-copper composite powder with controllable particle size is obtained; the particle size of tungsten-copper powder can be controlled by adjusting the hydrogen flow rate, powder spreading thickness, reduction time and temperature during the reduction process; (5) The tungsten copper powder was loaded into a rubber mold and subjected to cold isostatic pressing at 150 MPa for 30 min to prepare a green billet; the recycled billet was then encased in a vacuum chamber and the vacuum level reached 5.0 × 10⁻⁶. -3 After Pa, the alloy is sealed and then placed in a hot isostatic pressing (HIP) equipment for HIP treatment at 950℃ and 150 MPa for 4 h. After removing the cladding, a high copper content tungsten-copper alloy is obtained.

[0025] Example 4 (1) Disperse the alkylolamide in 50 mL of n-nonanol to make the concentration of the alkylolamide 1.8 mol / L to obtain solution I; prepare 0.1 mol / L ammonium metatungstate aqueous solution as solution II and 200 mL of 1.0 mol / L copper nitrate solution as solution III according to the copper-tungsten mass ratio of 9:1. (2) Add solution II dropwise to solution I and stir until homogeneous to obtain mixture S1. Add solution III to mixture S1 and stir until homogeneous to obtain mixture S2. (3) The prepared 1.0 mol / L ethanolamine solution was added dropwise to the mixture S2, the pH was adjusted to 6.0, and the reaction was carried out by oil bath heating and stirring at 75℃ for 10 h and stirring rate of 150 r / min. The precursor obtained from the reaction was filtered, the filtrate was first washed with distilled water until neutral, then washed with ethanol 2-3 times, and finally dried at 100℃ for 36 h to obtain the precursor. (4) The precursor obtained in step (3) is calcined in air at a heating rate of 10℃ / min and a calcination temperature of 500℃ for 4 h. After calcination, a two-stage reduction is carried out in a hydrogen atmosphere. The first stage of hydrogen reduction is carried out at a temperature of 400℃ for 6 h and a hydrogen flow rate of 20 m³ / min. 3 / h, powder spreading height ≤2 / 3; second-stage hydrogen reduction temperature is 780℃, time is 3 h, hydrogen flow rate is 15 m³ / h. 3 / h, with a powder spreading height ≤2 / 3, tungsten-copper composite powder with controllable particle size is obtained; the particle size of tungsten-copper powder can be controlled by adjusting the hydrogen flow rate, powder spreading thickness, reduction time and temperature during the reduction process; (5) The tungsten copper powder was loaded into a rubber mold and subjected to cold isostatic pressing at 200 MPa for 20 min to prepare a green billet; the recycled billet was then encased in a vacuum chamber and the vacuum level reached 8.0 × 10⁻⁶. -4 After Pa, the alloy is sealed and then placed in a hot isostatic pressing (HIP) machine for 5 hours at 950℃ and 130 MPa. After removing the cladding, a high copper content tungsten-copper alloy is obtained.

[0026] Example 5 (1) Disperse alkylphenol sulfonate in 50 mL of n-nonanol to make the concentration of alkylolamide 2 mol / L to obtain solution I; prepare 0.2 mol / L sodium tungstate aqueous solution as solution II and 200 mL of 2 mol / L copper nitrate solution as solution III according to the copper-tungsten mass ratio of 9.5:0.5; (2) Add solution II dropwise to solution I and stir until homogeneous to obtain mixture S1. Add solution III to mixture S1 and stir until homogeneous to obtain mixture S2. (3) The prepared 0.7 mol / L ethanolamine solution was added dropwise to the mixture S2, the pH was adjusted to 6.0, and the reaction was carried out by oil bath heating and stirring at 110℃ for 3 h and stirring rate of 200 r / min. The precursor obtained from the reaction was filtered, the filtrate was first washed with distilled water until neutral, then washed with ethanol 2-3 times, and finally dried at 110℃ for 30 h to obtain the precursor. (4) The precursor obtained in step (3) is calcined in air at a heating rate of 15℃ / min and a calcination temperature of 500℃ for 2 h. After calcination, a two-stage reduction is carried out in a hydrogen atmosphere. The first stage of hydrogen reduction is performed at a temperature of 400℃ for 4 h and a hydrogen flow rate of 18 m³ / min. 3 / h, powder spreading height ≤2 / 3; second-stage hydrogen reduction temperature is 750℃, time is 4 h, hydrogen flow rate is 20 m³ / h. 3 / h, with a powder spreading height ≤2 / 3, tungsten-copper composite powder with controllable particle size is obtained; the particle size of tungsten-copper powder can be controlled by adjusting the hydrogen flow rate, powder spreading thickness, reduction time and temperature during the reduction process; (5) The tungsten copper powder was loaded into a rubber mold and subjected to cold isostatic pressing at 120 MPa for 40 min to prepare a green billet; the recycled billet was then encased in a vacuum chamber and the vacuum level reached 6.0 × 10⁻⁶. -4After Pa, the alloy is sealed and then placed in a hot isostatic pressing (HIP) machine for 4 hours at 900℃ and 150 MPa. After removing the cladding, a high copper content tungsten-copper alloy is obtained.

[0027] Figure 1 The image shows a TEM image of the tungsten-copper composite powder prepared in step (4) of Example 2. As can be seen from the image, the powder is nearly spherical, with uniform particle size and a particle size of about 35-50 nm.

[0028] Figure 2 This is a BSEM image of the high-copper-content tungsten-copper alloy prepared in Example 2, with a copper content of 70% and a tungsten content of 30%. Figure 2 The dark areas are copper phase and the gray areas are tungsten phase. The tungsten-copper alloy has a uniform and dense structure, with tungsten particles evenly distributed in the copper matrix. The tungsten particle size is less than 2μm and no voids can be observed.

[0029] Figure 3 This is a BSEM image of the high copper content tungsten-copper alloy prepared in Example 3, with a copper mass content of 80% and a tungsten mass content of 20%. Figure 3 The dark areas are copper phase and the light areas are tungsten phase. A large number of nano-sized tungsten particles are evenly distributed in the copper matrix. The larger tungsten particles are composed of multiple particles, and the largest tungsten particle size is less than 2μm. No voids can be observed.

[0030] Figure 4 This is a SEM image of the tungsten-copper composite powder prepared in step (4) of Example 4. Figure 4 It can be seen that the tungsten-copper composite powder has a uniform and fine particle size, with large particles composed of multiple small particles.

[0031] Figure 5 This is a BSEM image of the high copper content tungsten-copper alloy prepared in Example 4, with a copper mass content of 90% and a tungsten mass content of 10%. Figure 3 The dark-colored areas are copper phase, and the light-colored areas are tungsten phase. Tungsten particles are evenly distributed in the copper matrix, and the size of the tungsten particles is less than 2μm. No voids can be observed.

[0032] The density, electrical conductivity, and hardness of the high-copper-content tungsten-copper alloys prepared in Examples 1-5 were tested, and the results are shown in Table 1. Table 1. Performance of high-copper-content tungsten-copper alloys prepared in Examples 1-5 As shown in Table 1, the high copper content tungsten-copper alloy prepared by this invention exhibits increased density and electrical conductivity, but decreased hardness, with increasing copper content. This high copper content tungsten-copper alloy material has a significantly higher hardness (40HV) than annealed (soft) copper, and its electrical conductivity meets the requirements for contact materials. It can replace some silver-containing contacts, thereby reducing contact material costs. It can also be used for EDM electrode processing and spot welding heads. Furthermore, as a point-strengthened copper alloy, it maintains high conductivity while retaining high hardness, solving the problem of pure copper softening and deforming at higher temperatures, which limits its applications.

[0033] The above description is merely an embodiment of the present invention and is not intended to limit the present invention in any way. The present invention can also have other embodiments based on the above structure and function, which will not be listed hereafter. Therefore, any simple modifications, equivalent changes, and alterations made by those skilled in the art to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A preparation process for a high-copper-content tungsten-copper alloy, characterized in that... Includes the following steps: 1) Disperse the anionic surfactant in nonanol as solution I, prepare a soluble tungsten salt aqueous solution as solution II, and prepare a soluble copper salt aqueous solution as solution III. Add solution II dropwise to solution I and stir until homogeneous to obtain mixture S1. Then add solution III to mixture S1 and stir until homogeneous to obtain mixture S2. The concentration of anionic surfactant in solution I is 0.5~2 mol / L; the concentration of tungsten salt in solution II is 0.01~2 mol / L; the concentration of copper salt in solution III is 0.5~2.0 mol / L; and the mass ratio of copper to tungsten is (60~99):(1~40). 2) Add the ethanolamine solution dropwise to the mixture S2, stir until homogeneous, control the pH of the mixture to 5-6.4, then heat and stir in an oil bath, filter the precursor obtained from the reaction, wash the filtrate with distilled water until neutral, then wash with ethanol 2-3 times, and dry to obtain the precursor. 3) The precursor obtained in step 2) is calcined in air at a heating rate of 10~20℃ / min, a calcination temperature of 500~650℃, and a calcination time of 1~5 h; then it is reduced in a hydrogen atmosphere to obtain tungsten-copper composite powder. 4) The tungsten-copper composite powder is loaded into a rubber mold and subjected to cold isostatic pressing to produce a green blank; 5) Vacuum the obtained green billet, and then put the vacuum-sealed green billet into a hot isostatic pressing (HIP) equipment for HIP treatment. The HIP temperature is 850~1000℃, the pressure is 90~150 MPa, and the treatment time is 2~6 h. After removing the cladding, a high copper content tungsten-copper alloy is obtained.

2. The preparation process of the high copper content tungsten-copper alloy as described in claim 1, characterized in that... The anionic surfactant in step 1) is fatty alcohol polyoxyethylene ether sulfate, alkyl alcohol amide, or alkylphenol sulfonate; the soluble tungsten salt is selected from one or more of ammonium metatungstate, sodium tungstate, ammonium paratungstate, and potassium tungstate; the soluble copper salt is selected from one or more of copper nitrate, copper chloride, copper sulfate, and copper oxalate.

3. The preparation process of the high copper content tungsten-copper alloy as described in claim 1, characterized in that... In step 1), the volume ratio of nonanol to solution III is 1:

4.

4. The preparation process of the high copper content tungsten-copper alloy as described in claim 1, characterized in that... In step 2), the concentration of the ethanolamine solution is 0.1~1.5 mol / L; the oil bath heating and stirring reaction temperature is 75~110℃, the time is 2~12 h, and the stirring rate is 50~500 r / min.

5. The preparation process of the high copper content tungsten-copper alloy as described in claim 1, characterized in that... Step 3) involves a two-stage hydrogen reduction. The first stage involves a hydrogen reduction at a temperature of 400–550°C for 1–3 hours, with a hydrogen flow rate of 10 m³ / h. 3 / h~20m 3 / h, powder spreading height ≤2 / 3; second-stage hydrogen reduction temperature 750~800℃, time 1~4 h, hydrogen flow rate 15 m³ / h. 3 / h~25m 3 / h, powder spreading height ≤2 / 3.

6. The preparation process of the high copper content tungsten-copper alloy as described in claim 1, characterized in that... The pressure for cold isostatic pressing is 110~200 MPa, and the time is 20~60 min.

7. The preparation process of the high copper content tungsten-copper alloy according to any one of claims 1 to 6, characterized in that... The prepared high-copper-content tungsten-copper alloys contain 60-99% copper and 1-40% tungsten by mass.

8. The preparation process of the high copper content tungsten-copper alloy according to any one of claims 1 to 6, characterized in that... The prepared high-copper-content tungsten-copper alloys have an electrical conductivity of 70.5–92% IACS, a hardness of 75–209 HV, and a density of 98.6–99.5%.

9. A high-copper-content tungsten-copper alloy prepared by the preparation process according to any one of claims 1 to 6.

10. The application of the high copper content tungsten-copper alloy prepared by the preparation process according to any one of claims 1 to 6 in contact materials.

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