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CN119900009B - Copper-tungsten alloy and its preparation process - Google Patents

Copper-tungsten alloy and its preparation process

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Publication number
CN119900009B
CN119900009B CN202510085850.4A CN202510085850A CN119900009B CN 119900009 B CN119900009 B CN 119900009B CN 202510085850 A CN202510085850 A CN 202510085850A CN 119900009 B CN119900009 B CN 119900009B
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copper
tungsten
powder
sintering
alloy
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CN119900009A (en
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钱旦
胡镖
刘通宇
史静雯
孟瑜
孙崇锋
宋忠孝
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Xian Jiaotong University
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Powder Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention belongs to the technical field of tungsten-copper alloy materials, and particularly relates to a copper-tungsten alloy and a preparation process thereof, wherein after tungsten powder is dried and ball-milled, plasma activation treatment is carried out on the surface of the tungsten powder under the action of ultrasonic vibration; under the action of ultrasonic vibration, a magnetron sputtering method is adopted to sputter a copper coating on the surface of the activated tungsten powder to obtain copper-clad tungsten composite powder, the copper-clad tungsten composite powder and the copper powder are uniformly mixed and subjected to vacuum hot-pressing sintering to prepare an initial state copper-tungsten alloy block, and the initial state copper-tungsten alloy block is subjected to semi-liquid state sintering to prepare the copper-tungsten alloy. According to the invention, a layer of high-purity copper with a certain thickness is coated on the surface of the tungsten powder based on the magnetron sputtering method, so that the copper-tungsten interface is effectively modified, the impurity elements in the tungsten-copper alloy can be obviously reduced, the tissue uniformity of the tungsten-copper alloy is improved, and finally the tungsten-copper alloy with uniform tissue and high compactness is obtained.

Description

Copper-tungsten alloy and preparation process thereof
Technical Field
The invention belongs to the technical field of tungsten-copper alloy materials, and relates to a copper-tungsten alloy and a preparation process thereof.
Background
The tungsten-copper alloy has high density, high strength, high ablation resistance and fusion welding resistance, good heat and electric conduction performance and high temperature performance, and is widely applied to electric contact materials of various high-voltage circuit breaker core components, electrode materials for electric spark machining, materials for devices for transmitting large heat flow and the like. Tungsten-copper alloy is used as a typical pseudoalloy, and the high melting point characteristic of tungsten determines that tungsten-copper can only be prepared by special preparation technologies such as powder metallurgy technology. The preparation process generally involves two key links of powder preparation and powder molding.
Powder preparation is a key technical basis for obtaining tungsten-copper alloy. Because the melting points of tungsten and copper are very different, the tungsten-copper alloy powder is not feasible to prepare by the traditional technical means of atomizing and other alloy powder. At present, the composite powder used for preparing the tungsten-copper alloy can be mixed powder of tungsten and copper, the powder is generally obtained by a mechanical stirring mode such as a mixer or ball mill, the uniformity of the obtained mixed powder is poor, unnecessary impurities are often introduced in the ball mill mixing process, the heat conduction performance and the like of the tungsten-copper alloy are extremely unfavorable, coating type powder can be used for preparing the tungsten-copper alloy, the structure uniformity of the powder is generally obviously better than that of the tungsten-copper mixed powder obtained by mixing through mechanical means, and the interface bonding effect of tungsten and copper in the obtained composite powder is better, so that the tungsten-copper alloy is extremely favorable for preparing the high-performance tungsten-copper alloy.
At present, the coated composite powder has good microscopic uniformity and good surface bonding effect. At present, many researches on preparation of coated composite powder are carried out, and various methods are presented. The coating methods which are widely used at present are chemical vapor deposition, precipitation, sol-gel, chemical plating and the like. These methods are all in the field of chemistry. In general, the chemical method introduces more metal impurities such as carbon, oxygen atoms, iron and the like into the precipitated metal micro-nano particles, and the impurity elements weaken the purity of tungsten-copper alloy prepared by chemical coating powder and influence the tissue uniformity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a copper-tungsten alloy and a preparation process thereof, wherein copper is plated on tungsten powder by a magnetron sputtering method under a vacuum condition to obtain high-activity copper-coated tungsten composite powder with uniform structure and high purity, and further vacuum hot-pressing sintering is adopted to obtain a copper-tungsten block alloy. The obtained alloy has few impurity elements, uniform structure and high density, and meanwhile, the copper layer coated by magnetron sputtering is in a metastable state, so that the sintering time in the hot-pressing sintering process is short and the energy consumption is low. The invention solves the problems of uneven structure and higher impurity content of the copper-tungsten alloy prepared by the traditional method, and effectively reduces the sintering energy consumption.
The invention is realized by the following technical scheme.
The invention provides a preparation process of a copper-tungsten alloy, which comprises the following steps:
and (3) drying and ball milling the tungsten powder, and then performing plasma activation treatment on the surface of the tungsten powder under the action of ultrasonic vibration. The method can remove residual impurities on the surface of the tungsten powder, increase the surface energy of the tungsten powder, and better combine with coated metal and is stronger in combination.
And sputtering a copper coating on the surface of the activated tungsten powder particles by adopting a magnetron sputtering method under the action of ultrasonic vibration until the thickness of the copper coating is 0.2-20 mu m, so as to obtain the copper-coated tungsten composite powder. After the tungsten powder particles are activated, the surface energy is improved to ensure that the tungsten powder and copper form firm chemical bond combination, the tungsten powder is in a continuous vibration state in the film coating process, and meanwhile, the film coating speed is controlled, so that uniform coating of each surface of the particles is realized, an important foundation is laid for the tissue uniformity of tungsten-copper block alloy, and the sputtering process is completely finished under a high vacuum condition because targets used by magnetron sputtering are high in purity (99.99%), so that the purity of the obtained copper-clad tungsten composite powder is high, and the existence of impurity components in the particles is avoided.
Uniformly mixing the copper-clad tungsten composite powder and the pure copper powder, and performing vacuum hot-pressing sintering to prepare an initial state copper-tungsten alloy block.
And (3) performing semi-liquid sintering on the initial state copper-tungsten alloy block, wherein part of pure copper is melted in the semi-liquid sintering process, and the melted liquid copper is filled into the micro-nano holes of the initial state copper-tungsten alloy block to prepare the copper-tungsten alloy. The copper-clad tungsten powder particles have some tiny gaps in the hot pressing process, and partial holes exist in the hot pressing sintered block due to the gaps, which are unavoidable phenomena including vacuum hot pressing sintering, plasma rapid sintering, high-pressure sintering and the like in the traditional sintering technology. According to the invention, on the basis of hot-pressed sintering, the micro-nano holes in the hot-pressed sintered primary blank are effectively filled by semi-liquid sintering (namely, partial melting of pure copper under the sintering temperature condition), and the molten liquid copper is beneficial to improving the bonding effect and compactness of a sintering structure.
In the preferred embodiment of the invention, the plasma activation treatment is carried out by adopting continuous magnetron sputtering coating equipment, and the platform is kept to vibrate during the treatment process, wherein the specific parameters are that the protective atmosphere is Ar, the working air pressure is 0.5 Pa-1.0 Pa, the treatment time is 5 min-30 min, the temperature is room temperature, the power is 200W-600W, and the bias voltage is 80V-200V.
In the preferred embodiment of the invention, continuous magnetron sputtering coating equipment is adopted for magnetron sputtering, a platform is kept to vibrate in the deposition process, the parameters are that the working atmosphere is Ar, the working air pressure is 0.2 Pa-0.6 Pa, the magnetron sputtering power is 800W-1200W, the sputtering time is 50 min-120 min, and the heating temperature of a vacuum chamber is 40 ℃ to 80 ℃.
In the preferred embodiment of the invention, the mass ratio of the copper-clad tungsten composite powder to the pure copper powder is 0.26-0.75:1.
In the preferred embodiment of the invention, during vacuum hot-pressing sintering, the vacuum degree is 1X 10 -3 Pa, the sintering pressure is 20 MPa-60 MPa, the temperature is 850-950 ℃, the heat preservation time is 20-60 min, and the cooling mode is furnace-following cooling.
In the preferred embodiment of the invention, the vacuum degree is 1X 10 -3 Pa, the vacuum degree is 20MPa to 60MPa, the vacuum degree is 1085 ℃ to 1200 ℃, the heat preservation time is 20min to 60min, and the cooling mode is furnace-following cooling.
In a preferred embodiment of the invention, after semi-liquid sintering, the ratio of the mass of the copper tungsten powder to the mass of the pure copper in the copper tungsten alloy is 0.16-0.55:1.
In a preferred embodiment of the invention, the particle size of the tungsten powder is 1-8 μm, and the tungsten powder is ball-milled for 0.5h after being dried. The purity of the copper target material and copper powder used in the magnetron sputtering is more than or equal to 99.99 percent.
The invention also provides the copper-tungsten alloy prepared by the preparation process.
Compared with the prior art, the invention has the following beneficial effects:
the invention copper-plating tungsten powder by a magnetron sputtering method under vacuum condition to obtain high-activity copper-clad tungsten composite powder with uniform structure and high purity, and then carrying out vacuum hot-pressing sintering and semi-liquid sintering to obtain copper-tungsten alloy, wherein the prepared copper-tungsten alloy has high purity and uniform structure, and the specific mechanism is as follows:
The method comprises the steps of carrying out plasma activation treatment on tungsten powder particles before coating, not only removing residual impurities on the surfaces of the tungsten powder, but also increasing the surface energy of the tungsten powder, better combining with coated metal and stronger combining, carrying out magnetron sputtering copper plating in an ultrasonic vibration environment, enabling the tungsten powder particles to form firm chemical bond combination with copper by lifting the surface energy after the activation of the tungsten powder particles, and simultaneously controlling the coating speed in the coating process, thereby realizing uniform coating of each surface of the particles, laying an important foundation for the tissue uniformity of tungsten copper block alloy, and completing the sputtering process completely under high vacuum condition because the target material used by magnetron sputtering is high-purity (99.99%), so that the purity of the obtained copper-coated tungsten composite powder is high, and the existence of impurity components in the particles is avoided.
The copper-clad tungsten powder particles have some tiny gaps in the hot pressing process, and partial holes exist in the hot pressing sintered block due to the gaps, which are unavoidable phenomena including vacuum hot pressing sintering, plasma rapid sintering, high-pressure sintering and the like in the traditional sintering technology. According to the invention, on the basis of hot-pressed sintering, the micro-nano holes in the hot-pressed sintered primary blank are effectively filled by semi-liquid sintering (namely, partial melting of pure copper under the sintering temperature condition), and the molten liquid copper is beneficial to improving the bonding effect and compactness of a sintering structure.
Drawings
In fig. 1, (a) is a cross-sectional view of the copper-clad tungsten composite powder obtained in step 1 of example 1, (b) and (c) are EDS spectrum element distribution diagrams of the copper-clad tungsten composite powder, wherein (b) is tungsten element and (c) is copper element.
Fig. 2 is an SEM image of the as-spun copper tungsten alloy block obtained in step 2 of example 1.
Fig. 3 is an SEM image of the copper-tungsten alloy obtained in step 3 of example 1.
Fig. 4 is an SEM image of the copper-tungsten alloy obtained in comparative example 1.
Fig. 5 is a gold phase diagram of the copper-tungsten alloy obtained in comparative example 1.
FIG. 6 is a gold phase diagram of the copper tungsten alloy obtained in step 3 of example 1.
FIG. 7 is a graph of the grain size of the copper-tungsten alloy obtained in step 3 of example 1.
Fig. 8 is a graph of the grain size of the copper-tungsten alloy obtained in comparative example 1.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting. The experimental methods and the detection methods described in the following examples are conventional methods unless otherwise specified, and the reagents and materials are commercially available.
Example 1
A preparation process of copper-tungsten alloy comprises the following steps:
step 1, preparation of copper-clad tungsten composite powder
1) Dispersing tungsten powder into a cavity of oven equipment, wherein the granularity of the tungsten powder is 1-8 mu m, drying the tungsten powder at 100 ℃ for 0.5h and then ball-milling for 0.5h before copper plating by a magnetron sputtering method, so that the agglomerated tungsten powder is fully dispersed.
2) Uniformly spreading tungsten powder particles obtained in the step 1) on a heating platform by adopting continuous magnetron sputtering coating equipment, then placing the platform on a conveyor belt, keeping the platform vibrating in the deposition process, and adjusting parameters to perform plasma activation treatment on the tungsten powder particles, wherein the specific parameters are that the temperature is room temperature, the working atmosphere is Ar, the working air pressure is 0.8Pa, the cleaning time is 10min, the power is 400W, and the bias voltage is 100V.
3) And (3) using the same equipment to adjust the magnetron sputtering parameters, namely Ar as working atmosphere, 0.6Pa as working air pressure, 1000W as magnetron sputtering power, 50min as sputtering time and 50 ℃ as heating temperature of a vacuum chamber, and obtaining the copper-clad tungsten composite powder. The thickness of the copper plating layer is distributed within 0.2-1.1 mu m. The post-treatment process of magnetron sputtering plating comprises vacuum drying and vacuum encapsulation.
Step 2, vacuum hot-pressing sintering
The copper-clad tungsten composite powder and the high-purity copper powder are poured into a phi 30 graphite die, and the ratio of the two powders is about 0.75:1. Then placing the mixture into a vacuum hot-pressing sintering furnace, vacuumizing and pressurizing, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 50MPa, the temperature is 850 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is cooling along with the furnace, so as to obtain the initial state copper-tungsten alloy block.
Step 3, semi-liquid sintering
5) And (3) placing the initial state copper-tungsten alloy block into a phi 50 graphite mold, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 50MPa, the temperature is 1085 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is furnace-following cooling, so that the copper-tungsten alloy is prepared.
Example 2
A preparation process of copper-tungsten alloy comprises the following steps:
step 1, preparation of copper-clad tungsten composite powder
1) Dispersing tungsten powder into a cavity of oven equipment, wherein the granularity of the tungsten powder is 1-8 mu m, drying the tungsten powder at 100 ℃ for 0.5h and then ball-milling for 0.5h before copper plating by a magnetron sputtering method, so that the agglomerated tungsten powder is fully dispersed.
2) Uniformly spreading tungsten powder particles obtained in the step 1) on a heating platform by adopting continuous magnetron sputtering coating equipment, then placing the platform on a conveyor belt, keeping the platform vibrating in the deposition process, and adjusting parameters to perform plasma activation treatment on the tungsten powder particles, wherein the specific parameters are that the temperature is room temperature, the working atmosphere is Ar, the working air pressure is 0.8Pa, the cleaning time is 10min, the power is 400W, and the bias voltage is 100V.
3) And (3) using the same equipment to adjust the magnetron sputtering parameters, namely Ar as working atmosphere, 0.6Pa as working air pressure, 1000W as magnetron sputtering power, 80min as sputtering time and 50 ℃ as heating temperature in a vacuum chamber, so as to obtain the copper-clad tungsten composite powder. The thickness of the copper plating layer is distributed at 7-8 mu m. The post-treatment process of magnetron sputtering plating comprises vacuum drying and vacuum encapsulation.
Step 2, vacuum hot-pressing sintering
Pouring the copper-clad tungsten composite powder and the high-purity copper powder into a phi 30 graphite die, wherein the ratio of the two powders is about 0.7:1. Then placing the mixture into a vacuum hot-pressing sintering furnace, vacuumizing and pressurizing, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 60MPa, the temperature is 950 ℃, the heat preservation time is 30min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is cooling along with the furnace, so as to obtain the initial state copper-tungsten alloy block.
Step 3, semi-liquid sintering
5) And (3) placing the initial state copper-tungsten alloy block into a phi 50 graphite mold, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 50MPa, the temperature is 1085 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is furnace-following cooling, so that the copper-tungsten alloy is prepared.
Example 3
A preparation process of copper-tungsten alloy comprises the following steps:
step 1, preparation of copper-clad tungsten composite powder
1) Dispersing tungsten powder into a cavity of oven equipment, wherein the granularity of the tungsten powder is 1-8 mu m, drying the tungsten powder at 100 ℃ for 0.5h and then ball-milling for 0.5h before copper plating by a magnetron sputtering method, so that the agglomerated tungsten powder is fully dispersed.
2) Uniformly spreading tungsten powder particles obtained in the step 1) on a heating platform by adopting continuous magnetron sputtering coating equipment, then placing the platform on a conveyor belt, keeping the platform vibrating in the deposition process, and adjusting parameters to perform plasma activation treatment on the tungsten powder particles, wherein the specific parameters are that the temperature is room temperature, the working atmosphere is Ar, the working air pressure is 0.8Pa, the cleaning time is 10min, the power is 400W, and the bias voltage is 100V.
3) And (3) using the same equipment to adjust the magnetron sputtering parameters, namely Ar as working atmosphere, 0.6Pa as working air pressure, 1000W as magnetron sputtering power, 110min as sputtering time and 50 ℃ as heating temperature in a vacuum chamber, so as to obtain the copper-clad tungsten composite powder. The thickness of the copper plating layer is distributed at 18-19 mu m. The post-treatment process of magnetron sputtering plating comprises vacuum drying and vacuum encapsulation.
Step 2, vacuum hot-pressing sintering
Pouring the copper-clad tungsten composite powder and the high-purity copper powder into a phi 30 graphite die, wherein the ratio of the two powders is about 0.7:1. Then placing the mixture into a vacuum hot-pressing sintering furnace, vacuumizing and pressurizing, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 20MPa, the temperature is 900 ℃, the heat preservation time is 60min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is cooling along with the furnace, so that the initial state copper-tungsten alloy block is prepared.
Step 3, semi-liquid sintering
5) And (3) placing the initial state copper-tungsten alloy block into a phi 50 graphite mold, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 20MPa, the temperature is 1200 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is furnace-following cooling, so that the copper-tungsten alloy is prepared.
Example 4
A preparation process of copper-tungsten alloy comprises the following steps:
step 1, preparation of copper-clad tungsten composite powder
1) Dispersing tungsten powder into a cavity of oven equipment, wherein the granularity of the tungsten powder is 1-8 mu m, drying the tungsten powder at 100 ℃ for 0.5h and then ball-milling for 0.5h before copper plating by a magnetron sputtering method, so that the agglomerated tungsten powder is fully dispersed.
2) Uniformly spreading tungsten powder particles obtained in the step 1) on a heating platform by adopting continuous magnetron sputtering coating equipment, then placing the platform on a conveyor belt, keeping the platform vibrating in the deposition process, and adjusting parameters to perform plasma activation treatment on the tungsten powder particles, wherein the specific parameters are that the temperature is room temperature, the working atmosphere is Ar, the working air pressure is 0.5Pa, the cleaning time is 30min, the power is 600W and the bias voltage is 80V.
3) And (3) using the same equipment to adjust the magnetron sputtering parameters, namely Ar as working atmosphere, 0.2Pa as working air pressure, 800W as magnetron sputtering power, 110min as sputtering time and 50 ℃ as heating temperature in a vacuum chamber, so as to obtain the copper-clad tungsten composite powder. The thickness of the copper plating layer is distributed at 19-20 mu m. The post-treatment process of magnetron sputtering plating comprises vacuum drying and vacuum encapsulation.
Step 2, vacuum hot-pressing sintering
Pouring the copper-clad tungsten composite powder and the high-purity copper powder into a phi 30 graphite die, wherein the ratio of the two powders is about 0.7:1. Then placing the mixture into a vacuum hot-pressing sintering furnace, vacuumizing and pressurizing, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 50MPa, the temperature is 850 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is cooling along with the furnace, so as to obtain the initial state copper-tungsten alloy block.
Step 3, semi-liquid sintering
5) And (3) placing the initial state copper-tungsten alloy block into a phi 50 graphite mold, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 50MPa, the temperature is 1100 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is furnace-following cooling, so that the copper-tungsten alloy is prepared.
Example 5
A preparation process of copper-tungsten alloy comprises the following steps:
step 1, preparation of copper-clad tungsten composite powder
1) Dispersing tungsten powder into a cavity of oven equipment, wherein the granularity of the tungsten powder is 1-8 mu m, drying the tungsten powder at 100 ℃ for 0.5h and then ball-milling for 0.5h before copper plating by a magnetron sputtering method, so that the agglomerated tungsten powder is fully dispersed.
2) Uniformly spreading tungsten powder particles obtained in the step 1) on a heating platform by adopting continuous magnetron sputtering coating equipment, then placing the platform on a conveyor belt, keeping the platform vibrating in the deposition process, and adjusting parameters to perform plasma activation treatment on the tungsten powder particles, wherein the specific parameters are that the temperature is room temperature, the working atmosphere is Ar, the working air pressure is 1Pa, the cleaning time is 5min, the power is 200W, and the bias voltage is 200V.
3) And (3) using the same equipment to adjust the magnetron sputtering parameters, namely Ar as working atmosphere, 0.2Pa as working air pressure, 1200W as magnetron sputtering power, 120min as sputtering time and 50 ℃ as heating temperature in a vacuum chamber, and obtaining the copper-clad tungsten composite powder. The thickness of the copper plating layer is distributed at 19-20 mu m. The post-treatment process of magnetron sputtering plating comprises vacuum drying and vacuum encapsulation.
Step 2, vacuum hot-pressing sintering
Pouring the copper-clad tungsten composite powder and the high-purity copper powder into a phi 30 graphite die, wherein the ratio of the two powders is about 0.7:1. Then placing the mixture into a vacuum hot-pressing sintering furnace, vacuumizing and pressurizing, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 50MPa, the temperature is 850 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is cooling along with the furnace, so as to obtain the initial state copper-tungsten alloy block.
Step 3, semi-liquid sintering
5) And (3) placing the initial state copper-tungsten alloy block into a phi 50 graphite mold, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 50MPa, the temperature is 1085 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is furnace-following cooling, so that the copper-tungsten alloy is prepared.
Comparative example 1
Compared with example 1, the method adopts one-step sintering, and specifically comprises the following steps:
step 1, preparation of copper-clad tungsten composite powder
1) Dispersing tungsten powder into a cavity of oven equipment, wherein the granularity of the tungsten powder is 1-8 mu m, drying the tungsten powder at 100 ℃ for 0.5h and then ball-milling for 0.5h before copper plating by a magnetron sputtering method, so that the agglomerated tungsten powder is fully dispersed.
2) Uniformly spreading tungsten powder particles obtained in the step 1) on a heating platform by adopting continuous magnetron sputtering coating equipment, then placing the platform on a conveyor belt, keeping the platform vibrating in the deposition process, and adjusting parameters to perform plasma activation treatment on the tungsten powder particles, wherein the specific parameters are that the temperature is room temperature, the working atmosphere is Ar, the working air pressure is 0.8Pa, the cleaning time is 10min, the power is 400W, and the bias voltage is 100V.
3) And (3) using the same equipment to adjust the magnetron sputtering parameters, namely Ar as working atmosphere, 0.6Pa as working air pressure, 1000W as magnetron sputtering power, 50min as sputtering time and 50 ℃ as heating temperature of a vacuum chamber, and obtaining the copper-clad tungsten composite powder. The thickness of the copper plating layer is distributed within 0.2-1.1 mu m. The post-treatment process of magnetron sputtering plating comprises vacuum drying and vacuum encapsulation.
Step 2, vacuum hot-pressing sintering
The copper-clad tungsten composite powder and the high-purity copper powder are poured into a phi 30 graphite die, and the ratio of the two powders is about 0.75:1. Then placing the mixture into a vacuum hot-pressing sintering furnace, vacuumizing and pressurizing, and after the vacuum degree is lower than 10Pa, starting sintering, wherein the sintering pressure is 50MPa, the temperature is 1085 ℃, the heat preservation time is 20min, the vacuum degree is 1 multiplied by 10 -3 Pa, and the cooling mode is furnace-following cooling, so that the initial state copper-tungsten alloy block is prepared.
In fig. 1, (a) is a cross-sectional view of the copper-clad tungsten composite powder obtained in step 1 of example 1, (b) and (c) are EDS spectrum element distribution diagrams of the copper-clad tungsten composite powder, wherein (b) is tungsten element and (c) is copper element. It can be seen that the copper coating is uniformly plated on the surface of the tungsten powder, and only the large-particle-size composite powder is exposed by part of tungsten after sample grinding.
Fig. 2 is an SEM image of the as-spun copper tungsten alloy block obtained in step 2 of example 1. It can be seen that the lower density, only some of the small particle powder and the large particle powder formed a sintering neck, and the large particles did not fuse completely.
Fig. 3 is an SEM image of the copper-tungsten alloy obtained in step 3 of example 1. Fig. 4 is an SEM image of the copper-tungsten alloy obtained in comparative example 1. In comparative example 1, the alloy was rough and uneven, and in example 1, the alloy structure was even.
Fig. 5 is a gold phase diagram of the copper-tungsten alloy obtained in comparative example 1. FIG. 6 is a gold phase diagram of the copper tungsten alloy obtained in step 3 of example 1. The alloy of fig. 6 is more dense than that of comparative example 1. The invention is characterized in that the vacuum hot-pressing sintering is firstly carried out, and then the semi-liquid state sintering is carried out, thereby being beneficial to improving the density of the alloy.
FIG. 7 is a graph of the grain size of the copper-tungsten alloy obtained in step 3 of example 1. Fig. 8 is a graph of the grain size of the copper-tungsten alloy obtained in comparative example 1. It can be seen that the copper tungsten alloy grain size distribution is more uniform and the grains are smaller in example 1 than in comparative example 1, and the copper tungsten alloy grain size is more dispersed and the grain size is larger in comparative example 1. The alloy prepared by the one-step sintering method is unfavorable for refining alloy grains. The other embodiments are similar to embodiment 1, and will not be described again.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that such modifications and variations be included herein within the scope of the appended claims and their equivalents.

Claims (6)

1.一种铜钨合金的制备工艺，其特征在于，包括以下步骤：1. A process for preparing a copper-tungsten alloy, comprising the following steps: 将钨粉末干燥球磨后，在超声振动作用下，对钨粉末表面进行等离子活化处理；After the tungsten powder is dried and ball-milled, the surface of the tungsten powder is plasma activated under the action of ultrasonic vibration; 超声振动作用下，采用磁控溅射方法在活化后的钨粉末表面上溅射铜镀层，获得铜包钨复合粉末；磁控溅射铜镀层的厚度为0.2μm~20μm；Under the action of ultrasonic vibration, a copper coating is sputtered on the surface of the activated tungsten powder by magnetron sputtering to obtain a copper-coated tungsten composite powder; the thickness of the magnetron sputtered copper coating is 0.2μm~20μm; 将铜包钨复合粉末和铜粉末均匀混合，进行真空热压烧结，制备初态铜钨合金块体；铜包钨复合粉末和铜粉末的质量比为0.26~0.75:1；The copper-coated tungsten composite powder and copper powder are uniformly mixed and vacuum hot-pressed to prepare an initial copper-tungsten alloy block; the mass ratio of the copper-coated tungsten composite powder to the copper powder is 0.26-0.75:1; 将所述初态铜钨合金块体进行半液态烧结，半液态烧结过程中，部分铜熔融，熔融的液态铜填充至所述初态铜钨合金块体存在的微纳米孔洞内，制得铜钨合金；半液态烧结时，真空条件下，烧结压强为20MPa~60MPa，温度为1085℃~1200℃，保温时间为20min~60min。The initial copper-tungsten alloy block is semi-liquid sintered. During the semi-liquid sintering process, part of the copper melts, and the molten liquid copper fills the micro-nano pores in the initial copper-tungsten alloy block to produce a copper-tungsten alloy. During the semi-liquid sintering, under vacuum conditions, the sintering pressure is 20MPa~60MPa, the temperature is 1085℃~1200℃, and the holding time is 20min~60min. 2.根据权利要求1所述的铜钨合金的制备工艺，其特征在于，采用连续磁控溅射镀膜设备进行等离子活化处理，处理过程中保持平台振动，具体参数为：工作气氛为Ar，工作气压为0.5Pa~1.0Pa，处理时间为5min~30min，温度为室温，功率为200W~600W，偏压为80V~200V。2. The preparation process of the copper-tungsten alloy according to claim 1 is characterized in that a continuous magnetron sputtering coating device is used for plasma activation treatment, and the platform is kept vibrating during the treatment process. The specific parameters are: working atmosphere is Ar, working pressure is 0.5 Pa ~ 1.0 Pa, treatment time is 5 min ~ 30 min, temperature is room temperature, power is 200 W ~ 600 W, and bias voltage is 80 V ~ 200 V. 3.根据权利要求1所述的铜钨合金的制备工艺，其特征在于，采用连续磁控溅射镀膜设备进行磁控溅射，沉积过程中保持平台振动，参数为：工作气氛为Ar，工作气压为0.2Pa~0.6Pa，磁控溅射功率为800W~1200W，溅射时间为50min~120min，真空室加热温度为40℃~80℃。3. The preparation process of copper-tungsten alloy according to claim 1 is characterized in that continuous magnetron sputtering coating equipment is used for magnetron sputtering, the platform vibration is maintained during the deposition process, and the parameters are: working atmosphere is Ar, working pressure is 0.2Pa~0.6Pa, magnetron sputtering power is 800W~1200W, sputtering time is 50min~120min, and vacuum chamber heating temperature is 40°C~80°C. 4.根据权利要求1所述的铜钨合金的制备工艺，其特征在于，真空热压烧结时，真空条件下，烧结压强为20MPa~60MPa，温度为850℃~950℃，保温时间为20min~60min。4. The preparation process of the copper-tungsten alloy according to claim 1 is characterized in that during vacuum hot pressing sintering, under vacuum conditions, the sintering pressure is 20 MPa to 60 MPa, the temperature is 850° C. to 950° C., and the holding time is 20 min to 60 min. 5.根据权利要求1所述的铜钨合金的制备工艺，其特征在于，原料钨粉末的粒径为1μm~8μm，磁控溅射使用的铜靶材的纯度≥99.99%，铜粉末的纯度≥99.99%。5. The preparation process of the copper-tungsten alloy according to claim 1 is characterized in that the particle size of the raw tungsten powder is 1 μm to 8 μm, the purity of the copper target used in magnetron sputtering is ≥99.99%, and the purity of the copper powder is ≥99.99%. 6.根据权利要求1~5任一项所述的制备工艺制备的铜钨合金。6. A copper-tungsten alloy prepared according to the preparation process according to any one of claims 1 to 5.
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