CN105798319B - Preparation method of silver-tungsten electrical contact material, electrical contact material and electrical contact - Google Patents

Preparation method of silver-tungsten electrical contact material, electrical contact material and electrical contact Download PDF

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CN105798319B
CN105798319B CN201410853437.XA CN201410853437A CN105798319B CN 105798319 B CN105798319 B CN 105798319B CN 201410853437 A CN201410853437 A CN 201410853437A CN 105798319 B CN105798319 B CN 105798319B
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silver
tungsten
electrical contact
solution
contact material
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CN105798319A (en
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赖奕坚
刘楠
赵斌元
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Schneider Electric Industries SAS
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Schneider Electric Industries SAS
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Abstract

The embodiment of the invention relates to a preparation method of a silver-tungsten electrical contact material, which comprises the following steps: (1) mixing a silver-containing precursor solution and a sodium tungstate solution, and then adding acid to adjust the pH value of the solution; (2) adding a reducing agent into the obtained mixed solution to obtain silver powder coated by the tungsten-containing sol; and (3) carrying out heat treatment on the silver powder in a reducing atmosphere to obtain the silver-tungsten electrical contact material. Embodiments of the invention also relate to a preparation device of the silver-tungsten electrical contact material, the silver-tungsten electrical contact material prepared by the preparation method, and an electrical contact prepared by the silver-tungsten electrical contact material.

Description

Preparation method of silver-tungsten electrical contact material, electrical contact material and electrical contact
Technical Field
Embodiments of the present invention relate to the field of electrical contacts, and in particular, to a method and apparatus for preparing a silver-tungsten electrical contact material, and the prepared silver-tungsten electrical contact material and electrical contact.
Background
The electric contact is a key element of an electric switch, an instrument and a meter and the like and is used for switching on, bearing and breaking normal current and fault current. In the electrical contact material for manufacturing the electrical contact, the Ag-W contact material has good arc corrosion resistance, wear resistance, and low and stable contact resistance, so that the Ag-W contact material is widely applied to electrical contact materials of low-voltage electrical appliances, such as various frame-type universal circuit breakers, molded case circuit breakers, heavy load switches, electromagnetic switches, voltage regulating switches, and the like. The Ag-W contact material is prepared by dispersing tungsten particles with high melting point in a silver matrix, when an electric arc burns between contacts, the melted silver is attracted by capillaries of a framework, the silver can be vaporized only at high temperature, and the temperature of the tungsten particles is lower than the melting point of the tungsten particles due to vaporization, so that the melting loss of the contact material is reduced. The existing preparation method of the silver-tungsten composite material mainly comprises the following steps: powder metallurgy and infiltration. The powder metallurgy method is to prepare the contact material by the conventional powder mixing, pressing and sintering processes of silver powder and tungsten powder. The method is easy to generate segregation during powder mixing so that the metallographic structure of the product is unevenly distributed, stress is easy to generate inside the contact during pressing, and the easy-to-delaminate forming is difficult; the infiltration method is that the tungsten skeleton and silver blank containing partial silver (as induction silver in infiltration) or not containing silver are pressed, the skeleton is presintered at high temperature, then the two are overlapped and placed in a special infiltration sintering furnace, liquid phase winding is carried out above the melting point of silver, and the silver is filled into the skeleton pores under the melting state through capillary action, thus forming a compact interconnected integral material. The product prepared by the method has uniform metallographic structure and few pores, but has higher requirement on the granularity of the tungsten powder, an ideal framework structure can be formed only when the granularity of the tungsten powder is proper, so that liquid silver can be filled in the framework structure, and meanwhile, the problems of poor compactness and the like of the material are easily caused due to poor wettability of the silver to the tungsten.
It is known that CN102392170B discloses a processing method for manufacturing silver-tungsten composite contact material, which is to put tungsten powder into a reaction vessel, add water and a proper amount of reducing agent, spray silver-ammonia complexing solution while stirring, after cleaning and drying, high-energy ball milling treatment is carried out on the silver-tungsten coated powder, after stress removal treatment, primary pressing is carried out on the silver-tungsten powder, and presintering, infiltration sintering and re-pressing are carried out in reducing atmosphere to obtain the silver-tungsten composite contact material. The tungsten powder adopted by the invention is 2-10 mu m, the particle size is larger, silver and tungsten are not compounded in atomic scale, the size of tungsten particles depends on the size of the raw material tungsten powder and the parameters of high-energy ball milling, the tungsten powder can be broken to generate a new surface in the process of high-energy ball milling, and the silver-tungsten combination property is reduced.
Disclosure of Invention
In view of the defects in the prior art, embodiments of the present invention provide a method and an apparatus for preparing a silver-tungsten electrical contact material, so as to obtain an electrical contact material in which silver powder particles have uniform size, small particle size, and are easy to control, and the silver powder and a tungsten particle film layer form a dense combination.
According to a first aspect of the present invention, there is provided a method of making a silver-tungsten electrical contact material, comprising the steps of:
(1) mixing a silver-containing precursor solution and a sodium tungstate solution, and then adding acid to adjust the pH value of the solution;
(2) adding a reducing agent into the obtained mixed solution to obtain silver powder coated by the tungsten-containing sol; and
(3) and carrying out heat treatment on the silver powder in a reducing atmosphere to obtain the silver-tungsten electrical contact material.
In one embodiment of the invention, the acid is added to adjust the pH of the solution to less than 7.
In another embodiment of the present invention, the step (2) comprises: adding the reducing agent into the obtained mixed solution, separating the suspension obtained by the reaction, and drying the separated precipitate to obtain the silver powder coated by the tungsten-containing sol.
In another embodiment of the present invention, the step (2) comprises: and when the reducing agent is added into the obtained mixed solution, stirring or ultrasonic oscillation is carried out, wherein the stirring or ultrasonic oscillation temperature is 20-40 ℃, and the time is 0.5-6.0 h.
In still another embodiment of the invention, the silver-containing precursor solution is a silver nitrate solution with a concentration of 1-1000 ppm, the concentration of the sodium tungstate solution is 0.0010-10 wt%, and the mixing ratio of the sodium tungstate solution to the silver nitrate solution is 0.06-2.66: 1, based on the mass of the sodium tungstate and the silver nitrate.
In yet another embodiment of the present invention, the acid is acetic acid or nitric acid.
In yet another embodiment of the present invention, the reducing agent is selected from one or more of formaldehyde, glyoxal, ethylenediamine, glucose, sodium potassium tartrate, sodium citrate, hydrazine hydrate, vitamin C, sodium borohydride, and ascorbic acid.
In yet another embodiment of the present invention, the reducing atmosphere may be hydrogen gas, a hydrogen-containing mixture gas, or ammonia gas.
In still another embodiment of the present invention, the heat treatment is baking at 500 to 900 ℃ for 1 to 12 hours.
In still another embodiment of the present invention, the mass percentage of silver in the silver-tungsten electrical contact material is 30-95%.
In yet another embodiment of the present invention, the tungsten particles in the silver-tungsten electrical contact material are all on the micro-nanometer scale.
In still another embodiment of the present invention, the step (3) includes: and pressing and sintering the silver-tungsten composite powder subjected to heat treatment to prepare the silver-tungsten electrical contact material.
According to a second aspect of the present invention, there is provided an apparatus for preparing a silver-tungsten electrical contact material, comprising:
a mixing reaction device for mixing the silver-containing precursor solution, the sodium tungstate solution and the acid, and adding a reducing agent into the obtained mixed solution to obtain silver powder coated by the tungsten-containing sol; and
and the heat treatment device is used for carrying out heat treatment on the silver powder in a reducing atmosphere to prepare the silver-tungsten electrical contact material.
In another embodiment of the present invention, the preparation apparatus further comprises a separation apparatus for separating the suspension obtained by the reaction in the mixed reaction apparatus, and a drying apparatus for drying the precipitate obtained by the separation in the separation apparatus.
In another embodiment of the invention, the preparation device further comprises a stirring device or an ultrasonic oscillation device for stirring or ultrasonically oscillating the solution in the mixing reaction device, wherein the stirring or ultrasonically oscillating temperature is 20-40 ℃ and the time is 0.5-6.0 h.
In still another embodiment of the present invention, the manufacturing apparatus further includes a pressing apparatus and a sintering apparatus for pressing and sintering the heat-treated silver-tungsten mixed powder to manufacture the silver-tungsten electrical contact material.
According to a third aspect of the invention, a silver-tungsten electrical contact material is provided, which is prepared by the preparation method of the silver-tungsten electrical contact material according to the first aspect of the invention, wherein the silver-tungsten electrical contact material comprises silver powder and a continuous and uniform film layer composed of micro-nano tungsten particles coated on the surface of the silver powder.
According to another aspect of the present invention, there is provided an electrical contact, which is made of the silver-tungsten electrical contact material according to the third aspect of the present invention, and the silver-tungsten electrical contact material includes a silver powder and a continuous and uniform film layer composed of micro-nano tungsten particles coated on the surface of the silver powder.
According to the preparation method of the silver-tungsten electrical contact material, an in-situ synthesis liquid phase reduction method is adopted, silver and tungsten are compounded in atomic scale, so that the silver powder and the tungsten particle film layer are combined compactly, the film layer formed on the surface of the silver powder by the tungsten particle film layer is uniform and continuous, and the tungsten particles and the silver powder are fully and uniformly mixed; the silver powder obtained by reduction has uniform particle size, small particle size and adjustable size; controllable tungsten content, higher tungsten content than that of the dipping method and silver saving. In addition, the electrical contact material has the advantages of low preparation cost, simple process and low energy consumption.
Drawings
Embodiments of the invention will now be described, by way of example only, with reference to the accompanying schematic drawings in which similar elements are designated by the same reference numerals, and in which:
figure 1 is a flow diagram of a method of making a silver-tungsten electrical contact material according to one embodiment of the present invention;
fig. 2 is an X-ray diffraction pattern of a silver-tungsten sample prepared according to one embodiment of the preparation method of the present invention;
fig. 3 is a SEM photograph of a silver-tungsten sample prepared according to one embodiment of the preparation method of the present invention;
figure 4 is a schematic view of an apparatus for making silver-tungsten electrical contact material according to one embodiment of the present invention;
figure 5 is a schematic view of an apparatus for making silver-tungsten electrical contact material according to another embodiment of the present invention; and
figure 6 is a schematic view of an apparatus for making silver-tungsten electrical contact material according to an exemplary embodiment of the present invention.
Detailed Description
The principles and spirit of the present invention will be described with reference to exemplary embodiments. It should be understood that these examples are described only to enable those skilled in the art to better understand and to implement the present invention, and are not intended to limit the scope of the present invention in any way.
The preparation method of the silver-tungsten electrical contact material provided by the embodiment of the invention is simply to prepare the silver powder with the surface coated with the micro-nano tungsten particles by adopting in-situ synthesis liquid phase reduction, separation, drying and roasting. Specifically, the preparation method comprises the following steps: (1) mixing a silver-containing precursor solution and a sodium tungstate solution, and then adding acid to adjust the pH value of the solution; (2) adding a reducing agent into the obtained mixed solution to obtain silver powder coated by the tungsten-containing sol; and (3) carrying out heat treatment on the silver powder in a reducing atmosphere to obtain the silver-tungsten electrical contact material. In one embodiment of the present invention, as shown in fig. 1, the preparation conditions and process steps are:
A) preparation of the Mixed solution
Firstly, a silver-containing precursor solution and a sodium tungstate solution are respectively prepared, wherein the concentration of the prepared silver nitrate solution is 1-1000 ppm, and the concentration of the sodium tungstate solution is 0.0010-10 wt%.
And then mixing the silver-containing precursor solution (such as a silver nitrate solution) and a sodium tungstate solution according to a certain proportion, wherein the mass ratio of sodium tungstate to silver nitrate is 0.06-2.66: 1. Specifically, a sodium tungstate solution is added to a silver-containing precursor solution with stirring, followed by addition of an acid such as nitric acid, acetic acid, or the like, to adjust the pH of the solution to less than 7.
B) Reduction precipitation reaction
Adding a reducing agent into the mixed solution for carrying out reduction precipitation reaction, wherein the reducing agent is selected from one or more of formaldehyde, glyoxal, ethylenediamine, glucose, potassium sodium tartrate, sodium citrate, hydrazine hydrate, vitamin C, sodium borohydride and ascorbic acid, stirring or ultrasonic oscillation is carried out while the reducing agent is added, the temperature is 20-40 ℃, the time is 0.5-6.0 h, standing is carried out for a period of time after the reaction, and as a result, a continuous tungsten-containing sol thin layer is coated on the simple substance silver while the simple substance silver is reduced.
C) Separating and drying
The suspension of the mixture obtained by the reduction-precipitation reaction is separated, for example, by filtration such as plate and frame filter pressing, centrifugation or negative pressure suction filtration, and the precipitate obtained by the separation is dried to obtain silver powder coated with a tungsten-containing sol.
D) Thermal treatment
And (2) carrying out heat treatment, namely roasting, on the silver powder coated by the obtained tungsten-containing sol in a reducing atmosphere, wherein the heat treatment temperature is 500-900 ℃, and the time is 1-12 h, the tungsten-containing sol is reduced into micro-nano tungsten particles in the reducing atmosphere, and the silver powder coated with a uniform and continuous film layer formed by the micro-nano tungsten particles on the surface is obtained.
E) Powder metallurgy treatment
And performing powder metallurgy treatment such as pressing and sintering on the silver powder coated with the uniform and continuous film layer consisting of the micro-nano tungsten particles and subjected to heat treatment in a reducing atmosphere to prepare the silver-tungsten composite powder into the silver-tungsten electrical contact material.
The method has simple production process and low cost, and is suitable for industrial production; the prepared silver-tungsten powder reaches micro-nano level, and the silver powder and the tungsten particle film layer form compact combination and uniform mixing.
The present invention will be further explained with reference to the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
(1) Respectively preparing a sodium tungstate solution with the concentration of 0.001 wt% (by weight) and a silver nitrate solution with the concentration of 1ppm, uniformly mixing and stirring the sodium tungstate solution and the silver nitrate solution according to the proportion of 0.06:1 (by mass ratio of sodium tungstate to silver nitrate), for example, mixing 6kg of the sodium tungstate solution with 1000kg of the silver nitrate solution, and then dropwise adding an acetic acid solution to adjust the pH value of the solution to 6.0;
(2) adding a proper amount of ascorbic acid solution into the solution obtained in the step (1), stirring and reacting for 6h at 20 ℃, standing, separating, drying, roasting for 6h at 800 ℃ in a pure hydrogen atmosphere to obtain silver-tungsten composite powder, and then carrying out a conventional contact material preparation procedure to obtain the silver-tungsten electrical contact material.
Example 2
(1) Respectively preparing a sodium tungstate solution with the concentration of 10 wt% and a silver nitrate solution with the concentration of 1000ppm, uniformly mixing and stirring the sodium tungstate solution and the silver nitrate solution according to the proportion (by mass ratio of sodium tungstate to silver nitrate) of 2.66:1, for example, mixing 26.6g of the sodium tungstate solution with 1kg of the silver nitrate solution, then dropwise adding an acetic acid solution, and adjusting the pH value of the solution to be 6.5;
(2) and (2) adding a proper amount of ethylenediamine solution into the solution obtained in the step (1), carrying out ultrasonic oscillation reaction for 30min at 40 ℃, standing, separating, drying, roasting for 1h at 900 ℃ in a pure hydrogen atmosphere to obtain silver-tungsten composite powder, and then carrying out a conventional contact material preparation procedure to obtain the silver-tungsten electrical contact material.
Example 3
(1) Respectively preparing a sodium tungstate solution with the concentration of 2 wt% and a silver nitrate solution with the concentration of 100ppm, uniformly mixing and stirring the sodium tungstate solution and the silver nitrate solution according to the proportion (by mass ratio of sodium tungstate to silver nitrate) of 0.32:1, for example, mixing 16g of the sodium tungstate solution with 10kg of the silver nitrate solution, then dropwise adding an acetic acid solution, and adjusting the pH value of the solution to be 3.5;
(2) adding a proper amount of ascorbic acid solution into the solution obtained in the step (1), stirring and reacting for 30min at 25 ℃, standing, separating, drying, roasting for 12h at 650 ℃ in an ammonia atmosphere to prepare silver-tungsten composite powder, and then performing a conventional contact material preparation procedure to obtain the silver-tungsten electrical contact material.
The silver-tungsten composite powder obtained in the embodiment is subjected to SEM morphology analysis and XRD phase analysis, fig. 2 shows an X-ray diffraction pattern of a powder sample, and by comparing with a corresponding XRD software database, it can be known that three peak diffraction angles and corresponding crystal planes representing silver powder are found out, and the sample contains a diffraction angle corresponding to a corresponding crystal plane of a substance tungsten, which can prove that the nano-mixed powder contains tungsten, and the analysis also conforms to the result obtained by ICP-MS mass spectrometry. FIG. 3 is a SEM photograph of the powder sample, from which it can be seen that silver powder is uniformly distributed in the microstructure of the sample, and the silver powder particles may have solid matter coating on the surface, and the analysis can determine that the solid matter is tungsten.
Example 4
(1) Respectively preparing a sodium tungstate solution with the concentration of 5 wt% and a silver nitrate solution with the concentration of 500ppm, uniformly mixing and stirring the sodium tungstate solution and the silver nitrate solution according to the proportion (by mass ratio of sodium tungstate to silver nitrate) of 1.5:1, for example, mixing 30g of the sodium tungstate solution with 2kg of the silver nitrate solution, then dropwise adding an acetic acid solution, and adjusting the pH value of the solution to be 5.0;
(2) adding a proper amount of sodium borohydride solution into the solution obtained in the step (1), stirring and reacting for 2 hours at 20 ℃, standing, separating, drying, roasting for 2 hours at 500 ℃ in a hydrogen-argon mixed gas atmosphere to obtain silver-tungsten composite powder, and then performing a conventional contact material preparation procedure to obtain the silver-tungsten electrical contact material.
Example 5
(1) Respectively preparing a sodium tungstate solution with the concentration of 1 wt% and a silver nitrate solution with the concentration of 100ppm, uniformly mixing and stirring the sodium tungstate solution and the silver nitrate solution according to the proportion (by mass ratio of sodium tungstate to silver nitrate) of 2.0:1, for example, mixing 200g of the sodium tungstate solution with 10kg of the silver nitrate solution, then dropwise adding an acetic acid solution, and adjusting the pH value of the solution to be 4.7;
(2) adding a proper amount of glucose solution into the solution obtained in the step (1), stirring and reacting for 30min at 30 ℃, standing, separating, drying, roasting for 3h at 900 ℃ in a pure hydrogen atmosphere to obtain silver-tungsten composite powder, and then carrying out a conventional contact material preparation procedure to obtain the silver-tungsten electrical contact material.
Figure 4 is a block diagram illustrating an apparatus for preparing silver-tungsten electrical contact material according to one embodiment of the present invention, including;
a mixing reaction device 1 for mixing the silver-containing precursor solution, the sodium tungstate solution and the acid, and adding a reducing agent to the obtained mixed solution to obtain silver powder coated by the tungsten-containing sol; and
and the heat treatment device 4 is used for carrying out heat treatment on the silver powder in a reducing atmosphere to prepare the silver-tungsten electrical contact material.
In one embodiment, as shown in fig. 5, the preparation apparatus further includes:
a separation device 2 for separating the suspension obtained by the reaction in the mixing reaction device 1, and a drying device 3 for drying the precipitate obtained by the separation in the separation device 1.
In one embodiment of the present invention, as shown in fig. 6, in the above-mentioned manufacturing apparatus, the mixing reaction means may be a mixing tank 10, for example, mixing the silver nitrate solution and the sodium tungstate solution in a tank, adding acetic acid to adjust the pH, adding ascorbic acid to perform reduction precipitation reaction to generate mixture suspension containing simple substance silver, pouring the mixture suspension into a filtering device such as a plate-and-frame filter press 20 (or a negative pressure suction filter, a centrifugal filter) for filtering, putting the silver-tungsten-containing sol precipitate obtained by filtering into a drying device such as a vacuum oven 30 for drying, thereby obtaining silver powder coated with tungsten-containing sol, and finally, putting the silver powder into a heat treatment device such as a muffle furnace 40 (or a tunnel kiln, a mesh belt furnace, a rotary furnace and the like) for heat treatment (baking), thereby finally obtaining the silver-tungsten electrical contact material. In addition, the preparation device also comprises a pressing device and a sintering device, and the pressing device and the sintering device are used for pressing and sintering the silver-tungsten mixed powder subjected to heat treatment to prepare the silver-tungsten electric contact material.
In addition, the silver-tungsten electrical contact material can be prepared by the preparation method of the silver-tungsten electrical contact material of the embodiment of the invention. Further, electrical contacts were made using the silver-tungsten electrical contact materials of embodiments of the present invention.
The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will occur to those skilled in the art.

Claims (11)

1. A preparation method of a silver-tungsten electrical contact material comprises the following steps:
(1) mixing a silver-containing precursor solution and a sodium tungstate solution, and then adding acid to adjust the pH value of the solution;
(2) adding a reducing agent into the obtained mixed solution to obtain silver powder coated by the tungsten-containing sol; and
(3) and carrying out heat treatment on the silver powder in a reducing atmosphere to obtain the silver-tungsten electrical contact material.
2. The method of claim 1, wherein the addition of the acid adjusts the pH of the solution to less than 7.
3. The method of claim 1, wherein the step (2) comprises:
adding the reducing agent into the obtained mixed solution, separating the suspension obtained by the reaction, and drying the separated precipitate to obtain the silver powder coated by the tungsten-containing sol.
4. The method of claim 3, wherein the step (2) comprises:
and when the reducing agent is added into the obtained mixed solution, stirring or ultrasonic oscillation is carried out, wherein the stirring or ultrasonic oscillation temperature is 20-40 ℃, and the time is 0.5-6.0 h.
5. The method according to claim 1, wherein the silver-containing precursor solution is a silver nitrate solution with a concentration of 1-1000 ppm, the concentration of the sodium tungstate solution is 0.0010-10 wt%, and the mixing ratio of the sodium tungstate solution to the silver nitrate solution is 0.06-2.66: 1 based on the mass of the sodium tungstate and the silver nitrate.
6. The method of claim 1, wherein the acid is acetic acid or nitric acid; the reducing agent is one or more selected from formaldehyde, glyoxal, ethylenediamine, glucose, potassium sodium tartrate, sodium citrate, hydrazine hydrate, vitamin C, sodium borohydride and ascorbic acid.
7. The method of claim 1, wherein the heat treatment is baking at 500 to 900 ℃ for 1 to 12 hours.
8. The method of claim 1, wherein the silver-tungsten electrical contact material comprises 30-95% silver by mass and the tungsten particles are on the micro-nanometer scale.
9. The method of claim 1, wherein the step (3) comprises: and pressing and sintering the silver-tungsten composite powder subjected to heat treatment to prepare the silver-tungsten electrical contact material.
10. A silver-tungsten electrical contact material produced by the production method according to any one of claims 1 to 9, wherein the silver-tungsten electrical contact material comprises a continuous and uniform film layer composed of silver powder and micro-nano tungsten particles coated on the surface of the silver powder.
11. An electrical contact made using the silver-tungsten electrical contact material of claim 10, comprising a continuous uniform film of silver powder and micro-nano tungsten particles coated on the surface of the silver powder.
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CN106876199B (en) * 2017-01-23 2018-10-02 西安工程大学 A kind of preparation method of the siller tin oxide alloy as electric contact material of even tissue
CN110129603B (en) * 2019-04-15 2021-03-30 福达合金材料股份有限公司 Method for manufacturing silver-tungsten contact material and product thereof
CN112170862A (en) * 2020-09-30 2021-01-05 桂林金格电工电子材料科技有限公司 Preparation method of silver-tungsten contact material
CN114192774B (en) * 2021-11-23 2023-05-09 浙江福达合金材料科技有限公司 Silver-tungsten electrical contact material with high dispersity and high compactness and preparation method thereof

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