CN114086015A - Copper-tungsten alloy part and manufacturing method thereof - Google Patents

Copper-tungsten alloy part and manufacturing method thereof Download PDF

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Publication number
CN114086015A
CN114086015A CN202111429513.0A CN202111429513A CN114086015A CN 114086015 A CN114086015 A CN 114086015A CN 202111429513 A CN202111429513 A CN 202111429513A CN 114086015 A CN114086015 A CN 114086015A
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tungsten
copper
powder
paraffin
degreasing
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CN114086015B (en
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胡可
韩胜利
申正焱
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Institute of New Materials of Guangdong Academy of Sciences
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Institute of New Materials of Guangdong Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a copper-tungsten alloy part and a manufacturing method thereof, and belongs to the technical field of copper-tungsten alloy parts. The method comprises the following steps: banburying and granulating tungsten-copper mixed powder obtained by mixing tungsten powder and copper powder to obtain feed, then injecting the feed into a part green blank, and then carrying out degreasing, high-temperature sintering and hot isostatic pressing treatment; wherein the tungsten powder is spherical tungsten powder with the particle size of less than 10 mu m, the copper powder is spherical copper powder with the particle size of less than 15 mu m, and the mass fraction of the tungsten powder in the tungsten-copper mixed powder is 70-90%. The method is suitable for manufacturing the micro copper-tungsten alloy parts, particularly the micro copper-tungsten alloy parts with complex shapes, does not need or only needs little subsequent processing treatment, has low cost and high efficiency, increases the degree of freedom of part design, and has great technical and economic advantages in preparing copper-tungsten products with small sizes and complex shapes. The manufactured copper-tungsten alloy part has high precision, high density and excellent physical and mechanical properties.

Description

Copper-tungsten alloy part and manufacturing method thereof
Technical Field
The invention relates to the technical field of copper-tungsten alloy parts, in particular to a copper-tungsten alloy part and a manufacturing method thereof.
Background
The tungsten-copper alloy is composed of tungsten with high melting point, high hardness and low thermal expansion and copper with high electric and thermal conductivity. Tungsten and copper are not solid-soluble with each other and are typical pseudoalloys. Therefore, the tungsten-copper alloy has the high strength, high hardness and low thermal expansion performance of tungsten, and simultaneously has the high plasticity and good heat conduction and electric conductivity of copper. The tungsten-copper alloy is widely applied to the fields of high-voltage electric appliances, electronics and electricians, weapons and the like. Tungsten and copper are immiscible, the difference of melting points is large, the preparation difficulty of a casting method is large, and the tungsten-copper alloy is generally prepared by a powder metallurgy method in industry.
The traditional powder metallurgy process is to press and sinter tungsten powder to obtain a porous tungsten skeleton, and then to perform copper infiltration treatment on the tungsten skeleton to obtain the tungsten-copper alloy. The tungsten-copper alloy prepared by the process has high density and excellent performance, but for parts with complex shapes, a large amount of machining is needed subsequently, the cost is high, and the efficiency is low. With the high complexity and miniaturization of integrated circuits, tungsten copper alloy parts used for electronic packaging are also complicated in shape and miniaturized, the shape and size of part of precise parts are even required to be smaller than 1mm, and the parts have micro-nano structures. The traditional powder metallurgy process is difficult to satisfy the manufacturing of the copper-tungsten alloy part of the type.
In view of this, the invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a method for manufacturing a copper-tungsten alloy part, which is suitable for manufacturing a micro-copper-tungsten alloy part, in particular a micro-copper-tungsten alloy part with a complex shape, does not need or only needs few processing treatment in the subsequent process, has low cost and high efficiency, increases the degree of freedom of part design, and has great technical and economic advantages in preparing copper-tungsten products with small size and complex shape.
The second object of the present invention is to provide a copper-tungsten alloy part manufactured by the above manufacturing method.
The application can be realized as follows:
the application provides a manufacturing method of a copper-tungsten alloy part, which comprises the following steps: banburying and granulating tungsten-copper mixed powder obtained by mixing tungsten powder and copper powder to obtain feed, then injecting the feed into a part green blank, and then carrying out degreasing, high-temperature sintering and hot isostatic pressing treatment;
the tungsten powder is spherical tungsten powder with the particle size of less than 10 mu m, and the copper powder is spherical copper powder with the particle size of less than 15 mu m; the mass fraction of the tungsten powder in the tungsten-copper mixed powder is 70-90%.
In an alternative embodiment, the tungsten powder has a particle size of 2-3 μm.
In an alternative embodiment, the particle size of the copper powder is 6-8 μm.
In an alternative embodiment, the banburying is performed after mixing the tungsten-copper mixed powder with the polymer binder.
In an alternative embodiment, the polymeric binder is a paraffin-based binder.
In an alternative embodiment, the paraffin-based binder includes at least three of paraffin wax, microcrystalline wax, high density polyethylene, polypropylene, vinyl acetate copolymer, stearic acid, and pentaerythritol tetrastearate.
In an alternative embodiment, the paraffin-based binder is comprised of paraffin wax, microcrystalline wax, polypropylene, vinyl acetate copolymer, and stearic acid.
In an alternative embodiment, the paraffin-based binder is composed of, by mass, 50%: 18%: 20%: 10%: 2% of paraffin wax, microcrystalline wax, polypropylene, vinyl acetate copolymer and stearic acid.
In an alternative embodiment, the paraffin-based binder is used in an amount of 4 to 8 wt% of the feed.
In an alternative embodiment, the injection temperature is 140-.
In an alternative embodiment, degreasing comprises solvent degreasing and thermal degreasing performed sequentially.
In an alternative embodiment, solvent degreasing is to soak the green part in 40-50 ℃ n-heptane or kerosene for 12-24 h; the thermal degreasing is to perform negative pressure thermal degreasing on the green part subjected to solvent degreasing for 1-2h at the temperature of 400-600 ℃ to obtain the ash blank of the part.
In an alternative embodiment, the sub-atmospheric thermal degreasing is performed in a nitrogen atmosphere.
In an alternative embodiment, the sintering temperature is 1200-1400 ℃.
In an alternative embodiment, the sintering atmosphere is pure hydrogen or ammonia decomposition gas.
In an alternative embodiment, sintering is carried out by loading the degreased ash blank of the part into a boat and embedding the boat in alumina.
In an alternative embodiment, hot isostatic pressing treatment is further performed on the sintered part after sintering.
In an alternative embodiment, the hot isostatic pressing temperature is 800-1000 ℃ and the pressure is 100-150 MPa.
The application also provides a copper-tungsten alloy part which is manufactured by the manufacturing method.
In an optional embodiment, the copper-tungsten alloy part is a three-dimensional part, and the three-dimensional part has dimensions smaller than 2mm in three dimensions of an x axis, a y axis and a z axis.
In an optional embodiment, the compactness of the copper-tungsten alloy part is more than 98%, and the hardness is between 180 HB and 270 HB.
The beneficial effect of this application includes:
the tungsten powder and the copper powder with specific particle size, particle shape and specific proportion are adopted, and deformation can be well avoided in the processes of banburying, degreasing and the like. The particle size of the copper powder is not more than 8 microns, so that the situation that the performance of the final alloy part does not reach the standard due to the fact that the copper powder cannot be filled in part of the micro copper-tungsten alloy part specific to the application and even cannot be filled in the part after the particle size of the copper powder exceeds 8 microns can be avoided; on the other hand, the problem that tungsten copper powder particles are unevenly distributed in the feeding process easily after the particle size exceeds 8 mu m can be avoided, the difficulty in controlling the size precision in the subsequent degreasing and sintering process is greatly increased, the production cost is improved, and the yield and the production efficiency are reduced.
The method is suitable for manufacturing the micro copper-tungsten alloy parts, particularly the micro copper-tungsten alloy parts with complex shapes, does not need or only needs little subsequent processing treatment, has low cost and high efficiency, increases the degree of freedom of part design, and has great technical and economic advantages in preparing copper-tungsten products with small sizes and complex shapes. The manufactured copper-tungsten alloy part has high precision, high density and excellent physical and mechanical properties.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the copper-tungsten alloy part and the method for manufacturing the same provided in the present application.
The application provides a manufacturing method of a copper-tungsten alloy part, which comprises the following steps: mixing tungsten powder and copper powder to obtain tungsten-copper mixed powder, banburying, granulating to obtain feed, injecting the feed into a part green blank, and performing degreasing, high-temperature sintering and hot isostatic pressing treatment.
In the application, the tungsten powder is spherical tungsten powder with the particle size of less than 10 microns, and the copper powder is spherical copper powder with the particle size of less than 15 microns.
It is emphasized that the spherical tungsten powder and copper powder adopted by the method have better fluidity than other forms, and are beneficial to being uniformly mixed with the high-molecular binder.
The particle size of the tungsten powder may be, by reference, less than 10 μm, less than 9 μm, less than 8 μm, less than 7 μm, less than 6 μm, less than 5 μm, less than 4 μm, less than 3 μm, less than 2 μm, less than 1 μm, or the like. In some preferred embodiments, the tungsten powder has a particle size of 2 to 3 μm.
In alternative embodiments, the particle size of the copper powder may be less than 15 μm, less than 14 μm, less than 13 μm, less than 12 μm, less than 11 μm, less than 10 μm, less than 9 μm, less than 8 μm, less than 7 μm, less than 6 μm, less than 5 μm, less than 4 μm, less than 3 μm, less than 2 μm, or less than 1 μm, and the like. In some preferred embodiments, the copper powder has a particle size of 6-8 μm.
It is worth explaining that the tungsten powder and the copper powder with the particle sizes are fine, and can be well molded after being mixed with the high polymer binder, so that the shape of the high polymer binder can be effectively kept in the subsequent process of removing the high polymer binder, and the problem of deformation is avoided.
The particle size of the copper powder is not more than 8 mu m, especially 30 mu m, on one hand, the copper powder can not be filled in part of the micro copper-tungsten alloy part, even the copper powder can not be filled in the part after pressing, and the performance of the final alloy part can not reach the standard; on the other hand, the problem that tungsten copper powder particles are unevenly distributed in the feeding process easily after the particle size exceeds 8 mu m can be avoided, the difficulty in controlling the size precision in the subsequent degreasing and sintering process is greatly increased, the production cost is improved, and the yield and the production efficiency are reduced.
Preferably, the mass fraction of the tungsten powder in the tungsten-copper mixed powder may be 70 to 90%, such as 70%, 75%, 80%, 85%, or 90%, and may be any other value within a range of 70 to 90%. Wherein, the higher the content of the tungsten powder is, the higher the hardness of the corresponding tungsten-copper alloy part is.
The tungsten powder and the copper powder can be mechanically mixed to obtain tungsten-copper mixed powder.
Bearing on the above, the particle size of the tungsten powder and the copper powder has a great influence on the dimensional accuracy and performance of the microminiature tungsten-copper alloy part, and the inventor researches and proposes that: the tungsten powder and the copper powder are spherical powder, the particle size of the tungsten powder is less than 10 mu m, and the average particle size is 2-3 mu m; when the particle size of the copper powder is less than 15 mu m and the average particle size is 6-8 mu m, the size precision and the performance of the microminiature tungsten-copper alloy part are better.
Further, banburying, crushing and granulating the tungsten-copper mixed powder to obtain a feed (tungsten-copper alloy feed).
Wherein, the banburying can be carried out after mixing the tungsten-copper mixed powder and the macromolecular binder.
The high molecular binder used herein is, by reference, a paraffin-based binder, and may include, for example, at least three of Paraffin Wax (PW), Microcrystalline Wax (MW), High Density Polyethylene (HDPE), polypropylene (PP), vinyl acetate copolymer (EVA), Stearic Acid (SA), and pentaerythritol tetrastearate (PETS).
The inventor proposes that: compared with other binders such as polymer-based binders and the like, the paraffin-based binder has better fluidity, and the tungsten-copper alloy feed after banburying has good compatibility of each component, good fluidity and good filling effect, and is more suitable for injecting micro tungsten-copper alloy part green bodies.
In some preferred embodiments, the paraffin-based binder is comprised of paraffin wax, microcrystalline wax, polypropylene, vinyl acetate copolymer, and stearic acid. Preferably, the paraffin-based binder consists of, by mass, 50%: 18%: 20%: 10%: 2% of paraffin wax, microcrystalline wax, polypropylene, vinyl acetate copolymer and stearic acid.
The amount of paraffin-based binder may, by reference, be from 4 to 8 wt%, such as 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, or 8 wt% of the feed, and the like, and may be any other value within the range of from 4 to 8 wt%. In addition, the mass ratio of the paraffin-based binder in the tungsten-copper alloy feed can be adjusted according to the mass fraction of tungsten powder in the mixed powder.
Compared with a plastic-based binder, on the basis of using the same amount of tungsten-copper mixed powder, the amount of the paraffin-based binder which needs to be used in combination is about 10% lower than that of the plastic-based binder, and the plastic-based binder has poorer flowability, so that the processing of raw materials with specific particle sizes in the application is not facilitated, and micro tungsten-copper alloy parts with better compactness and hardness cannot be obtained.
Crushing and granulating can be referred to the prior art, and will not be described in detail herein.
In the present application, the injection temperature can be 140-160 ℃, such as 140 ℃, 145 ℃, 150 ℃, 155 ℃ or 160 ℃ or any other value within the range of 140-160 ℃ during the injection process.
The temperature of the mold may be 30-40 deg.C, such as 32 deg.C, 35 deg.C, 38 deg.C or 40 deg.C, or may be any other value within the range of 30-40 deg.C.
It should be emphasized that if the injection temperature is higher than 160 ℃, such as 180-; in addition, the viscosity of the polymer binder is reduced due to the excessively high injection temperature, which causes the polymer binder to flow faster in the mold runner, and causes the metal powder and the polymer to separate into two phases, resulting in uneven distribution of components in the product.
As for the temperature of the die, the temperature of the die needs to be controlled to be 30-40 ℃, and cannot be set to be higher than 60 ℃, otherwise, the die can be seriously deformed after being demoulded.
On the basis, under the injection conditions, the green compact of the micro tungsten-copper alloy part obtained by injection has high density and few defects, two-phase separation is not generated, and the surface quality of the green compact is high.
Further, the green part is degreased.
In this application, degreasing includes solvent degreasing and thermal degreasing, which are performed sequentially, unlike conventional catalytic degreasing principles and methods. In this application, solvent degreasing is used to dissolve the paraffin-based substances, and thermal degreasing is used to decompose the rest of the paraffin-based binder into gas.
In some embodiments, solvent degreasing may be by soaking the green part in 40-50 deg.C n-heptane or kerosene for 12-24 h. The thermal degreasing can be realized by thermally degreasing the green part subjected to solvent degreasing for 1-2h under negative pressure at the temperature of 400-600 ℃ to obtain the ash blank of the part.
The above negative pressure thermal degreasing is performed in a nitrogen atmosphere.
Further, the part gray blank is sintered.
The sintering temperature may be 1200-1400 deg.C, such as 1200 deg.C, 1250 deg.C, 1300 deg.C, 1350 deg.C or 1400 deg.C, or any other value within the range of 1200-1400 deg.C.
In the above process, the sintering atmosphere may be pure hydrogen or ammonia decomposition gas.
In some embodiments, sintering is performed by loading the degreased part ash into a boat and embedding the boat in alumina (e.g., corundum). The alumina plays a role in supporting and protecting the shape in the process.
Further, hot isostatic pressing treatment can be carried out on the sintered part after sintering.
The hot isostatic pressing treatment temperature is 800-1000 ℃, and the pressure is 100-150 MPa.
The hot isostatic pressing temperature may be 800-1000 ℃, such as 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, or any other value within the range of 800-1000 ℃.
The hot isostatic pressure may, by reference, be 100-.
Correspondingly, the application also provides a copper-tungsten alloy part which is manufactured by the manufacturing method.
The copper-tungsten alloy part is a three-dimensional part, and the size of the three-dimensional part in the x axis, the y axis and the z axis is less than 2 mm.
In some embodiments, the compactness of the copper-tungsten alloy part is more than 98%, and the hardness is between 180 HB and 270 HB.
In summary, by the manufacturing process provided by the application, the micro tungsten-copper alloy parts with three dimensions smaller than 2mm can be produced in large scale, and the produced micro tungsten-copper alloy parts are high in size precision, high in density, excellent in physical mechanical property, strong in controllability, few or no machining is needed subsequently, and low in cost. The compactness of the micro tungsten-copper alloy part obtained by the method is more than 98%, and the hardness is adjustable within the range of 180 HB and 270HB according to the components of the tungsten-copper alloy.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a manufacturing method of a micro tungsten-copper alloy part, which specifically comprises the following steps:
selecting spherical tungsten powder with the particle size of less than 10 mu m and the average particle size of 2-3 mu m and spherical copper powder with the particle size of less than 15 mu m and the average particle size of 6-8 mu m, adding the spherical tungsten powder and the spherical copper powder into a mixer according to the mass ratio of 90:10, and mechanically mixing the spherical tungsten powder and the spherical copper powder for 10 hours to obtain tungsten-copper mixed powder.
And banburying the tungsten-copper mixed powder with a paraffin-based binder consisting of PW, MW, PP, EVA and SA, and crushing and granulating to obtain a tungsten-copper alloy feed. Wherein the mass fraction of the paraffin-based binder in the tungsten-copper alloy feed is 8%. The mass ratio of PW, MW, PP, EVA and SA is 50%: 18%: 20%: 10%: 2 percent.
Injecting the tungsten-copper alloy feed into a pre-designed mould cavity on an injection machine, wherein the injection temperature is 140 ℃, the mould temperature is 30 ℃, and demoulding to obtain the micro tungsten-copper alloy part green body.
And soaking the green compact of the microminiature tungsten-copper alloy part in 40 ℃ n-heptane for 24 hours, then carrying out negative pressure thermal degreasing in nitrogen atmosphere at the degreasing temperature of 600 ℃ for 2 hours, and finally obtaining the gray compact of the microminiature tungsten-copper alloy part.
And (3) loading the ash blank of the microminiature tungsten-copper alloy part into a boat, embedding the boat into corundum sand, and sintering the boat at the high temperature of 1400 ℃ in ammonia decomposition gas to obtain the microminiature tungsten-copper alloy sintered part.
And finally, carrying out surface hot isostatic pressing treatment on the micro tungsten-copper alloy sintered part at the temperature of 1000 ℃ and the pressure of 150MPa to obtain the micro tungsten-copper alloy part.
The compactness and hardness of the obtained micro tungsten-copper alloy part are detected according to GB/T3850 and GB/T231, and the results show that: the compactness of the micro tungsten-copper alloy part is 98.5%, and the hardness is 265.2 HB.
Example 2
The embodiment provides a manufacturing method of a micro tungsten-copper alloy part, which specifically comprises the following steps:
selecting spherical tungsten powder with the particle size of less than 10 mu m and the average particle size of 2-3 mu m and spherical copper powder with the particle size of less than 15 mu m and the average particle size of 6-8 mu m, adding the spherical tungsten powder and the spherical copper powder into a mixer according to the mass ratio of 80:20, and mechanically mixing the spherical tungsten powder and the spherical copper powder for 10 hours to obtain tungsten-copper mixed powder.
And banburying the tungsten-copper mixed powder and a paraffin-based binder consisting of PW, MW, PP, EVA and SA, and crushing and granulating to obtain a tungsten-copper alloy feed. Wherein the mass fraction of the paraffin-based binder in the tungsten-copper alloy feed is 6%. The mass ratio of PW, MW, PP, EVA and SA is 50%: 18%: 20%: 10%: 2 percent.
Injecting the tungsten-copper alloy feed into a pre-designed mould cavity on an injection machine, wherein the injection temperature is 150 ℃, the mould temperature is 30 ℃, and demoulding to obtain the micro tungsten-copper alloy part green body.
And soaking the green compact of the microminiature tungsten-copper alloy part in 40 ℃ n-heptane for 15 hours, then carrying out negative pressure thermal degreasing in nitrogen atmosphere at the degreasing temperature of 600 ℃ for 1 hour, and finally obtaining the ash compact of the microminiature tungsten-copper alloy part.
And (3) loading the ash blank of the microminiature tungsten-copper alloy part into a boat, embedding the boat into corundum sand, and sintering the boat at a high temperature in ammonia decomposition gas, wherein the sintering temperature is 1300 ℃ to obtain the microminiature tungsten-copper alloy sintered part.
And finally, carrying out hot isostatic pressing treatment on the micro tungsten-copper alloy sintered part at the temperature of 900 ℃ and under the pressure of 150MPa to obtain the micro tungsten-copper alloy part.
The microminiature tungsten-copper alloy parts obtained in example 2 were tested by the same measurement method as in example 1, and the results thereof showed that: the compactness of the micro tungsten-copper alloy part is 99 percent, and the hardness is 220.3 HB.
Example 3
The embodiment provides a manufacturing method of a micro tungsten-copper alloy part, which specifically comprises the following steps:
selecting spherical tungsten powder with the particle size of less than 10 mu m and the average particle size of 2-3 mu m and spherical copper powder with the particle size of less than 15 mu m and the average particle size of 6-8 mu m, adding the spherical tungsten powder and the spherical copper powder into a mixer according to the mass ratio of 70:30, and mechanically mixing the spherical tungsten powder and the spherical copper powder for 10 hours to obtain tungsten-copper mixed powder.
And banburying the tungsten-copper mixed powder and a paraffin-based binder consisting of PW, MW, PP, EVA and SA, and crushing and granulating to obtain a tungsten-copper alloy feed. Wherein the mass fraction of the paraffin-based binder in the tungsten-copper alloy feed is 4%. The mass ratio of PW, MW, PP, EVA and SA is 50%: 18%: 20%: 10%: 2 percent.
Injecting the tungsten-copper alloy feed into a pre-designed mould cavity on an injection machine, wherein the injection temperature is 160 ℃, the mould temperature is 40 ℃, and demoulding to obtain the micro tungsten-copper alloy part green body.
And soaking the green compact of the microminiature tungsten-copper alloy part in 40 ℃ n-heptane for 12 hours, then carrying out negative pressure thermal degreasing in nitrogen atmosphere at the degreasing temperature of 600 ℃ for 1 hour, and finally obtaining the gray compact of the microminiature tungsten-copper alloy part.
And (3) loading the ash blank of the microminiature tungsten-copper alloy part into a boat, embedding the boat into corundum sand, and sintering the boat at high temperature in ammonia decomposition gas, wherein the sintering temperature is 1200 ℃ to obtain the microminiature tungsten-copper alloy sintered part.
And finally, carrying out surface hot isostatic pressing treatment on the micro tungsten-copper alloy sintered part at the temperature of 800 ℃ and under the pressure of 100MPa to obtain the micro tungsten-copper alloy part.
The microminiature tungsten-copper alloy parts obtained in example 3 were tested by the same measurement method as in example 1, and the results thereof showed that: the compactness of the micro tungsten-copper alloy part is 99.5 percent, and the hardness is 182.5 HB.
Example 4
This example provides a method for manufacturing a micro tungsten-copper alloy part, which is different from example 1 in that: the paraffin-based binder consists of pentaerythritol tetrastearate, high-density polyethylene and solid paraffin in a mass ratio of 1:2: 7.
The solvent degreasing is to soak the green part in kerosene of 50 ℃ for 20h, the temperature of the negative pressure thermal degreasing is 600 ℃, and the heat preservation time is 1.5 h.
The sintering is carried out in a pure hydrogen atmosphere.
The microminiature tungsten-copper alloy parts obtained in example 3 were tested by the same measurement method as in example 1, and the results thereof showed that: the compactness of the micro tungsten-copper alloy part is 98.2%, and the hardness is 260.1 HB.
Comparative example
Taking example 1 as an example, comparative examples 1-8 were set up.
Comparative example 1 differs from example 1 in that: the copper powder is spherical copper powder with the particle size of 30 mu m;
comparative example 2 differs from example 1 in that: the mass fraction of the tungsten powder in the tungsten-copper mixed powder is 60 percent;
comparative example 3 differs from example 1 in that: the mass fraction of the tungsten powder in the tungsten-copper mixed powder is 95 percent;
comparative example 4 differs from example 1 in that: banburying is carried out after mixing tungsten-copper mixed powder and polystyrene (equal to a high-molecular binder);
comparative example 5 differs from example 1 in that: the injection temperature is 135 ℃;
comparative example 6 differs from example 1 in that: the injection temperature is 180 ℃;
comparative example 7 differs from example 1 in that: the temperature of the die is 65 ℃;
comparative example 8 differs from example 1 in that: degreasing the substrate with oxalic acid at 150 ℃.
The results of the tests on the microminiature tungsten copper alloy parts obtained in comparative examples 1 to 3 were shown in Table 1 by the same measuring method as in example 1.
TABLE 1 test results
Comparative example 1 Comparative example 2 Comparative example 3
Density (%) 92.8％ 99.3％ 90.6％
Hardness (HB) 211.4 140.4 220.8
Therefore, compared with the copper-tungsten alloy parts obtained by the comparative examples 1-3, the copper-tungsten alloy part obtained by the example 1 has higher compactness and hardness.
For comparative examples 4-8:
in comparison example 4, the shape retention of the degreased green body of the part is extremely poor, the yield is extremely low, and the tungsten-copper alloy part meeting the requirements cannot be obtained.
In comparative example 5, feeding injection was difficult and it was difficult to obtain a green part meeting the requirements.
Comparative example 6, injection temperature is too high, and paraffin burning loss is severe in the injection process, and a large amount of overlap burrs are produced on part unburned bricks surface, and the inside air that is very easily drawn into of part, can't obtain the part unburned bricks that satisfy the demands.
Comparative example 7 the green part was very susceptible to deformation during demolding, or even impossible.
In comparison example 8, the binder in the green part is difficult to remove under the environment of oxalic acid, and the degreasing effect is poor.
In summary, the particle shapes and the particle sizes of the tungsten powder and the copper powder as raw materials and the mass fraction of the tungsten powder in the tungsten-copper mixed powder are controlled, and the tungsten powder and the copper powder are subjected to injection, sintering and hot isostatic pressing under the conditions of a better injection and sintering process to obtain the micro tungsten-copper alloy part with three dimensions smaller than 2 mm.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A manufacturing method of a copper-tungsten alloy part is characterized by comprising the following steps: banburying and granulating tungsten-copper mixed powder obtained by mixing tungsten powder and copper powder to obtain feed, then injecting the feed into a part green body, and then carrying out degreasing, high-temperature sintering and hot isostatic pressing treatment;
the tungsten powder is spherical tungsten powder with the particle size of less than 10 mu m, and the copper powder is spherical copper powder with the particle size of less than 15 mu m; the mass fraction of the tungsten powder in the tungsten-copper mixed powder is 70-90%.
2. The production method according to claim 1, wherein the tungsten powder has a particle size of 2 to 3 μm.
3. The method according to claim 1, wherein the particle size of the copper powder is 6 to 8 μm.
4. The manufacturing method according to claim 1, wherein the banburying is performed after mixing the tungsten-copper mixed powder with a polymer binder;
preferably, the polymer binder is a paraffin-based binder;
preferably, the paraffin-based binder includes at least three of paraffin wax, microcrystalline wax, high density polyethylene, polypropylene, vinyl acetate copolymer, stearic acid, and pentaerythritol tetrastearate;
more preferably, the paraffin-based binder consists of paraffin wax, microcrystalline wax, polypropylene, vinyl acetate copolymer and stearic acid;
preferably, the paraffin-based binder consists of, by mass, 50%: 18%: 20%: 10%: 2 percent of solid paraffin, microcrystalline paraffin, polypropylene, vinyl acetate copolymer and stearic acid;
preferably, the paraffin-based binder is used in an amount of 4 to 8 wt% of the feed.
5. The method as claimed in claim 1, wherein the injection temperature is 140-160 ℃ and the mold temperature is 30-40 ℃ during the injection process.
6. The manufacturing method according to claim 1, wherein the degreasing includes solvent degreasing and thermal degreasing which are performed in this order;
preferably, the solvent degreasing is to soak the green part in n-heptane or kerosene with the temperature of 40-50 ℃ for 12-24 h; the thermal degreasing is to carry out negative pressure thermal degreasing on the green part subjected to solvent degreasing for 1-2h at the temperature of 400-600 ℃;
preferably, the negative pressure thermal degreasing is performed in a nitrogen atmosphere.
7. The method as claimed in claim 1, wherein the sintering temperature is 1200-1400 ℃;
preferably, the sintering atmosphere is pure hydrogen or ammonia decomposition gas;
preferably, the sintering is carried out by loading the degreased ash blank of the part into a boat and then embedding the boat in alumina.
8. The method of manufacturing of claim 1, further comprising subjecting the sintered compact to hot isostatic pressing;
preferably, the hot isostatic pressing treatment temperature is 800-1000 ℃, and the pressure is 100-150 MPa.
9. A copper-tungsten alloy part produced by the production method according to any one of claims 1 to 8.
10. The copper-tungsten alloy part according to claim 9, wherein the copper-tungsten alloy part is a three-dimensional solid part having dimensions of less than 2mm in all three dimensions of the x-axis, the y-axis and the z-axis;
preferably, the compactness of the copper-tungsten alloy part is more than 98%, and the hardness is between 180 HB and 270 HB.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015102732A2 (en) * 2013-10-25 2015-07-09 Golden Intellectual Property, Llc Amorphous alloy containing feedstock for powder injection molding
CN109402478A (en) * 2018-12-27 2019-03-01 广东省材料与加工研究所 A kind of tungsten-copper alloy and its injection molding technique
CN109530677A (en) * 2018-12-27 2019-03-29 广东省材料与加工研究所 A kind of tungsten-copper alloy feeding and preparation method thereof
CN110964963A (en) * 2019-12-16 2020-04-07 广东省材料与加工研究所 Tungsten-copper alloy pipe and preparation method thereof
CN113070474A (en) * 2021-03-29 2021-07-06 深圳市注成科技股份有限公司 Preparation and forming method of nano tungsten-copper alloy radiating fin

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015102732A2 (en) * 2013-10-25 2015-07-09 Golden Intellectual Property, Llc Amorphous alloy containing feedstock for powder injection molding
CN109402478A (en) * 2018-12-27 2019-03-01 广东省材料与加工研究所 A kind of tungsten-copper alloy and its injection molding technique
CN109530677A (en) * 2018-12-27 2019-03-29 广东省材料与加工研究所 A kind of tungsten-copper alloy feeding and preparation method thereof
CN110964963A (en) * 2019-12-16 2020-04-07 广东省材料与加工研究所 Tungsten-copper alloy pipe and preparation method thereof
CN113070474A (en) * 2021-03-29 2021-07-06 深圳市注成科技股份有限公司 Preparation and forming method of nano tungsten-copper alloy radiating fin

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