CN111411254B - Tungsten-reinforced copper composite material and preparation method thereof - Google Patents

Tungsten-reinforced copper composite material and preparation method thereof Download PDF

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CN111411254B
CN111411254B CN202010275667.8A CN202010275667A CN111411254B CN 111411254 B CN111411254 B CN 111411254B CN 202010275667 A CN202010275667 A CN 202010275667A CN 111411254 B CN111411254 B CN 111411254B
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copper
tungsten
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skeleton
composite material
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CN111411254A (en
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陈文革
周凯
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Xian University of Technology
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    • 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
    • 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
    • B22F3/1035—Liquid phase sintering
    • 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
    • B22F3/11—Making porous workpieces or articles
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • 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
    • C22C1/045—Alloys based on refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Abstract

The invention discloses a tungsten reinforced copper composite material which comprises the following components in percentage by volume, wherein copper powder is not less than 50%, and the balance is tungsten powder, and the sum of the volume percentages of the components is 100%; the invention also discloses a preparation method of the tungsten-reinforced copper composite material. According to the tungsten-reinforced copper composite material, the proportion of less tungsten and more copper is adopted, the high-temperature characteristic of insoluble metal tungsten and the high-conductivity characteristic of low-melting-point metal copper are fully exerted, and the special requirements of high temperature resistance and good conduction are met; the preparation method of the invention adopts the selective laser melting technology to prepare the porous tungsten skeleton, the pore shape, the number and the size of the tungsten skeleton are accurate and controllable, and the tungsten skeleton is metallurgically bonded, has high strength and isotropy and is in a network shape, so that the bonding phase copper is fully filled in the porous tungsten skeleton through the infiltration technology, thereby preparing the high-density tungsten reinforced copper composite material which can be used under various environments and having good practical value.

Description

Tungsten-reinforced copper composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of metal composite materials, and particularly relates to a tungsten-reinforced copper composite material and a preparation method of the tungsten-reinforced copper composite material.
Background
The tungsten-copper composite material is a typical pseudo alloy system, and the component tungsten has high melting point (3420 ℃), high strength, arc ablation resistance, higher conductivity (174W/m.K) and low nuclear fuel retention rate; the component copper has the characteristics of high electrical conductivity, high thermal conductivity (about 400W/m.K at room temperature) and the like. According to the phase diagram: copper and tungsten do not generate intermediate phase, so that the respective characteristics of two component metals can be exerted; on the other hand, different component contents can be prepared according to the requirements to obtain different performance requirements. Therefore, the tungsten-copper composite material is widely applied to the fields of power electronics, aerospace, military industry and nuclear energy.
The tungsten-copper alloy used at present is high in tungsten content mostly, and because of high tungsten (volume ratio is larger than 50%), the traditional powder metallurgy infiltration technology or the novel discharge plasma sintering technology can well maintain the skeleton structure, copper infiltration is facilitated, and the requirements of various fields such as high-voltage electrical contact materials, rocket engine throat lining materials and wear-resistant sliding block materials can be met. However, heat sink materials, nuclear fusion polarization filter materials or other materials for similar applications that require higher thermal and electrical conductivity and certain heat resistance properties require higher copper content, i.e., tungsten-copper composites with less tungsten (less than 50% by volume) and more copper. On the one hand, the skeleton phase tungsten prepared by the traditional method is difficult to maintain, and the bulk copper-tungsten composite material is difficult to prepare on the basis of the skeleton phase tungsten; on the other hand, the distribution of each phase and the shape and size of each phase cannot be changed randomly in the copper-tungsten composite material block prepared by the traditional method.
Disclosure of Invention
The invention aims to provide a tungsten-reinforced copper composite material, which solves the problem that the skeleton phase tungsten is difficult to maintain easily caused by less tungsten and more copper in the existing tungsten-copper composite material.
The second purpose of the invention is to provide a preparation method of the tungsten-reinforced copper composite material, which solves the problems that the tungsten phase is difficult to be metallurgically bonded, a reticular communicated structure cannot be formed, the tungsten-copper phase is not uniformly distributed and the like in the existing preparation method.
The first technical scheme adopted by the invention is that the tungsten reinforced copper composite material comprises the following components according to volume fraction, copper powder is not less than 50%, the balance is tungsten powder, and the sum of the volume percentages of the components is 100%.
The present invention is also characterized in that,
the tungsten powder is spherical tungsten powder with the purity not less than 99.9 percent and the particle size is 15-53 mu m.
The copper powder is irregular copper powder with the purity not less than 99.9 percent and the particle size is 50-70 mu m.
The second technical scheme adopted by the invention is that the preparation method of the tungsten reinforced copper composite material comprises the following steps:
step 1, selecting raw materials
Weighing the following components according to volume fraction, wherein copper powder is not less than 50%, and the balance is tungsten powder, and the sum of the volume percentages of the above components is 100%;
step 2, preparing a porous tungsten framework;
step 2.1, placing the tungsten powder in the step 1 in a powder loading bin of a selective laser melting device, inputting a prefabricated porous tungsten framework model, starting the selective laser melting device to print in a checkerboard mode, melting the selective laser melting device once every time powder is laid, and continuously introducing inert gas to protect in the printing process to obtain a prefabricated porous tungsten framework;
step 2.2, pickling the prefabricated porous tungsten skeleton obtained in the step 2.1 for 1-3 min, and then ultrasonically cleaning in alcohol for 3-5 min to obtain a porous tungsten skeleton;
step 3, preparing a copper-plated porous tungsten skeleton
Preparing electroplating solution, using a copper plate with the purity of 99% as an anode and the porous tungsten framework obtained in the step 2.2 as a cathode, and electroplating to obtain a copper-plated porous tungsten framework;
step 4, infiltration sintering of copper
Step 4.1, calculating the actually required amount M of infiltrated copper based on the porosity k of the porous tungsten skeleton model of step 2.1 and the peripheral volume V of the copper-plated porous tungsten skeleton of step 301.2M-1.2X 8.9kV, wherein 1.2 is infiltration loss coefficient 1.2, and copper powder in the step 1 is weighed;
step 4.2, placing the copper powder obtained in the step 4.1 in a steel pressing die with a die cavity diameter of 20-40 mm and a height of 50-200 mm, and pressing the copper powder into a block to be infiltrated into a pure copper pressed blank under the pressure condition of 3-5 tons/square centimeter;
and 4.3, placing the copper-plated porous tungsten skeleton in the step 3 in a graphite mold cavity, placing the copper green compact in the step 4.2 above the copper porous tungsten skeleton, covering a graphite cover, placing the copper green compact in a high-temperature sintering furnace for heating, then cooling the furnace, taking out the copper green compact, and removing copper floating on the surface to obtain the required tungsten-reinforced copper composite material.
The present invention is also characterized in that,
in the step 2.1, the porosity k of the prefabricated porous tungsten skeleton model is more than or equal to 50-90%.
In step 2.1, the printing parameters of the selective laser melting equipment are as follows: the diameter of a light spot is 45-100 mu m, the scanning interval is 60 mu m, the scanning speed is 550-650 mm/s, the thickness of a powder layer is 25 mu m, the laser power is 70-100W, and the laser energy is 80-130J/mm3；
The gas flow of the inert gas is 1-3 m3/h。
In step 2.2, the solution adopted by acid washing is as follows: HF and HNO with volume ratio of 8:1:213And H2O mixed solution;
ultrasonic parameters: the ultrasonic frequency is not less than 1MHz, and the temperature is room temperature.
In step 3, the electroplating solution is CuSO with the concentration of 60-100 g/L4Solution and H accounting for 2-5% of the total volume of the electroplating solution2SO4Mixing the solution;
the parameters of the electroplating are as follows: the temperature of the electro-coppering is 30-60 ℃, the time is 30-60 mins, and the working current density is 5-20A/dm2The thickness of the copper plating layer is 5-15 μm.
And 4.3, the parameters of the high-temperature sintering furnace are as follows: heating to 1200-1250 ℃, and then preserving heat for 60-90 min; and introducing hydrogen or nitrogen in the heating process, wherein the introduction amount is 1-3L/h.
In the step 4.3, the height of the graphite mold cavity is at least 30-100 mm higher than that of the copper-plated porous tungsten skeleton; the cross section of the graphite mold cavity is the same as the cross section of the copper-plated porous tungsten skeleton in size.
The invention has the beneficial effects that: according to the tungsten-reinforced copper composite material, the proportion of less tungsten and more copper is adopted, the high-temperature characteristic of insoluble metal tungsten and the high-conductivity characteristic of low-melting-point metal copper are fully exerted, and the special requirements of high temperature resistance and good conduction are met; the preparation method of the invention adopts the selective laser melting technology to prepare the porous tungsten skeleton, the pore shape, the number and the size of the tungsten skeleton are accurate and controllable, and the tungsten skeleton is metallurgically bonded, has high strength and isotropy and is in a network shape, so that the bonding phase copper is fully filled in the porous tungsten skeleton through the infiltration technology, thereby preparing the high-density tungsten reinforced copper composite material which can be used under various environments and having good practical value.
Drawings
Fig. 1 is a schematic structural diagram of a prefabricated porous tungsten skeleton model in a preparation method of a tungsten-reinforced copper composite material, wherein fig. 1(a) is a first tungsten skeleton model with anisotropy, fig. 1(b) is a second tungsten skeleton model with anisotropy, and fig. 1(c) is a tungsten skeleton model with isotropy;
FIG. 2 is a schematic structural view of an electroplating apparatus in a method for preparing a tungsten-reinforced copper composite material according to the present invention;
FIG. 3 is a schematic structural diagram of a graphite mold in a method for preparing a tungsten-reinforced copper composite material according to the present invention;
fig. 4 is a schematic structural diagram of a prefabricated porous tungsten skeleton in example 1 of a preparation method of a tungsten-reinforced copper composite material, where fig. 4(a) is a structural diagram of a macroscopic prefabricated porous tungsten skeleton and fig. 4(b) is a morphological diagram of a microscopic prefabricated porous tungsten skeleton;
fig. 5 is a micro-topography of a tungsten-copper composite material prepared in example 1 of the preparation method of a tungsten-reinforced copper composite material according to the present invention, wherein fig. 5(a) is an XY plane micro-topography, fig. 5(b) is a YZ plane micro-topography, and fig. 5(c) is a 60 ° plane micro-topography with respect to YZ.
In the figure, 1, a graphite cover, 2, a copper pressed compact, 3, a graphite mold and 4, a copper-plated porous tungsten framework.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The tungsten reinforced copper composite material comprises the following components, by volume, not less than 50% of copper powder, and the balance of tungsten powder, wherein the sum of the volume percentages of the components is 100%; the tungsten powder is spherical tungsten powder with the purity not less than 99.9 percent and the particle size of 15-53 mu m; the copper powder is irregular copper powder with the purity not less than 99.9 percent and the particle size is 50-70 mu m.
The spherical tungsten powder is mainly used for 3D printing, and the irregular copper powder is mainly used for infiltration.
A preparation method of a tungsten reinforced copper composite material comprises the following steps:
step 1, selecting raw materials
Weighing the following components according to volume fraction, wherein copper powder is not less than 50%, and the balance is tungsten powder, and the sum of the volume percentages of the above components is 100%;
step 2, preparing a porous tungsten framework;
step 2.1, placing the tungsten powder in the step 1 in a powder loading bin of selective laser area melting equipment, inputting a prefabricated porous tungsten skeleton model, starting selective laser area melting equipment to print, wherein the diameter of a light spot is 45-100 mu m, the scanning mode is a checkerboard mode, selective laser area melting is performed once each time powder is laid, the scanning interval is 60 mu m, the scanning speed is 550-650 mm/s, the thickness of the powder laying layer is 25 mu m, the laser power is 70-100W, and the laser energy is 80-130J/mm3Continuously introducing inert gas (argon/nitrogen) for protection in the printing process, wherein the gas flow is 1-3 m3Obtaining a prefabricated porous tungsten framework;
wherein, the porosity of prefabricated porous tungsten skeleton model is not less than 50 ~ 90%, in order to guarantee high porosity, sets for prefabricated porous tungsten skeleton model two kinds:
anisotropic tungsten skeleton-the dimensions of the holes in each direction are not uniform and are anisotropic;
the sizes of the holes in all directions of the isotropic tungsten skeleton-cube are the same.
As shown in fig. 1(a), the porosity k measured by anisotropy of a hexagonal through-hole tungsten skeleton is 61 to 76 vol.%; as shown in fig. 1(b), the porous material is a space cross tungsten skeleton and is anisotropic, and the measured porosity k is 85 to 90 vol.%; as shown in fig. 1(c), the porosity k measured by isotropic formation of a square through-hole tungsten skeleton is 80 to 92 vol.%.
Step 2.2, performing acid washing on the prefabricated porous tungsten skeleton obtained in the step 2.1 for 1-3 min to remove a surface oxide layer and oil stains, and then performing ultrasonic cleaning in alcohol for 3-5 min to obtain the porous tungsten skeleton, wherein the solution adopted by the acid washing is HF and HNO in a volume ratio of 8:1:213And H2O mixed solution; the ultrasonic frequency is not less than 1MHz, and the temperature is room temperature.
Step 3, preparing a copper-plated porous tungsten skeleton
Preparing electroplating solution, taking a copper plate with the purity of 99% as an anode and the porous tungsten framework in the step 2.2 as a cathode, placing the copper plate and the porous tungsten framework as shown in the figure 2, and electroplating to obtain a copper-plated porous tungsten framework;
the concentration of the electroplating solution is as follows: CuSO with concentration of 60-100 g/L4Solution and H accounting for 2-5% of the total volume of the electroplating solution2SO4Mixing the solution, adding H2SO4The reason for this is to make the plating solution acidic;
the parameters of the electroplating are as follows: the temperature of the electro-coppering is 30-60 ℃, the time is 30-60 mins, and the working current density is 5-20A/dm2The thickness of the copper plating layer is 5-15 μm.
Step 4, infiltration sintering of copper
Step 4.1, calculating the actually required amount M of infiltrated copper based on the porosity k of the porous tungsten skeleton model of step 2.1 and the peripheral volume V of the copper-plated porous tungsten skeleton of step 301.2M-1.2 x 8.9kV (g), in order to prevent the loss of copper in the infiltration process, the infiltration amount is multiplied by an infiltration loss coefficient of 1.2, namely the actual added infiltration copper is 1.2M, and 1.2M of copper powder in the step 1 is weighed;
step 4.2, placing the copper powder obtained in the step 4.1 in a steel pressing die with a die cavity diameter of 20-40 mm and a height of 50-200 mm, and pressing the copper powder into a block to be infiltrated into a pure copper pressed blank under the pressure condition of 3-5 tons/square centimeter;
and 4.3, as shown in figure 3, placing the copper-plated porous tungsten skeleton 4 in the step 3 in a cavity of a graphite mold 3, placing the copper pressed blank 2 in the step 4.2 above the copper pressed blank, covering a graphite cover 1, placing the copper pressed blank in a high-temperature sintering furnace, heating to 1200-1250 ℃, then preserving the temperature for 60-90 min, cooling the furnace, introducing hydrogen or nitrogen in the heating process at the introduction amount of 1-3L/h, taking out, and removing copper floating on the surface to obtain the required tungsten-reinforced copper composite material.
Height l of graphite mold cavity0At least higher than the height l of the copper-plated porous tungsten skeleton1The height is 30-100 mm; cross section of graphite mold cavity and copper plating porousThe cross-sectional dimensions of the tungsten skeleton are the same.
Example 1
The target is as follows: preparing an anisotropic copper-tungsten composite material, wherein the volume ratio of Cu is 60 vol.%, and the volume ratio of W powder is 40 vol.%.
Step 1, selecting raw materials
Weighing 60 vol.% of copper powder and the balance of tungsten powder according to the volume fraction, wherein the particle size of the pure tungsten powder is 15-53 mu m, and the sum of the volume percentages of the components is 100%;
step 2, preparing a porous tungsten framework;
2.1, placing the tungsten powder in the step 1 in a powder loading bin of selective laser area melting equipment, keeping the upper surface of powder in the bin to be level as much as possible, inputting a prefabricated porous tungsten skeleton model, starting the selective laser area melting equipment for printing, wherein the diameter of a light spot is 100 mu m, the scanning mode is a checkerboard mode, the selective laser area is melted once every powder laying, the scanning interval is 60 mu m, the scanning speed is 550mm/s, the thickness of a powder laying layer is 25 mu m, the laser power is 100W, and the laser energy is 110J/mm3Continuously introducing argon gas for protection in the printing process, wherein the gas flow is 1m3H, as shown in FIG. 4(a), obtaining a prefabricated porous tungsten skeleton;
wherein the porosity of the prefabricated porous tungsten skeleton model is 61.33 vol.%. As shown in fig. 1(a), the porous structure of the prefabricated porous tungsten skeleton model is that holes in the Z-axis direction are hexagonal through holes, the diameter of the outer circle of the hexagon is 1.8mm, and the wall thickness is 0.42 mm; the cross-sectional dimension of the holes along each opposite side of the hexagon is 0.4mm x 0.4mm (an equilateral triangle with the side length of 0.4mm is designed above the holes to prevent the overhang structure), the spacing between the holes in the Z axis is 1.0mm, and the overall dimension is 11.5 x 13.5 x 10 mm.
And 2.2, pickling the prefabricated porous tungsten skeleton obtained in the step 2.1 for 1min to remove a surface oxide layer and oil stains, and then ultrasonically cleaning in alcohol for 5min at the ultrasonic frequency of 2MHz and at the room temperature to obtain the porous tungsten skeleton.
Step 3, preparing a copper-plated porous tungsten skeleton
Preparing electroplating solution, using a copper plate with the purity of 99% as an anode and the porous tungsten framework obtained in the step 2.2 as a cathode, and electroplating to obtain a copper-plated porous tungsten framework;
the concentration of the electroplating solution is as follows: CuSO with concentration of 80g/L4Solution and 2% H of the total volume of the plating solution2SO4Mixing the solution, adding H2SO4The reason for this is to make the plating solution acidic;
the parameters of the electroplating are as follows: the temperature of the electro-coppering is 40 ℃, the time is 60mins, and the working current density is 10A/dm2The thickness of the copper plating layer was 15 μm.
Step 4, infiltration sintering of copper
Step 4.1, porosity k of the prefabricated porous tungsten skeleton model based on step 2.1 of 61.33 vol.% and peripheral volume V of the copper-plated porous tungsten skeleton in step 3 of 1.5525cm3Calculating the ideal required infiltration copper amount M equal to 8.9kV approximately equal to 8.49g, and the actual added infiltration copper amount is 1.2M equal to 10.17 g;
step 4.2, placing the copper powder obtained in the step 4.1 in a steel pressing die with a die cavity diameter of 25mm and a height of 100mm, and pressing the copper powder into a block to-be-infiltrated pure copper pressed blank under the pressure condition of 4 tons/square centimeter;
and 4.3, placing the copper-plated porous tungsten skeleton in the step 3 in a graphite mold cavity, placing the copper green compact in the step 4.2 above the copper green compact, covering a graphite cover, placing the copper green compact in a high-temperature sintering furnace, heating to 1250 ℃, then preserving heat for 90min, then cooling the furnace, introducing hydrogen or nitrogen in the heating process, wherein the introduction amount is 2L/h, removing redundant floating copper on the surface of a sintered part through machining after taking out, and observing XY planes, YZ planes and plane tissues forming an included angle of 60 degrees with YZ as shown in figures 5(a) to 5(c) to obtain the required tungsten-reinforced copper composite material.
Height l of graphite mold cavity0At least higher than the height l of the copper-plated porous tungsten skeleton1The height is 50 mm; the cross section of the graphite mold cavity is the same as the cross section of the copper-plated porous tungsten skeleton in size.
Example 2
The target is as follows: preparing an anisotropic copper-tungsten composite material, wherein the volume ratio of Cu is 90 vol.%, and the volume ratio of W powder is 10 vol.%.
Step 1, selecting raw materials
Weighing the following components according to volume fraction, wherein the volume ratio of copper powder Cu is 90 vol%, the balance is tungsten powder, and the sum of the volume percentages of the components is 100%;
step 2, preparing a porous tungsten framework;
2.1, placing the tungsten powder in the step 1 in a powder loading bin of a selective laser area melting device, inputting a prefabricated porous tungsten skeleton model, starting the selective laser area melting device to print, wherein the diameter of a light spot is 80 microns, the scanning mode is a chessboard type, the selective laser area is melted once every time powder is laid, the scanning interval is 60 microns, the scanning speed is 600mm/s, the thickness of the powder laying layer is 25 microns, the laser power is 100W, and the laser energy is 100J/mm3Continuously introducing argon gas for protection in the printing process, wherein the gas flow is 3m3Obtaining a prefabricated porous tungsten framework;
wherein the porosity of the prefabricated porous tungsten skeleton model is not less than 93.25 vol.%, and as shown in fig. 1(b), the prefabricated porous tungsten skeleton model designs the porous structure to be supported in a columnar shape
Figure BDA0002444691740000101
Each node is distributed in a spatial cross shape, the space between every two holes is 1.5mm, and the overall size is 11.25 × 11.1 × 11.2 mm.
And 2.2, pickling the prefabricated porous tungsten skeleton obtained in the step 2.1 for 3min to remove a surface oxide layer and oil stains, and then ultrasonically cleaning in alcohol for 3min at the ultrasonic frequency of 3MHz and at the room temperature to obtain the porous tungsten skeleton.
Step 3, preparing a copper-plated porous tungsten skeleton
Preparing electroplating solution, using a copper plate with the purity of 99% as an anode and the porous tungsten framework obtained in the step 2.2 as a cathode, and electroplating to obtain a copper-plated porous tungsten framework;
the concentration of the electroplating solution is as follows: CuSO with concentration of 80g/L4Solution and 3% H of the total volume of the plating solution2SO4Mixing the solution, adding H2SO4The reason for this is to make the plating solution acidic;
the parameters of the electroplating are as follows: the temperature of the electro-coppering is 50 ℃, the time is 60mins, and the working current density is 12A/dm2The thickness of the copper plating layer was 10 μm.
Step 4, infiltration sintering of copper
Step 4.1, porosity K of the prefabricated porous tungsten skeleton model based on step 2.1 of 93.25 vol.% and peripheral volume V of the copper-plated porous tungsten skeleton in step 3 of 1.3986cm3Calculating the ideal required infiltration copper amount M to be 8.9kV and approximately equal to 11.61g, and the actual added infiltration copper amount M to be 1.2M to be 13.93 g;
step 4.2, placing the copper powder obtained in the step 4.1 in a steel pressing die with a die cavity diameter of 25mm and a height of 150mm, and pressing the copper powder into a block to-be-infiltrated pure copper pressed blank under the pressure condition of 3 tons/square centimeter;
and 4.3, as shown in figure 3, placing the copper-plated porous tungsten skeleton in the step 3 in a graphite mold cavity, placing the copper green compact in the step 4.2 above the copper green compact, covering a graphite cover, placing the copper green compact in a high-temperature sintering furnace, heating to 1200 ℃, then preserving heat for 60min, cooling the furnace, introducing hydrogen in the heating process, wherein the introduction amount is 2L/h, grinding the redundant copper oxide by using a grinding machine, grinding by adopting a plurality of pieces of abrasive paper, and finally polishing until no scratch is formed, thus obtaining the required tungsten-reinforced copper composite material.
Height l of graphite mold cavity0At least higher than the height l of the copper-plated porous tungsten skeleton1The height is 60 mm; the cross section of the graphite mold cavity is the same as the cross section of the copper-plated porous tungsten skeleton in size.
Example 3
The target is as follows: preparing isotropic copper-tungsten composite material, wherein the volume ratio of Cu is 90 vol.%, and the volume ratio of W powder is 10 vol.%.
Step 1, selecting raw materials
Weighing the following components according to volume fraction, wherein the volume ratio of Cu is 90 vol.%, the balance is tungsten powder, and the sum of the volume percentages of the components is 100%;
step 2, preparing a porous tungsten framework;
2.1, placing the tungsten powder in the step 1 in a powder loading bin of a selective laser area melting device, inputting a prefabricated porous tungsten skeleton model, starting the selective laser area melting device to print, wherein the diameter of a light spot is 100 microns, the scanning mode is a chessboard type, the selective laser area is melted once every time powder is laid, the scanning interval is 60 microns, the scanning speed is 550mm/s, the thickness of the powder laying layer is 25 microns, the laser power is 90W, and the laser energy is 120J/mm3Continuously introducing nitrogen for protection in the printing process, wherein the gas flow is 2m3Obtaining a prefabricated porous tungsten framework;
wherein, the porosity of the prefabricated porous tungsten skeleton model is 90.62%, as shown in fig. 1(c), the porous structure is designed to be square through holes (1.5 × 1.5mm) in each direction, and the wall thickness is 0.3 mm; the hole pitch was 1.8mm and the overall size was 11.1 x 11.1 mm.
And 2.2, pickling the prefabricated porous tungsten skeleton obtained in the step 2.1 for 3min to remove a surface oxide layer and oil stains, and then ultrasonically cleaning in alcohol for 4min at the ultrasonic frequency of 1.2MHz and at the room temperature to obtain the porous tungsten skeleton.
Step 3, preparing a copper-plated porous tungsten skeleton
Preparing electroplating solution, using a copper plate with the purity of 99% as an anode and the porous tungsten framework obtained in the step 2.2 as a cathode, and electroplating to obtain a copper-plated porous tungsten framework;
the concentration of the electroplating solution is as follows: CuSO with concentration of 100g/L4Solution and 4% H of total volume of the plating solution2SO4Mixing the solution, adding H2SO4The reason for this is to make the plating solution acidic;
the parameters of the electroplating are as follows: the temperature of the electro-coppering is 60 ℃, the time is 50mins, and the working current density is 15A/dm2The height was 150mm, and the thickness of the copper plating layer was 5 μm.
Step 4, infiltration sintering of copper
Step 4.1, porosity k 90.62.% based on the prefabricated porous tungsten skeleton model of step 2.1 and peripheral volume V1.3676 cm of the copper-plated porous tungsten skeleton in step 33Calculating the ideal required infiltration copper amount M to be 8.9kV and approximately equal to 11.00g, namely the actual added infiltration copper is 1.2M, and weighing the copper powder 1.2M to be 13.20g in the step 1;
step 4.2, placing the copper powder obtained in the step 4.1 in a steel pressing die with a die cavity diameter of 20mm, and pressing the copper powder into a block to be infiltrated into a pure copper green compact under the pressure condition of 4 tons/square centimeter;
and 4.3, placing the copper-plated porous tungsten framework 4 in the step 3 into a cavity of a graphite mold 3, placing the copper pressed blank 2 in the step 4.2 above the copper pressed blank, covering a graphite cover 1, placing the copper pressed blank in a high-temperature sintering furnace, heating to 1250 ℃, then preserving heat for 90min, cooling the furnace, introducing hydrogen or nitrogen in the heating process, wherein the introducing amount is 3L/h, taking out, grinding the excessive copper by using a grinding machine, grinding by adopting a plurality of pieces of abrasive paper, and finally polishing until no scratch is formed, thus obtaining the required tungsten-reinforced copper composite material.
Height l of graphite mold cavity0At least higher than the height l of the copper-plated porous tungsten skeleton1The height is 60 mm; the cross section of the graphite mold cavity is the same as the cross section of the copper-plated porous tungsten skeleton in size.

Claims (6)

1. The preparation method of the tungsten reinforced copper composite material is characterized by comprising the following steps of:
step 1, selecting raw materials
Weighing the following components according to volume fraction, wherein copper powder is not less than 50%, and the balance is tungsten powder, and the sum of the volume percentages of the above components is 100%;
step 2, preparing a porous tungsten skeleton
Step 2.1, placing the tungsten powder in the step 1 in a powder loading bin of a selective laser melting device, inputting a prefabricated porous tungsten framework model, starting the selective laser melting device to print in a checkerboard mode, melting the selective laser melting device once every time powder is laid, and continuously introducing inert gas to protect in the printing process to obtain a prefabricated porous tungsten framework;
step 2.2, pickling the prefabricated porous tungsten skeleton obtained in the step 2.1 for 1-3 min, and then ultrasonically cleaning in alcohol for 3-5 min to obtain a porous tungsten skeleton;
step 3, preparing a copper-plated porous tungsten skeleton
Preparing electroplating solution, using a copper plate with the purity of 99% as an anode and the porous tungsten framework obtained in the step 2.2 as a cathode, and electroplating to obtain a copper-plated porous tungsten framework;
step 4, infiltration sintering of copper
Step 4.1, calculating the actually required amount M of infiltrated copper based on the porosity k of the porous tungsten skeleton model of step 2.1 and the peripheral volume V of the copper-plated porous tungsten skeleton of step 301.2M-1.2X 8.9kV, wherein 1.2 is infiltration loss coefficient 1.2, and copper powder in the step 1 is weighed;
step 4.2, placing the copper powder obtained in the step 4.1 in a steel pressing die with a die cavity diameter of 20-40 mm and a height of 50-200 mm, and pressing the copper powder into a block to be infiltrated into a pure copper pressed blank under the pressure condition of 3-5 tons/square centimeter;
4.3, placing the copper-plated porous tungsten skeleton in the step 3 in a graphite mold cavity, placing the copper green compact in the step 4.2 above the copper porous tungsten skeleton, covering a graphite cover, placing the copper green compact in a high-temperature sintering furnace for heating, then cooling the furnace, taking out the copper green compact, and removing copper floating on the surface to obtain the required tungsten-reinforced copper composite material;
the tungsten reinforced copper composite material comprises the following components, by volume, copper powder is not less than 50%, and the balance is tungsten powder, wherein the sum of the volume percentages of the components is 100%; the tungsten powder is spherical tungsten powder with the purity not less than 99.9%, and the particle size is 15-53 mu m; the copper powder is irregular copper powder with the purity not less than 99.9%, and the particle size is 50-70 mu m.
2. The method for preparing the tungsten-reinforced copper composite material as claimed in claim 1, wherein in the step 2.1, the printing parameters of the selective laser melting device are as follows: the diameter of a light spot is 45-100 mu m, the scanning interval is 60 mu m, the scanning speed is 550-650 mm/s, the thickness of a powder layer is 25 mu m, the laser power is 70-100W, and the laser energy is 80-130J/mm3；
The gas flow of the inert gas is 1-3 m3/h。
3. The method for preparing the tungsten-reinforced copper composite material as claimed in claim 1, wherein in the step 2.2, the acid washing is performed by using the following solutions: HF and HNO with volume ratio of 8:1:213And H2O mixed solution;
the ultrasonic parameters are as follows: the ultrasonic frequency is not less than 1MHz, and the temperature is room temperature.
4. The method as claimed in claim 1, wherein in the step 3, the electroplating solution is CuSO with a concentration of 60-100 g/L4Solution and solventH accounting for 2-5% of the total volume of the electroplating solution2SO4Mixing the solution;
the parameters of the electroplating are as follows: the temperature of the electro-coppering is 30-60 ℃, the time is 30-60 mins, and the working current density is 5-20A/dm2The thickness of the copper plating is 5-15 μm.
5. The method for preparing the tungsten-reinforced copper composite material according to claim 1, wherein the parameters of the high-temperature sintering furnace in the step 4.3 are as follows: heating to 1200-1250 ℃, and then preserving heat for 60-90 min; and introducing hydrogen or nitrogen in the heating process, wherein the introduction amount is 1-3L/h.
6. The method for preparing the tungsten-reinforced copper composite material as claimed in claim 1, wherein in the step 4.3, the height of the graphite mold cavity is at least 30-100 mm higher than that of the copper-plated porous tungsten skeleton; the cross section of the graphite mold cavity is the same as the cross section of the copper-plated porous tungsten skeleton in size.
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