CN109280833B - Preparation method of tungsten-copper composite material - Google Patents
Preparation method of tungsten-copper composite material Download PDFInfo
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- CN109280833B CN109280833B CN201811418537.4A CN201811418537A CN109280833B CN 109280833 B CN109280833 B CN 109280833B CN 201811418537 A CN201811418537 A CN 201811418537A CN 109280833 B CN109280833 B CN 109280833B
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- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 64
- 238000005238 degreasing Methods 0.000 claims abstract description 48
- 239000011230 binding agent Substances 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 22
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 238000001746 injection moulding Methods 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 7
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract 2
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- 238000010438 heat treatment Methods 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 44
- 238000002347 injection Methods 0.000 claims description 36
- 239000007924 injection Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 34
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
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- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 229960001484 edetic acid Drugs 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
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- 229910000881 Cu alloy Inorganic materials 0.000 description 1
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Images
Classifications
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- 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
-
- B22F1/0007—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
-
- 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
-
- 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
- B22F3/1025—Removal of binder or filler not by heating only
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
Abstract
The invention belongs to the technical field of composite materials, and discloses a preparation method of a tungsten-copper composite material. The method comprises the following steps: performing injection molding, degreasing and sintering on tungsten powder, copper powder, carbon nanotubes and a binder in a hydrogen atmosphere to obtain a high-conductivity and high-heat-conductivity tungsten-copper composite material; the dosage of the tungsten powder, the copper powder and the carbon nano tube meets the following conditions: according to the mass percentage, 74-84.8% of tungsten, 15-25% of copper and 0.2-1% of carbon nano tube; the adhesive comprises the following components in percentage by mass: 60-70% of paraffin, 10-16% of high-density polyethylene, 15-20% of ethylene-vinyl acetate copolymer, 1-4% of stearic acid and 0-0.5% of antioxidant. The obtained tungsten-copper composite material has high hardness and high electrical conductivity and thermal conductivity. The invention can inject the sample with complex shape by using the injection molding mode, and is suitable for the field of high-efficiency large-scale production.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a tungsten-copper composite material.
Background
The tungsten-copper composite material is a pseudo alloy consisting of tungsten with low thermal expansion and copper with high electrical conductivity and high thermal conductivity, has the advantages of high melting point, high strength, high hardness, good arc erosion resistance and the like, and is widely used for manufacturing high-temperature components such as electronic packaging materials, heat sink materials, electromachining electrodes, rocket nozzle throat linings, tail vanes and the like. With the rapid development of the electronic industry, the requirements for the tungsten-copper composite material with high thermal conductivity and high electrical conductivity are higher and higher, and the tungsten-copper composite material is developed towards the direction of more complex shape and higher dimensional precision. Because the difference between the physical properties of tungsten and copper is large (the existing tungsten-copper composite material is difficult to sinter and densify because tungsten and copper are not mutually soluble, the porosity is large, and the heat conduction and electric conductivity of the material is low), the tungsten-copper alloy cannot be produced by a fusion casting method, and is generally produced by a powder metallurgy method. However, most of the tungsten-copper composite materials produced by the existing powder metallurgy method are molded, and the shape and the size of products prepared by the traditional molding method are limited. In addition, the powder metallurgy method generally adopts copper infiltration to improve the density, but the sample needs to be processed by machining after the copper infiltration, so the production cost and the production period are increased, and the material is difficult to densify if the copper infiltration method is not adopted.
The Carbon Nanotubes (CNTs) have a special tubular structure, and have the characteristics of high specific stiffness, specific strength, high electrical conductivity, high thermal conductivity, high wear resistance, and the like, and the carbon nanotubes are used as a reinforcement of a composite material, so that the composite material can exhibit good mechanical properties and physical properties, but the carbon nanotubes cannot be uniformly dispersed in a sufficient content by using a simple method such as mechanical mixing or a solvent as a mixing means at present.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a high-electric-conductivity and high-thermal-conductivity tungsten-copper composite material. The invention adopts the injection molding method to prepare the sample with complex shape and high dimensional precision, and can realize large-batch high-efficiency production, thereby effectively reducing the production cost. Meanwhile, the carbon nano tubes are mixed in the binder, so that the agglomeration phenomenon of the CNTs is improved, the CNTs are effectively dispersed in a tungsten-copper matrix, and the electrical conductivity and the thermal conductivity of the composite material are improved; the method of the invention also improves the density and hardness of the material to a certain degree.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a tungsten-copper composite material comprises the following steps: performing injection molding, degreasing and sintering on tungsten powder, copper powder, carbon nanotubes and a binder in a hydrogen atmosphere to obtain a high-conductivity and high-heat-conductivity tungsten-copper composite material;
the dosage of the tungsten powder, the copper powder and the carbon nano tube meets the following conditions: the weight percentage of the raw materials is calculated,
74 to 84.8 percent of tungsten (W)
15 to 25 percent of copper (Cu)
0.2-1% of Carbon Nanotubes (CNTs)
And inevitable trace impurities.
The adhesive comprises the following components in percentage by mass:
the sum of the mass percentages of the components is 100 percent.
The volume ratio of the total consumption of the tungsten powder, the copper powder and the carbon nano tube to the binder is 1: (0.92-1.22). The total amount of the tungsten powder, the copper powder, the carbon nano tube and the binder is 48-55 vol%.
The purity of the tungsten powder is more than or equal to 99.95%, and the average particle size is 2.8-3.2 mu m; the purity of the copper powder is more than or equal to 99.50 percent, and the average particle size is 9.0-11.0 mu m; the carbon nanotube is a multi-walled carbon nanotube, and is formed by curling lamellar graphite, the diameter of the carbon nanotube is 60-100 nm, and the length of the carbon nanotube is 5-15 mu m.
The injection conditions are that the injection temperature is 120-160 ℃, the injection pressure is 80-120 bar, and the mold temperature is 30-50 ℃.
The degreasing comprises solvent degreasing and thermal degreasing, and means that solvent degreasing and thermal degreasing are sequentially carried out on the injection-molded green body; the solvent for solvent degreasing is n-heptane; the thermal degreasing is heating degreasing under the atmosphere of hydrogen; the temperature of solvent degreasing is 30-60 ℃, and the time of solvent degreasing is 2-10 h; the temperature of the hot degreasing is 600-900 ℃, and the time of the hot degreasing is 30-60 min.
When the thermal degreasing is carried out, staged heating degreasing is adopted; the method comprises the following specific steps: heating to 250-300 ℃ at a speed of 5-10 ℃/min under a hydrogen atmosphere, heating to 330-400 ℃ at a speed of 1-3 ℃/min, preserving heat for 20-35 min, heating to 450-500 ℃ at a speed of 1-3 ℃/min, preserving heat for 20-30 min, heating to 550 ℃ at a speed of 1-3 ℃/min, heating to 600-900 ℃ at a speed of 10 ℃/min, and preserving heat for 30-60 min.
The preparation method of the tungsten-copper composite material specifically comprises the following steps:
(1) mixing tungsten powder and copper powder to obtain mixed metal powder;
(2) mixing the carbon nano tube with a binder to obtain the carbon nano tube modified binder;
(3) mixing the modified binder of the carbon nano tube and the mixed metal powder, extruding, granulating, and performing injection molding to obtain a green body;
(4) sequentially degreasing the green body by using a solvent and thermally degreasing to obtain a degreased green body;
(5) and sintering the degreased green body to obtain the high-conductivity high-thermal-conductivity tungsten-copper composite material.
The mixing in the step (1) refers to mixing powder by using a V-shaped powder mixer;
the rotating speed of the V-shaped powder mixer is 20-40 r/min, and the powder mixing time is 10-15 h; the powder mixing cavity is made of stainless steel, and inert gas protection is not needed in the powder mixing process.
And (2) performing acid oxidation treatment, namely ultrasonically dispersing CNTs in a mixed solution of water, concentrated sulfuric acid and concentrated nitric acid, adding a chelating agent EDTA (ethylene diamine tetraacetic acid) for microwave heating, cooling, filtering, washing to be neutral, and drying to obtain the purified carbon nanotube.
The volume ratio of the water to the concentrated sulfuric acid (with the concentration of 98%) to the concentrated nitric acid (with the concentration of 67%) is 3:1:3, the ultrasonic dispersion time is 20-40 min, and the microwave medium-low fire heating time is 20-40 min; the mass ratio of the carbon nano tube to the EDTA is 1: 4.
The mixing condition in the step (2) is that the mixture is stirred for 0.8 to 1.5 hours at the temperature of 130 to 150 ℃.
The mixing temperature in the step (3) is 130-150 ℃, and the mixing time is 1.0-2.0 h.
The injection conditions in the step (3) are that the injection temperature is 120-160 ℃, the injection pressure is 80-120 bar, and the mold temperature is 30-50 ℃.
The solvent for solvent degreasing in the step (4) is n-heptane; the thermal degreasing is heating degreasing under the atmosphere of hydrogen.
The temperature of solvent degreasing is 30-60 ℃, the time of solvent degreasing is 2-10 h, and the temperature of thermal degreasing is 600-900 ℃ for 30-60 min.
When the thermal degreasing is carried out, staged heating degreasing is adopted; the method comprises the following specific steps: heating to 250-300 ℃ at a speed of 5-10 ℃/min under a hydrogen atmosphere, heating to 330-400 ℃ at a speed of 1-3 ℃/min, preserving heat for 20-35 min, heating to 450-500 ℃ at a speed of 1-3 ℃/min, preserving heat for 20-30 min, heating to 550 ℃ at a speed of 1-3 ℃/min, heating to 600-900 ℃ at a speed of 10 ℃/min, and preserving heat for 30-60 min.
The sintering temperature in the step (5) is 1050-1200 ℃, and the sintering time is 1-3 h.
The composite material and the preparation method have the following advantages and beneficial effects:
(1) the binder provided by the invention is a multi-component binder modified by purified CNTs, not only can be effectively removed during degreasing, but also can improve the agglomeration phenomenon of the CNTs, so that the CNTs are uniformly dispersed in a binder matrix, and the strength and the shape retention of a green body are improved.
(2) The tungsten-copper composite material provided by the invention is prepared by adding the carbon nano tube into tungsten copper, and the CNTs can improve the electrical conductivity and the thermal conductivity of the tungsten-copper composite material.
(3) After the tungsten-copper composite material provided by the invention is sintered, the action of capillary force is enhanced by the tiny layered hollow structure characteristic of the carbon nano tube, so that the density of the tungsten-copper composite material is improved in a small range, and meanwhile, the hardness and the wear resistance are improved.
(4) The tungsten-copper composite material provided by the invention can be formed into a relatively complex shape at one time by injection molding, has high production efficiency, does not need subsequent processing, and promotes the development of precision of the tungsten-copper composite material.
Drawings
FIG. 1 is an XRD spectrum of the mixed tungsten copper powder of example 1;
FIG. 2 is a TG-DSC graph of the binder after modification of carbon nanotubes in example 3;
FIG. 3 is an SEM image of an injected green body of example 5;
FIG. 4 is an SEM photograph of the sintered tungsten-copper composite material of example 5.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited to these examples. In the examples, CNTs are purified carbon nanotubes.
Example 1
Step 1: weighing W powder, Cu powder and CNTs according to the proportion of 79.5 wt% of W, 20 wt% of Cu and 0.5 wt% of CNTs, pouring the tungsten powder and the copper powder into a V-shaped powder mixer, adjusting the rotating speed to be 30r/min, mixing for 12h, and then sieving to obtain tungsten-copper powder with uniform components and no obvious agglomeration;
step 2: weighing the binder according to the proportion of 66.9 wt% PW, 20 wt% EVA, 10 wt% HDPE, 3 wt% SA and 0.1 wt% BHT; in addition, the volume ratio of the total consumption of the tungsten powder, the copper powder and the carbon nano tubes to the binder is 1: 1.2; adding the binder and the CNTs into a stirrer, and stirring for 1h at 150 ℃ to obtain a modified binder; adding the modified binder and tungsten copper powder into a rubber mixing mill, mixing for 2h at 140 ℃, extruding and granulating by an extruder, adding the prepared feed into an injection molding machine for injection, wherein the injection temperature is 160 ℃, the injection pressure is 110bar, and the mold temperature is 40 ℃ to obtain a green body;
and step 3: completely soaking the green body in 40 ℃ n-heptane for 6h to remove PW and SA in the green body, drying the green body, putting the dried green body into a tube furnace for thermal degreasing, heating to 300 ℃ at a speed of 10 ℃/min under a hydrogen atmosphere, heating to 330 ℃ at a speed of 3 ℃/min, preserving heat for 30min, heating to 450 ℃ at a speed of 3 ℃/min, preserving heat for 30min, heating to 550 ℃ at a speed of 1 ℃/min, heating to 700 ℃ at a speed of 10 ℃/min, and preserving heat for 30 min;
and 4, step 4: and sintering at 1200 ℃ in a hydrogen atmosphere by adopting a hydrogen furnace after thermal degreasing, preserving heat for 2 hours, and cooling along with the furnace to obtain the tungsten-copper composite material.
The hardness of the tungsten-copper composite material prepared by the embodiment is 47.5HRC, and the electric conductivity and the thermal conductivity are 26.2 IACS% and 195W/m.K respectively. The XRD pattern of the mixed tungsten copper powder of this example is shown in FIG. 1.
Example 2
Step 1: weighing W powder, Cu powder and CNTs according to the proportion of 79.0 wt% of W, 20 wt% of Cu and 1.0 wt% of CNTs; pouring tungsten powder and copper powder into a V-shaped powder mixer, adjusting the rotating speed to 30r/min, mixing for 12h, and then sieving to obtain tungsten-copper powder with uniform components and no obvious agglomeration;
step 2: weighing the binder according to the proportion of 66.9 wt% PW, 20 wt% EVA, 10 wt% HDPE, 3 wt% SA and 0.1 wt% BHT; in addition, the volume ratio of the total consumption of the tungsten powder, the copper powder and the carbon nano tubes to the binder is 1: 1.2; adding the binder and the CNTs into a stirrer, stirring for 1h at 150 ℃, then adding the mixed binder and tungsten-copper powder into a rubber mixing mill, mixing for 2h at 140 ℃, performing extrusion granulation through an extruder, adding the prepared feed into an injection molding machine for injection, wherein the injection temperature is 160 ℃, the injection pressure is 110bar, and the mold temperature is 40 ℃, so as to obtain an injection green body;
and step 3: completely immersing the injection green body in n-heptane at 40 ℃ for 6h to remove PW and SA in the injection green body, drying the green body, putting the dried green body into a tube furnace for thermal degreasing, heating to 300 ℃ at 10 ℃/min under the hydrogen atmosphere, heating to 330 ℃ at 3 ℃/min, preserving heat for 30min, heating to 450 ℃ at 3 ℃/min, preserving heat for 30min, heating to 550 ℃ at 1 ℃/min, heating to 700 ℃ at 10 ℃/min, and preserving heat for 30 min;
and 4, step 4: and sintering at 1200 ℃ in a hydrogen atmosphere by adopting a hydrogen furnace after thermal degreasing, preserving heat for 2 hours, and cooling along with the furnace to obtain the tungsten-copper composite material.
The hardness of the tungsten-copper composite material prepared by the embodiment is 42.2HRC, and the electric conductivity and the thermal conductivity are 27.7 IACS% and 201W/m.K respectively.
Example 3
Step 1: weighing W powder, Cu powder and CNTs according to the proportion of 79.8 wt% of W, 20 wt% of Cu and 0.2 wt% of CNTs; pouring tungsten powder and copper powder into a V-shaped powder mixer, adjusting the rotating speed to 30r/min, mixing for 12h, and then sieving to obtain tungsten-copper powder with uniform components and no obvious agglomeration;
step 2: weighing the binder according to the proportion of 66.9 wt% PW, 20 wt% EVA, 10 wt% HDPE, 3 wt% SA and 0.1 wt% BHT; in addition, the volume ratio of the total consumption of the tungsten powder, the copper powder and the carbon nano tubes to the binder is 1: 1.2; adding the binder and the CNTs into a stirrer, stirring for 1h at 150 ℃, then adding the mixed binder and tungsten-copper powder into a rubber mixing mill, mixing for 2h at 140 ℃, performing extrusion granulation through an extruder, adding the prepared feed into an injection molding machine for injection, wherein the injection temperature is 160 ℃, the injection pressure is 110bar, and the mold temperature is 40 ℃, so as to obtain an injection green body;
and step 3: completely immersing the injection green body in a normal heptane solution at 40 ℃ for 6h to remove PW and SA in the injection green body, then drying the green body, putting the dried green body into a tube furnace for thermal degreasing, heating to 300 ℃ at 10 ℃/min under a hydrogen atmosphere, heating to 330 ℃ at 3 ℃/min, preserving heat for 30min, heating to 450 ℃ at 3 ℃/min, preserving heat for 30min, heating to 550 ℃ at 1 ℃/min, heating to 700 ℃ at 10 ℃/min, and preserving heat for 30 min;
and 4, step 4: and sintering at 1200 ℃ in a hydrogen atmosphere by adopting a hydrogen furnace after thermal degreasing, preserving heat for 2 hours, and cooling along with the furnace to obtain the tungsten-copper composite material.
The hardness of the tungsten-copper composite material prepared by the embodiment is 49.1HRC, and the electric conductivity and the thermal conductivity are 23.2 IACS% and 177W/m.K respectively. The TG-DSC curve of the binder after carbon nanotube modification in this example is shown in FIG. 2.
Example 4
Step 1: weighing W powder, Cu powder and CNTs according to the proportion of 84.5 wt% of W, 15 wt% of Cu and 0.5 wt% of CNTs; pouring tungsten powder and copper powder into a V-shaped powder mixer, adjusting the rotating speed to 30r/min, mixing for 12h, and then sieving to obtain tungsten-copper powder with uniform components and no obvious agglomeration;
step 2: weighing the binder according to the proportion of 66.9 wt% PW, 20 wt% EVA, 10 wt% HDPE, 3 wt% SA and 0.1 wt% BHT; in addition, the volume ratio of the total consumption of the tungsten powder, the copper powder and the carbon nano tubes to the binder is 1: 1.2; adding the binder and the CNTs into a stirrer, stirring for 1h at 150 ℃, then adding the mixed binder and tungsten-copper powder into a rubber mixing mill, mixing for 2h at 140 ℃, performing extrusion granulation through an extruder, adding the prepared feed into an injection molding machine for injection, wherein the injection temperature is 160 ℃, the injection pressure is 110bar, and the mold temperature is 40 ℃, so as to obtain an injection green body;
and step 3: completely immersing the injection green body in a normal heptane solution at 40 ℃ for 6h to remove PW and SA in the injection green body, then drying the green body, putting the dried green body into a tube furnace for thermal degreasing, heating to 300 ℃ at 10 ℃/min under a hydrogen atmosphere, heating to 330 ℃ at 3 ℃/min, preserving heat for 30min, heating to 450 ℃ at 3 ℃/min, preserving heat for 30min, heating to 550 ℃ at 1 ℃/min, heating to 700 ℃ at 10 ℃/min, and preserving heat for 30 min;
and 4, step 4: and sintering at 1200 ℃ in a hydrogen atmosphere by adopting a hydrogen furnace after thermal degreasing, preserving heat for 2 hours, and cooling along with the furnace to obtain the tungsten-copper composite material.
The hardness of the tungsten-copper composite material prepared by the embodiment is 48.4HRC, and the electric conductivity and the thermal conductivity are 25.6 IACS% and 189W/m.K respectively.
Example 5
Step 1: weighing W powder, Cu powder and CNTs according to the proportion of 79.2 wt% of W, 20 wt% of Cu and 0.8 wt% of CNTs; pouring tungsten powder and copper powder into a V-shaped powder mixer, adjusting the rotating speed to 30r/min, mixing for 12h, and then sieving to obtain tungsten-copper powder with uniform components and no obvious agglomeration;
step 2: weighing the binder according to the proportion of 66.9 wt% PW, 20 wt% EVA, 10 wt% HDPE, 3 wt% SA and 0.1 wt% BHT; in addition, the volume ratio of the total consumption of the tungsten powder, the copper powder and the carbon nano tubes to the binder is 1: 1.2; adding the binder and the CNTs into a stirrer, stirring for 1h at 150 ℃, then adding the mixed binder and tungsten-copper powder into a rubber mixing mill, mixing for 2h at 140 ℃, performing extrusion granulation through an extruder, adding the prepared feed into an injection molding machine for injection, wherein the injection temperature is 160 ℃, the injection pressure is 110bar, and the mold temperature is 40 ℃, so as to obtain an injection green body;
and step 3: completely immersing the injection green body in a normal heptane solution at 40 ℃ for 6h to remove PW and SA in the injection green body, then drying the green body, putting the dried green body into a tube furnace for thermal degreasing, heating to 300 ℃ at 10 ℃/min under a hydrogen atmosphere, heating to 330 ℃ at 3 ℃/min, preserving heat for 30min, heating to 450 ℃ at 3 ℃/min, preserving heat for 30min, heating to 550 ℃ at 1 ℃/min, heating to 700 ℃ at 10 ℃/min, and preserving heat for 30 min;
and 4, step 4: and sintering at 1200 ℃ in a hydrogen atmosphere by adopting a hydrogen furnace after thermal degreasing, preserving heat for 2 hours, and cooling along with the furnace to obtain the tungsten-copper composite material.
The hardness of the tungsten-copper composite material prepared by the embodiment is 43.5HRC, and the electric conductivity and the thermal conductivity are 26.5 IACS% and 191W/m.K respectively. An SEM image of the injected green body of this example is shown in fig. 3; the SEM image of the sintered tungsten copper composite material is shown in fig. 4.
Comparative example 1 compression Molding method
Step 1: weighing W powder, Cu powder and CNTs according to the proportion of 79.2 wt% of W, 20 wt% of Cu and 0.8 wt% of CNTs, pouring the materials into a V-shaped powder mixer for mixing, adjusting the rotating speed to be 30r/min, mixing for 12h, and then sieving to obtain mixed powder;
step 2: pouring the mixed powder into a die, and placing the die under a press machine for pressing and forming, wherein the pressure is 200MPa, so as to obtain a composite material pressing green body;
and step 3: and (3) putting the green body into a hydrogen furnace, heating to 1200 ℃ at a speed of 10 ℃/min under the hydrogen atmosphere, sintering, keeping the temperature for 2 hours, and cooling along with the furnace to obtain the tungsten-copper composite material.
The hardness of the tungsten-copper composite material prepared by the embodiment is 37.4HRC, and the electric conductivity and the thermal conductivity are 16.3 IACS% and 177W/m.K respectively.
The above examples are preferred embodiments of the present invention, but the present invention is not limited by the examples, and any other insubstantial changes and substitutions based on the present invention are included in the scope of the present invention.
Claims (9)
1. A preparation method of a tungsten-copper composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing tungsten powder and copper powder to obtain mixed metal powder;
(2) mixing the carbon nano tube with a binder to obtain the carbon nano tube modified binder;
(3) mixing the modified binder of the carbon nano tube and the mixed metal powder, extruding, granulating, and performing injection molding to obtain a green body;
(4) sequentially degreasing the green body by using a solvent and thermally degreasing to obtain a degreased green body;
(5) sintering the degreased green body to obtain a tungsten-copper composite material;
the dosage of the tungsten powder, the copper powder and the carbon nano tube meets the following conditions: the weight percentage of the raw materials is calculated,
74 to 84.8 percent of tungsten
15 to 25 percent of copper
0.2-1% of carbon nano tube;
the adhesive comprises the following components in percentage by mass:
60 to 70 percent of paraffin
10-16% of high-density polyethylene
15-20% of ethylene-vinyl acetate copolymer
1 to 4 percent of stearic acid
0-0.5% of antioxidant.
2. The method for preparing the tungsten-copper composite material according to claim 1, wherein the method comprises the following steps: the volume ratio of the total consumption of the tungsten powder, the copper powder and the carbon nano tube to the binder is 1: (0.92-1.22);
the injection conditions are that the injection temperature is 120-160 ℃, the injection pressure is 80-120 bar, and the mold temperature is 30-50 ℃.
3. The method for preparing the tungsten-copper composite material according to claim 1, wherein the method comprises the following steps: the solvent for solvent degreasing is n-heptane; the thermal degreasing is heating degreasing under the atmosphere of hydrogen;
the temperature of solvent degreasing is 30-60 ℃, and the time of solvent degreasing is 2-10 h; the temperature of the hot degreasing is 600-900 ℃, and the time of the hot degreasing is 30-60 min.
4. The method for preparing the tungsten-copper composite material according to claim 3, wherein: when the thermal degreasing is carried out, staged heating degreasing is adopted; the method comprises the following specific steps: heating to 250-300 ℃ at a speed of 5-10 ℃/min under a hydrogen atmosphere, heating to 330-400 ℃ at a speed of 1-3 ℃/min, preserving heat for 20-35 min, heating to 450-500 ℃ at a speed of 1-3 ℃/min, preserving heat for 20-30 min, heating to 550 ℃ at a speed of 1-3 ℃/min, heating to 600-900 ℃ at a speed of 10 ℃/min, and preserving heat for 30-60 min.
5. The method for preparing the tungsten-copper composite material according to claim 1, wherein the method comprises the following steps: in the step (5), the sintering temperature is 1050-1200 ℃, the sintering time is 1-3 h, and the sintering is carried out in a hydrogen atmosphere;
and (3) the carbon nano tube in the step (2) is a purified carbon nano tube, and the purification refers to acid oxidation treatment.
6. The method for preparing the tungsten-copper composite material according to claim 5, wherein: the purification specifically comprises the steps of ultrasonically dispersing the carbon nano tube in a mixed solution of water, concentrated sulfuric acid and concentrated nitric acid, then adding a chelating agent EDTA (ethylene diamine tetraacetic acid) for microwave heating, cooling, filtering, washing to be neutral, and drying to obtain the purified carbon nano tube.
7. The method for preparing the tungsten-copper composite material according to claim 6, wherein: the volume ratio of the water to the concentrated sulfuric acid to the concentrated nitric acid is 3:1:3, the ultrasonic dispersion time is 20-40 min, and the microwave medium-low fire heating time is 20-40 min; the mass ratio of the carbon nano tube to the EDTA is 1: 4.
8. The method for preparing the tungsten-copper composite material according to claim 1, wherein the method comprises the following steps: the mixing condition in the step (2) is that the mixture is stirred for 0.8 to 1.5 hours at the temperature of 130 to 150 ℃;
the mixing temperature in the step (3) is 130-150 ℃, and the mixing time is 1.0-2.0 h;
the mixing in the step (1) refers to mixing powder by using a V-shaped powder mixer; the rotating speed of the V-shaped powder mixer is 20-40 r/min, and the powder mixing time is 10-15 h.
9. A tungsten-copper composite material obtained by the production method according to any one of claims 1 to 8.
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| 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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| CN101667498A (en) * | 2009-10-13 | 2010-03-10 | 昆明理工大学 | Preparation method of W-Cu electrical contact |
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