CN116497245A - Diamond doped tungsten copper alloy and preparation method thereof - Google Patents
Diamond doped tungsten copper alloy and preparation method thereof Download PDFInfo
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- CN116497245A CN116497245A CN202310417195.9A CN202310417195A CN116497245A CN 116497245 A CN116497245 A CN 116497245A CN 202310417195 A CN202310417195 A CN 202310417195A CN 116497245 A CN116497245 A CN 116497245A
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 108
- 239000010432 diamond Substances 0.000 title claims abstract description 108
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 54
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 30
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 238000007747 plating Methods 0.000 claims abstract description 11
- 239000011812 mixed powder Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 239000004519 grease Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 41
- 229910052802 copper Inorganic materials 0.000 claims description 35
- 238000001764 infiltration Methods 0.000 claims description 20
- 230000008595 infiltration Effects 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 19
- 238000003825 pressing Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003698 laser cutting Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 230000006698 induction Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000004100 electronic packaging Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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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
- C22C1/0475—Impregnated 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- 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
- B22F1/18—Non-metallic particles coated with metal
-
- 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
- B22F3/02—Compacting 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
- B22F3/1035—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
- B22F3/24—After-treatment of workpieces or articles
- B22F3/26—Impregnating
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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
- C22C1/045—Alloys based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/223—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating specially adapted for coating particles
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to the technical field of preparation of high-heat-conductivity materials, and discloses a preparation method of a doped diamond tungsten copper alloy, which comprises the following steps: step one, diamond tungsten plating: cleaning high-grade diamond particles, cleaning the diamond particles by using absolute ethyl alcohol and acetone to achieve the purpose of removing surface grease and impurities, and then depositing a uniform tungsten coating on the diamond particles by using magnetron sputtering; step two, mixing powder: weighing a certain amount of induced copper powder, tungsten powder and tungsten-plated diamond powder, and uniformly mixing in a powder mixer; step three, compression molding: and (3) mixing the mixed powder obtained in the step (II) with a forming agent, and then performing cold press forming in a die to obtain a green body. The method for doping the tungsten-copper alloy with the diamond has the advantages of convenient operation flow, low energy consumption, low equipment requirement, low cost, high production efficiency and easy industrialized popularization and large-scale production.
Description
Technical Field
The invention relates to the technical field of preparation of high-heat-conductivity materials, in particular to a diamond-doped tungsten-copper alloy and a preparation method thereof.
Background
As microelectronic packaging technology evolves toward multi-chip modules (MCM) and surface mount technology (SET), conventional packaging materials have failed to meet the high density packaging requirements, new composite materials must be developed, future metal-based packaging materials will evolve toward high performance, low cost, low density, and integration, and electronic packaging materials will evolve toward multi-phase compounding. In recent decades, in the fields of military, aerospace, high-end civil electronic devices and the like, higher requirements are put on several key factors of packaging materials, such as: high thermal conductivity, high packing density, lightweight requirements, price requirements, etc., with the most important properties being: high thermal conductivity, low and tunable coefficient of thermal expansion, low density (weight requirements field). In fact, conventional materials do not meet the development requirements at the same time. In order to further increase the heat transfer rate and ensure the safety and stability of electronic components, it is necessary to develop advanced materials to improve the overall thermal conductivity.
The tungsten-copper alloy is used as a third-generation electronic packaging material, so that the heat conductivity coefficient of the W-Cu composite material is improved, and the heat conductivity coefficient of the whole packaging material is improved. The addition of a third phase to the W-Cu composite to improve its microstructure and properties is an important approach, where diamond has a relatively high thermal conductivity (2200W-m-1-K-1), much higher than W and Cu, and its low density may make the composite overall tend to be lightweight. Therefore, the addition of a proper amount of diamond into the W-Cu composite material is beneficial to further improving the performance of the W-Cu composite material. Some metals such as Cu and Ag have poor wettability with diamond, but in composite materials containing the metals and the diamond, the uncoated diamond is only mechanically combined with a metal matrix, so that the combination has poorer wettability, and more gaps are formed at the combination, which is unfavorable for heat conduction. Studies have shown that surface metallization of diamond particles is an effective way to improve the diamond to metal matrix interface combination. W is selected as the coating metal and can be easily combined with W in the W-Cu matrix during sintering. W can also react with C in the diamond, and some carbide interlayers are formed between the diamond and the W coating, which is beneficial to improving the interface strength. In addition, tungsten carbide formed during the plating process has a relatively high thermal conductivity compared to other carbide forming elements. Until now, reports and researches on adding diamond into W-Cu composite materials are mainly completed by using methods of microwave pressure sintering, spark plasma sintering, vacuum hot-pressing sintering and high-temperature high-pressure sintering, but the sintering means can obtain the tungsten-copper diamond composite materials with high compactness and higher performance, but the equipment is very expensive, the requirements on sintering conditions are high, and the method is difficult to be applied to low-cost, large-scale and easy-to-operate production.
Therefore, the invention adopts the metallized diamond as the additive phase, and utilizes the pressureless infiltration method to attempt to achieve the purposes of improving the heat conductivity of the W-Cu alloy and realizing low-cost and large-scale production of the tungsten-copper doped diamond composite material.
Disclosure of Invention
The proposal provided by the invention solves the defect of doping the third component in the prior tungsten-copper alloy, namely: the invention improves the thermal conductivity and simultaneously provides a method and a way for the large-scale production of the tungsten-copper diamond composite material from a laboratory.
The invention is realized by adopting the following technical scheme:
the preparation method of the doped diamond tungsten copper alloy comprises the following steps:
step one, diamond tungsten plating:
cleaning high-grade diamond particles, cleaning the diamond particles by using absolute ethyl alcohol and acetone to achieve the purpose of removing surface grease and impurities, and then depositing a uniform tungsten coating on the diamond particles by using magnetron sputtering;
step two, mixing powder:
weighing a certain amount of induced copper powder, tungsten powder and tungsten-plated diamond powder, and uniformly mixing in a powder mixer;
step three, compression molding:
mixing the mixed powder obtained in the step two with a forming agent, and then cold-pressing the mixed powder into a green body in a die;
step four, infiltration sintering:
placing the green compact formed by cold pressing in a sintering boat, placing a infiltration copper block to be infiltrated at the upper end of the compact, burying the periphery by nano-scale alumina powder, then placing the compact in a high-temperature atmosphere tube furnace for heating and heat preservation, and then cooling along with the furnace to obtain a diamond-doped tungsten-copper alloy;
step five, post-treatment:
and (3) performing wire cutting on the diamond-doped tungsten-copper alloy obtained in the step (III) to remove redundant cladding copper, cutting a sample into a required size by utilizing laser cutting, and polishing by a surface grinder with gradually increasing mesh number to obtain a finished product.
Preferably, in step one, a tungsten coating is deposited on the diamond particles by means of direct current magnetron sputtering to obtain a uniform and dense tungsten-plated diamond, wherein the diameter of the pure tungsten target with purity of 99.95% isThe thickness was 4mm, and in addition, the model of the magnetron sputtering system was JGP-450A.
Preferably, in the step 1, the magnetron sputtering deposition time can be changed to obtain tungsten coatings with different thicknesses, and the specific deposition time is: 20/30/60min.
Preferably, the use amounts of the copper powder, the tungsten-plated diamond powder and the copper infiltration block induced in the second step and the third step are as follows: the tungsten powder is mixed with coarse powder and fine powder, the weight percentage of the coarse powder and the fine powder is 75 percent and 25 percent respectively, the induced copper powder accounts for 2 to 3 percent of the total weight of the tungsten powder, the tungsten plating diamond powder accounts for 1 to 3 percent of the total weight of the tungsten powder, and the rest of the green blank gaps are filled into infiltration copper blocks.
Preferably, the particle size of the tungsten powder in the second step is 0.1-20 microns, and the particle size of the induced copper powder is 50 microns.
Preferably, stearic acid (CAS number: 57-11-4, purity not less than 99.0%) is added in the process of pressing the blank in the second step to obtain a mass ratio of 0.5%, and the die size isThe pressing pressure is 260-600 MPa.
Preferably, the copper infiltration block in the third step is oxygen-free copper, the heating temperature is 1200-1300 ℃, the heating temperature rising rate is 200-300 ℃/h, and the heat preservation time is 30-60 min.
Preferably, in the third step, argon is used for atmosphere protection, and the gas flow is 1-2L/h.
The invention also provides a doped diamond tungsten copper alloy which is prepared by adopting the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the tungsten-copper diamond powder with controllable and uniform tungsten coating thickness is efficiently obtained by utilizing a magnetron sputtering method, so that the wetting relation between diamond and tungsten and copper is improved, and then the tungsten-copper diamond composite material is prepared by the method of mixing powder, mould pressing and infiltration sintering, so that the coating efficiency of the coated diamond is improved, and the thermal property of the coated diamond is improved by optimizing an interface structure, thereby remarkably improving the heat conducting property of the tungsten-copper composite material, reducing the thermal expansion coefficient and promoting the application of the diamond as a reinforcing phase in the aspect of thermal management materials.
The method for doping the tungsten-copper alloy with the diamond has the advantages of convenient operation flow, low energy consumption, low equipment requirement, low cost, high production efficiency and easy industrialized popularization and large-scale production.
Drawings
FIG. 1 is a scanning photograph of diamond particles after tungsten plating (a) (b) and EDS spectroscopy analysis (c);
FIG. 2 is a Raman analysis of diamond particles in a tungsten copper doped diamond green body;
FIG. 3 is a gold phase diagram (a) of a tungsten copper alloy doped with 40vol.% diamond;
FIG. 4 is a graph of fracture morphology (b) of tungsten-copper alloy doped with 40vol.% diamond;
FIG. 5 is a graph of thermal conductivity of tungsten-copper alloy doped with different amounts of diamond;
fig. 6 is a graph of thermal expansion data analysis of tungsten-copper alloy doped with different amounts of diamond.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, wherein it is to be understood that, on the premise of no conflict, the following embodiments or technical features may be arbitrarily combined to form new embodiments.
Example 1:
the preparation of the W80Cu20 alloy doped with 10vol.% diamond is carried out according to the following steps:
step one, diamond tungsten plating:
the commercial diamond powder with the diameter of 70-100 μm is ultrasonically cleaned in acetone solution for 3-5 min and dried in air to remove residues such as grease, impurities and the like attached to the surface. Immediately placing the cleaned diamond powder on a sample base of a magnetron sputtering system, and adopting a direct current magnetron sputtering mode to deposit and prepare a tungsten coating on the diamond particles, wherein the deposition time is 30min, so that uniform and compact tungsten-plated diamond is obtained, and the thickness of the coating is about 300-500 nm.
Step two, mixing powder:
the volume occupied by tungsten powder and tungsten-plated diamond powder is calculated according to the composition of the prepared W-20Cu alloy doped with 10vol.% diamond, the relative density of the pressed green compact is calculated to be the duty ratio of theoretical density, the rest volume is copper, and all raw materials are weighed (the calculation method of the weighing amount is that the volume of each powder is multiplied by the theoretical density). Then adding 2% of induction copper powder, mechanically mixing the induction copper powder with tungsten powder and tungsten-plated diamond powder in a V-shaped powder mixer for more than 6 hours, and taking care that a mixing bottle cap needs to be sealed during mixing.
Preparing a tungsten and tungsten-plated diamond compact:
according to the size of the pressed sample and the specific component requirements, 15g of mixed powder of the materials mixed in the step 2 is weighed and put into a steel pressing moldAnd (3) cold press molding, wherein the selected press pressure is 210MPa, and the obtained green compact has a relative density of 68%.
And step four, infiltration sintering:
the green body formed by cold pressing in the third step is arranged in a sintering boat, a infiltration copper block (which can be processed by pure copper section materials or can be formed by pure copper powder) to be infiltrated is placed at the upper end of the pressed blank (the volume of gaps in the green body is multiplied by the density of copper, and the balance can be reserved), the periphery of the pressed blank is buried by nano-scale alumina powder, then the pressed blank is placed in a high-temperature atmosphere tube furnace for slow heating (the heating rate is 5-8 ℃/mm), the temperature is increased to 500 ℃ for 0.5h for degreasing, the temperature is increased to 1250 ℃ for 1h for cooling, and then the protective atmosphere for cooling along with the furnace is argon, and the gas flow is 1-2L/h.
Step 5, post-treatment:
and (3) performing wire cutting on the diamond-doped tungsten-copper alloy obtained in the step four to remove redundant cladding copper, cutting a sample into a required size by utilizing laser cutting, and polishing the surface by using a grinder with gradually increasing mesh number (100-240 meshes) to obtain a finished product. The relative density of the finished product is 97.2%, the thermal conductivity is 207W/(mK), and the thermal expansion coefficient is 6.64 multiplied by 10 < -6 >/K.
Example 2:
the preparation of the W80Cu20 alloy doped with 20vol.% diamond is carried out according to the following steps:
step one, diamond tungsten plating:
the commercial diamond powder with the diameter of 70-100 μm is ultrasonically cleaned in acetone solution for 3-5 min and dried in air to remove residues such as grease, impurities and the like attached to the surface.
Immediately placing the cleaned diamond powder on a sample base of a magnetron sputtering system, and adopting a direct current magnetron sputtering mode to deposit and prepare a tungsten coating on the diamond particles, wherein the deposition time is 30min, so that uniform and compact tungsten-plated diamond is obtained, and the thickness of the coating is about 300-500 nm.
Step two, mixing powder:
the volume occupied by tungsten powder and tungsten-plated diamond powder is calculated according to the composition of the prepared W-20Cu alloy doped with 20vol.% diamond, the relative density of the pressed green compact is calculated to be the duty ratio of theoretical density, the rest volume is copper, and all raw materials are weighed (the calculation method of the weighing amount is that the volume of each powder is multiplied by the theoretical density). Then adding 2% of induction copper powder, mechanically mixing the induction copper powder with tungsten powder and tungsten-plated diamond powder in a V-shaped powder mixer for more than 6 hours, and taking care that a mixing bottle cap needs to be sealed during mixing.
Preparing a tungsten and tungsten-plated diamond compact:
according to the size of the pressed sample and the specific component requirements, 15g of mixed powder of the materials mixed in the step two is weighed and put into a steel pressing moldAnd (3) cold press molding, wherein the selected press pressure is 200MPa, and the obtained green compact has a relative density of 68%.
And step four, infiltration sintering:
the green compact formed by cold pressing in the step four is arranged in a sintering boat, a infiltration copper block (which can be processed by pure copper section materials or can be formed by pure copper powder) to be infiltrated is placed at the upper end of the pressed compact (the volume of gaps in the green compact is multiplied by the density of copper, and the balance can be reserved), the periphery is buried by nano-scale alumina powder, then the green compact is placed in a high-temperature atmosphere tube furnace for slow heating (the heating rate is 5-8 ℃/mm), the green compact is heated to 500 ℃ for heat preservation for 0.5h for degreasing, then the green compact is heated to 1250 ℃ for heat preservation for 1h, and then the green compact is cooled along with the furnace, wherein the used protective atmosphere is argon, and the gas flow is 1-2L/h.
Step five, post-treatment:
and (3) performing wire cutting on the diamond-doped tungsten-copper alloy obtained in the step four to remove redundant cladding copper, cutting a sample into a required size by utilizing laser cutting, and polishing the surface by using a grinder with gradually increasing mesh number (100-240 meshes) to obtain a finished product. The relative density of the finished product is 97.7%, the thermal conductivity is 214W/(mK), and the thermal expansion coefficient is 7.49 multiplied by 10 < -6 >/K.
Example 3:
the preparation of the W80Cu20 alloy doped with 30vol.% diamond is carried out according to the following steps:
step one, diamond tungsten plating:
the commercial diamond powder with the diameter of 70-100 μm is ultrasonically cleaned in acetone solution for 3-5 min and dried in air to remove residues such as grease, impurities and the like attached to the surface.
Immediately placing the cleaned diamond powder on a sample base of a magnetron sputtering system, and adopting a direct current magnetron sputtering mode to deposit and prepare a tungsten coating on the diamond particles, wherein the deposition time is 30min, so that uniform and compact tungsten-plated diamond is obtained, and the thickness of the coating is about 300-500 nm.
Step two, mixing powder:
the volume occupied by tungsten powder and tungsten-plated diamond powder is calculated according to the composition of the prepared W-20Cu alloy doped with 30vol.% diamond, the relative density of the pressed green compact is calculated to be the duty ratio of theoretical density, the rest volume is copper, and all raw materials are weighed (the calculation method of the weighing amount is that the volume of each powder is multiplied by the theoretical density). Then adding 2% of induction copper powder, mechanically mixing the induction copper powder with tungsten powder and tungsten-plated diamond powder in a V-shaped powder mixer for more than 6 hours, and taking care that a mixing bottle cap needs to be sealed during mixing.
Preparing a tungsten and tungsten-plated diamond compact:
weighing the materials mixed in the step two according to the size of the pressed sample and the specific component requirement15g of mixed powder is taken and put in a steel pressing moldAnd (3) cold press molding, wherein the selected press pressure is 190MPa, and the obtained green compact has a relative density of 68%.
And step four, infiltration sintering:
the green body formed by cold pressing in the third step is arranged in a sintering boat, a infiltration copper block (which can be processed by pure copper section materials or can be formed by pure copper powder) to be infiltrated is placed at the upper end of the pressed blank (the volume of gaps in the green body is multiplied by the density of copper, and the balance can be reserved), the periphery of the pressed blank is buried by nano-scale alumina powder, then the pressed blank is placed in a high-temperature atmosphere tube furnace for slow heating (the heating rate is 5-8 ℃/mm), the temperature is raised to 500 ℃ for 0.5h for degreasing, the temperature is raised to 1250 ℃ for 1h for cooling along with the furnace, and the used protective atmosphere is argon gas with the gas flow of 1-2L/h.
Step five, post-treatment:
and (3) performing wire cutting on the diamond-doped tungsten-copper alloy obtained in the step four to remove redundant cladding copper, cutting a sample into a required size by utilizing laser cutting, and polishing the surface by using a grinder with gradually increasing mesh number (100-240 meshes) to obtain a finished product. The relative density of the finished product is 98.1%, the thermal conductivity is 226W/(mK), and the thermal expansion coefficient is 7.62X10-6/K.
Example IV
The preparation of the W80Cu20 alloy doped with 40vol.% diamond is carried out according to the following steps:
step one, diamond tungsten plating:
the commercial diamond powder with the diameter of 70-100 μm is ultrasonically cleaned in acetone solution for 3-5 min and dried in air to remove residues such as grease, impurities and the like attached to the surface.
Immediately placing the cleaned diamond powder on a sample base of a magnetron sputtering system, and depositing and preparing a tungsten coating on diamond particles by adopting a direct current magnetron sputtering mode, wherein the deposition time is 30min, so that uniform and compact tungsten-plated diamond is obtained, the thickness of the coating is about 300-500 nm, and the morphology of the particles is shown in figure 1.
Step two, mixing powder:
the volume occupied by tungsten powder and tungsten-plated diamond powder is calculated according to the composition of the prepared W-20Cu alloy doped with 40vol.% diamond, the relative density of the pressed green compact is calculated to be the duty ratio of theoretical density, the rest volume is copper, and all raw materials are weighed (the calculation method of the weighing amount is that the volume of each powder is multiplied by the theoretical density). Then adding 2% of induction copper powder, mechanically mixing the induction copper powder with tungsten powder and tungsten-plated diamond powder in a V-shaped powder mixer for more than 6 hours, and taking care that a mixing bottle cap needs to be sealed during mixing.
Preparing a tungsten and tungsten-plated diamond compact:
according to the size of the pressed sample and the specific component requirements, 15g of mixed powder of the materials mixed in the step two is weighed and put into a steel pressing moldCold press forming, the selected press pressure was 180MPa, the relative density of the green body was 68%, and raman analysis was performed on the green body as shown in fig. 2.
And step four, infiltration sintering:
the green body formed by cold pressing in the third step is arranged in a sintering boat, a infiltration copper block (which can be processed by pure copper section materials or can be formed by pure copper powder) to be infiltrated is placed at the upper end of the pressed blank (the volume of gaps in the green body is multiplied by the density of copper, and the balance can be reserved), the periphery of the pressed blank is buried by nano-scale alumina powder, then the pressed blank is placed in a high-temperature atmosphere tube furnace for slow heating (the heating rate is 5-8 ℃/mm), the temperature is raised to 500 ℃ for 0.5h for degreasing, the temperature is raised to 1250 ℃ for 1h for cooling along with the furnace, and the used protective atmosphere is argon gas with the gas flow of 1-2L/h.
Step five, post-treatment:
and (3) performing wire cutting on the diamond-doped tungsten-copper alloy obtained in the step four to remove redundant cladding copper, cutting a sample into a required size by utilizing laser cutting, and polishing the surface by using a grinder with gradually increasing mesh number (100-240 meshes) to obtain a finished product. The metallographic structure and fracture morphology of the sample are obtained as shown in figure 3. The relative density of the finished product is 98.7%, the thermal conductivity is 220W/(mK), and the thermal expansion coefficient is 7.83 multiplied by 10 < -6 >/K.
From the above examples, it can be seen that the thermal conductivity of the doped diamond tungsten copper alloy is between 200 and 230W, with 30vol.% of the diamond tungsten copper alloy having the best thermal conductivity and a thermal conductivity of 226W/(m·k).
Referring to fig. 2, raman scattering spectroscopy analysis was performed on a green body of tungsten-copper doped diamond, and it was found that the diamond peaks were distinct and no impurity peaks were present.
Referring to fig. 3 and 4, which are respectively a metallographic structure photograph and a fracture morphology diagram before and after doping 40vol.% diamond with tungsten-copper alloy, it can be seen that the doped diamond particles are uniformly distributed and the interface bonding is good.
Referring to fig. 5 and 6, it can be seen from the thermal property change that the doped diamond tungsten copper alloy prepared by the invention has obvious improvement on both thermal expansion coefficient and thermal conductivity.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (9)
1. The preparation method of the diamond-doped tungsten-copper alloy is characterized by comprising the following steps of:
step one, diamond tungsten plating:
cleaning high-grade diamond particles, cleaning the diamond particles by using absolute ethyl alcohol and acetone to achieve the purpose of removing surface grease and impurities, and then depositing a uniform tungsten coating on the diamond particles by using magnetron sputtering;
step two, mixing powder:
weighing a certain amount of induced copper powder, tungsten powder and tungsten-plated diamond powder, and uniformly mixing in a powder mixer;
step three, compression molding:
mixing the mixed powder obtained in the step two with a forming agent, and then cold-pressing the mixed powder into a green body in a die;
step four, infiltration sintering:
placing the green compact formed by cold pressing in a sintering boat, placing a infiltration copper block to be infiltrated at the upper end of the compact, burying the periphery by nano-scale alumina powder, then placing the compact in a high-temperature atmosphere tube furnace for heating and heat preservation, and then cooling along with the furnace to obtain a diamond-doped tungsten-copper alloy;
step five, post-treatment:
and (3) performing wire cutting on the diamond-doped tungsten-copper alloy obtained in the step (III) to remove redundant cladding copper, cutting a sample into a required size by utilizing laser cutting, and polishing by a surface grinder with gradually increasing mesh number to obtain a finished product.
2. The method of preparing a doped diamond tungsten copper alloy according to claim 1, wherein in the first step, a direct current magnetron sputtering method is adopted to deposit and prepare a tungsten coating on diamond particles, so as to obtain uniform and compact tungsten-plated diamond, wherein the diameter of a pure tungsten target material with purity of 99.95% isThe thickness was 4mm, and in addition, the model of the magnetron sputtering system was JGP-450A.
3. The method of claim 1, wherein in step 1, the magnetron sputtering deposition time is changed to obtain tungsten coatings with different thicknesses, and the specific deposition time is: 20/30/60min.
4. The method for preparing a doped diamond tungsten copper alloy according to claim 1, wherein the use amounts of the copper powder, tungsten-plated diamond powder and copper infiltration block induced in the second and third steps are as follows: the tungsten powder is mixed with coarse powder and fine powder, the weight percentage of the coarse powder and the fine powder is 75 percent and 25 percent respectively, the induced copper powder accounts for 2 to 3 percent of the total weight of the tungsten powder, the tungsten plating diamond powder accounts for 1 to 3 percent of the total weight of the tungsten powder, and the rest of the green blank gaps are filled into infiltration copper blocks.
5. The method of claim 1, wherein the particle size of the tungsten powder in the second step is 0.1-20 microns, and the particle size of the induced copper powder is 50 microns.
6. The method for preparing a doped diamond tungsten copper alloy according to claim 1, wherein stearic acid (CAS number: 57-11-4, purity: 99.0%) is added in the process of pressing the blank in the second step to a mass ratio of 0.5%, and the die size isThe pressing pressure is 260-600 MPa.
7. The method for preparing a doped diamond tungsten copper alloy according to claim 1, wherein the infiltration copper block in the third step is oxygen-free copper, the heating temperature is 1200-1300 ℃, the heating temperature rising rate is 200-300 ℃/h, and the heat preservation time is 30-60 min.
8. The method according to claim 1, wherein in the third step, argon is used for atmosphere protection, and the gas flow is 1-2L/h.
9. A doped diamond tungsten copper alloy produced by the method of any one of claims 1 to 8.
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