CN116287830B - High-strength tungsten copper alloy and preparation method thereof - Google Patents
High-strength tungsten copper alloy and preparation method thereof Download PDFInfo
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- CN116287830B CN116287830B CN202310338044.4A CN202310338044A CN116287830B CN 116287830 B CN116287830 B CN 116287830B CN 202310338044 A CN202310338044 A CN 202310338044A CN 116287830 B CN116287830 B CN 116287830B
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 159
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 61
- 238000005245 sintering Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000005751 Copper oxide Substances 0.000 claims abstract description 41
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000007747 plating Methods 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 20
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 116
- 239000010937 tungsten Substances 0.000 claims description 115
- 238000003756 stirring Methods 0.000 claims description 59
- 239000011259 mixed solution Substances 0.000 claims description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 39
- 238000007772 electroless plating Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 26
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 238000009423 ventilation Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 13
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 13
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 12
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 12
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 4
- KIMPPGSMONZDMN-UHFFFAOYSA-N sodium;dihydrogen phosphite Chemical compound [Na+].OP(O)[O-] KIMPPGSMONZDMN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 14
- 229910045601 alloy Inorganic materials 0.000 abstract description 13
- 229910052804 chromium Inorganic materials 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 23
- 238000006722 reduction reaction Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000011651 chromium Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- GQLSFFZMZXULSF-UHFFFAOYSA-N copper;oxotungsten Chemical compound [Cu].[W]=O GQLSFFZMZXULSF-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 8
- 235000019799 monosodium phosphate Nutrition 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005474 detonation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- -1 palladium ions Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910001432 tin ion Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 102220469587 Voltage-dependent L-type calcium channel subunit beta-2_D60K_mutation Human genes 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
-
- 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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
- B22F1/17—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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1841—Multistep pretreatment with use of metal first
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
Abstract
The invention provides a high-strength tungsten-copper alloy and a preparation method thereof, which belong to the technical field of tungsten-copper alloy, wherein graphene oxide-tungsten-copper oxide is prepared by a chemical coprecipitation method, then graphene oxide reduction and hydrogen reduction are carried out to prepare the graphene-tungsten-copper alloy, ni-Cr activated graphene-tungsten-copper alloy is prepared by a chemical plating method, then the graphene-tungsten-copper alloy is added into an ethanol solution of aluminum isopropoxide, water is added, and sol-gel reaction is carried out to prepare the high-strength tungsten-copper alloy. The high-strength tungsten-copper alloy prepared by the method has the advantages of high hardness, good mechanical property, high heat resistance, good heat conduction performance and good electric conduction performance, the high-strength tungsten-copper alloy obtained by vacuum pressure sintering has compact structure, few gaps, no influence on structural performance, and the mutual dissolution of the tungsten-copper alloy promoted by the doping of Ni and Cr, so that the obtained alloy has greatly improved performance and wide application prospect.
Description
Technical Field
The invention relates to the technical field of tungsten copper alloy, in particular to a high-strength tungsten copper alloy and a preparation method thereof.
Background
Tungsten copper has very good thermal conductivity, electrical conductivity, arc ablation resistance, high temperature performance, plasticity and processing manufacturability, and is used as a perspiration material, an electric contact material and the like, and the alloy has very similar thermal expansion coefficient with a semiconductor silicon material, so that the alloy is widely used as a heat sink material and a packaging material, and is used as a shell-breaking charge liner material due to high density, high sound velocity and high plasticity.
Tungsten and copper have large differences in melting points and thermal expansion coefficients, and two metal elements are mutually insoluble, and a composite material consisting of W and Cu is a typical pseudoalloy. The tungsten-copper alloy prepared by adopting the powder metallurgy method is easy to expand during sintering, is difficult to sinter and compact, and the highest density is generally only 92-95% of theoretical density. Compared with the common powder metallurgy method, the infiltration method has high relative density (the density reaches more than 98% of theoretical density) of the tungsten-copper composite material and good mechanical property, and becomes one of the main technical methods for preparing the tungsten-copper material. The infiltration method is a method of pressing W powder into briquettes, presintering at a certain temperature to prepare a porous W matrix skeleton with certain density and strength, then melting Cu metal with a lower melting point, and infiltrating into the W skeleton to obtain a denser W-Cu alloy.
The tungsten-copper alloy prepared by the traditional infiltration method has different sintering activities of materials due to different powder particle sizes in the preparation process of a tungsten matrix skeleton, a large number of closed gaps are formed in the skeleton, and in addition, the two phases are insoluble, so that the composition segregation of the tungsten-copper two phases is easily caused in the infiltration process, and a copper enrichment region with a relatively large size exists. When the tungsten-copper alloy is used as a heat sink material and a die casting die material, the thermal stress deformation cracking is caused by the larger difference of thermal expansion coefficients of tungsten and copper. The shaped charge liner is of a warhead type which realizes the aim of penetration and damage by means of high-speed metal jet flow, and the metal jet flow becomes a final bearing unit of explosive energy and a carrier of the damage function. The metal jet is formed by super-dynamic instant overturning of the shaped charge liner material under the action of detonation waves of the explosive. If the liner material is uneven in structure and the deformation behavior of the liner material is inconsistent under the action of detonation waves, collision occurs at different parts in the overturning process of the liner material, penetration kinetic energy of explosive is greatly consumed, the length of jet flow is reduced, and therefore penetration power is reduced.
In addition, in order to solve the problems of poor thermal shock performance and low strength of the material, the material needs to be reinforced, and the fiber composite material reinforcement is a method for effectively improving the material performance, especially the high temperature performance, wherein the C-Cf composite material is a typical representation of the reinforcement at high temperature, and the C-Cf composite material, namely the composite material formed by connecting carbon fibers with carbon, is mainly used for heat insulation refractory materials, medium temperature structural materials, ablation resistant materials, biomedical materials and the like at present, and has excellent performances such as light weight, high strength (the strength is higher than that of steel and the density is lower than that of aluminum), heat insulation, high temperature resistance, impact resistance, high statics performance and the like. The main toughening mechanism is a fiber toughening mechanism.
In the preparation method of the tungsten-copper composite material with the fiber and particle hybrid structure of the Chinese patent CN105039876B, firstly, a blank body containing tungsten fibers is prepared through normal temperature mould pressing, and then a tungsten-based composite material containing a large amount of tungsten fibers is finally prepared through hot pressing sintering.
Disclosure of Invention
The invention aims to provide a high-strength tungsten-copper alloy and a preparation method thereof, which have the advantages of high hardness, good mechanical property, high heat resistance, good heat conduction and good electric conduction, and the high-strength tungsten-copper alloy obtained through vacuum pressure sintering has compact structure, little gaps, no influence on structural performance, and the mutual dissolution of the tungsten-copper alloy promoted by the doping of Ni and Cr, so that the obtained alloy has greatly improved performance and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a high-strength tungsten copper alloy, which comprises the steps of preparing graphene oxide-tungsten copper oxide by a chemical coprecipitation method, preparing the graphene-tungsten copper alloy by reduction of graphene oxide and reduction of hydrogen, preparing the Ni-Cr activated graphene-tungsten copper alloy by a chemical plating method, adding water into an ethanol solution of aluminum isopropoxide, and preparing the high-strength tungsten copper alloy by sol-gel reaction.
As a further improvement of the invention, the method comprises the following steps:
s1, preparing graphene oxide-tungsten copper oxide: adding concentrated nitric acid into copper nitrate to prepare mixed solution A, adding graphene oxide into ammonium tungstate solution, stirring and dissolving to prepare mixed solution B, adding the mixed solution A into the mixed solution B, stirring to perform coprecipitation reaction, filtering, ball-milling and roasting to prepare graphene oxide-tungsten copper oxide;
s2, reduction of graphene oxide: dispersing the graphene oxide-tungsten copper oxide prepared in the step S1 in water, adding ammonia water and hydrazine hydrate, heating for reaction, filtering, washing and drying to obtain the graphene-tungsten copper oxide;
s3, preparing graphene-tungsten copper alloy: reducing the graphene-tungsten copper oxide prepared in the step S2 by low-temperature hydrogen to obtain graphene-tungsten copper alloy;
s4, pretreatment of chemical plating: adding the graphene-tungsten copper alloy prepared in the step S3 into a mixed solution of stannic chloride and hydrochloric acid, stirring and reacting for a first time period, filtering, washing, adding the mixed solution of palladium chloride and hydrochloric acid, stirring and reacting for a second time period, and preparing the pretreated graphene-tungsten copper alloy;
s5, preparing an electroless plating solution: dissolving sodium dihydrogen phosphite, potassium dihydrogen phosphate, nickel sulfate, chromium sulfate and EDTA disodium in water to prepare chemical plating solution;
s6, chemical plating: adding the pretreated graphene-tungsten copper alloy prepared in the step S4 into the chemical plating solution prepared in the step S5, heating, stirring, reacting, filtering, washing and drying to prepare the Ni-Cr activated graphene-tungsten copper alloy;
s7, preparing high-strength tungsten-copper alloy: and (3) adding the Ni-Cr activated graphene-tungsten copper alloy prepared in the step (S6) into an ethanol solution of aluminum isopropoxide, dropwise adding water, stirring for reaction, filtering, washing, roasting under the protection of inert gas, and then performing vacuum pressurizing sintering to obtain the high-strength tungsten copper alloy.
As a further improvement of the invention, the concentration of the concentrated nitric acid in the step S1 is 5.5-6mol/L, the mass ratio of the concentrated nitric acid to the copper nitrate is 1-2:7-10, and the mass ratio of the graphene oxide to the ammonium tungstate is 3-5:17-22, wherein the time of the coprecipitation reaction is 0.5-1h, the roasting temperature is 200-300 ℃, the time is 1-3h, and the time of ball milling is 1-2h.
As a further improvement of the invention, the mass ratio of the graphene oxide-tungsten copper oxide, the ammonia water and the hydrazine hydrate in the step S2 is 100:3-7:1-3, wherein the concentration of the ammonia water is 25-30wt%, the heating temperature is 80-100 ℃, and the reaction time is 1-3h.
As a further improvement of the invention, the low-temperature hydrogen reduction in the step S3 adopts a strong drainage ventilation type tubular furnace to introduce hydrogen at 650-750 ℃ for reduction for 2-4h, and the ventilation amount of the hydrogen is 12-17L/min.
As a further improvement of the invention, the concentration of the tin chloride in the mixed solution of the tin chloride and the hydrochloric acid in the step S4 is 10-15g/L, the concentration of the hydrochloric acid is 0.5-1mol/L, the concentration of the tin chloride in the mixed solution of the palladium chloride and the hydrochloric acid is 0.3-0.5g/L, the concentration of the hydrochloric acid is 0.5-1mol/L, the first time period is 4-5min, and the second time period is 30-40min.
As a further improvement of the present invention, the mass ratio of the sodium dihydrogen phosphite, the potassium dihydrogen phosphate, the nickel sulfate, the chromium sulfate, the disodium EDTA and the water in the step S5 is 40-50:12-15:10-20:15-25:5-10:1000.
as a further improvement of the invention, the mass ratio of the pretreated graphene-tungsten copper alloy to the electroless plating solution in the step S6 is 30-50:1000, the temperature of the heating and stirring reaction is 35-40 ℃, and the time is 10-20min.
As a further improvement of the invention, in the step S7, the mass ratio of the Ni-Cr activated graphene-tungsten copper alloy to the aluminum isopropoxide to the water is 100:15-17:5-10, the stirring reaction time is 0.5-1h, the roasting temperature is 300-500 ℃ and the time is 1-2h, and the vacuum pressure sintering conditions are as follows: the sintering time is 40-60min at room temperature-600 ℃, the pressure is 30-35MPa, the sintering time is 50-70min, the sintering time is 850-1000 ℃ and the sintering time is 70-90min.
The invention further protects the high-strength tungsten copper alloy prepared by the preparation method.
The invention has the following beneficial effects: the tungsten-copper composite material has excellent thermal and electrical properties, higher hardness and low thermal expansion coefficient, and has been well applied to electronic devices and high-temperature resistant devices in recent years. With the further development of the electronics industry, the need for high performance tungsten copper materials is becoming more and more urgent. However, the melting point and physical properties of the two metals are greatly different, the two metals are mutually incompatible, the wettability of the tungsten-copper interface is poor, the tungsten-copper interface is difficult to compact in the sintering process, and the ideal microstructure and performance are difficult to obtain.
The carbon nano material and the ceramic particles have excellent characteristics of high thermal conductivity, high Young modulus, high mechanical strength and the like, and are extremely promising tungsten-copper doped materials, and the strengthening mechanism is mainly characterized by the excellent inherent characteristics of the carbon nano material and the ceramic particles and the fact that the precipitated WC particles inhibit the growth of crystal grains through crystal boundary pinning so as to produce fine grain strengthening on the alloy. However, the current tungsten copper alloy reinforced with carbon nanomaterial and ceramic particles has a difficulty in uniformly dispersing the carbon nanomaterial and ceramic particles in tungsten copper powder by conventional methods. Therefore, in the invention, firstly, graphene oxide is added when the tungsten copper oxide is prepared by a coprecipitation method, and the graphene oxide can be uniformly distributed on the surface of the tungsten copper oxide by forming hydrogen bonds by utilizing the better solubility of the graphene oxide in aqueous solution, so that the graphene oxide-tungsten copper oxide is prepared, and then, the graphene oxide is reduced by utilizing hydrazine hydrate, and the tungsten copper oxide is reduced by hydrogen, so that the graphene-tungsten copper alloy is prepared, and the mechanical property, hardness, heat conduction, electric conduction and the like of the tungsten copper alloy are obviously improved.
Furthermore, the activation doping of the graphene-tungsten copper alloy is realized by adding the trace activating elements, the performance of the tungsten copper alloy is improved, and the uniform and compact tissue structure and the excellent comprehensive performance of the tungsten copper alloy are realized. According to the invention, firstly, graphene-tungsten copper alloy is sensitized and activated, palladium ions and tin ions on the surface undergo a reduction reaction to generate metal Pd which is used as a reaction catalyst for electroless plating, electroless plating of Ni and Cr is promoted, the liquid alumina corrosion resistance of the tungsten copper alloy prepared by using Ni and Cr as activating elements is improved, and the existence of the activating elements can enhance an evaporative cooling mechanism in the corrosion process. Cr element is used as a transition element of tungsten and copper phases, has a key effect on the combination of material interfaces, and Cr atoms at the interfaces can diffuse from one end of the Cu-Cr alloy to one end of the W-Cu alloy to form a solid solution of tungsten and chromium, so that the interface strengthening of tungsten and copper is achieved. Under the synergistic effect of Ni and Cr, the heat conducting property, the electric conducting property and the mechanical strength of the tungsten-copper alloy are further improved, so that the performance of the tungsten-copper alloy is enhanced.
Then, the prepared Ni-Cr activated graphene-tungsten copper alloy is added into an ethanol solution of aluminum isopropoxide, and through dropwise adding of water, sol-gel reaction is carried out, so that aluminum hydroxide is filled in pores of the Ni-Cr activated graphene-tungsten copper alloy, aluminum oxide is generated under the roasting condition, and the graphene/aluminum oxide modified Ni-Cr activated tungsten copper alloy is prepared, so that the mechanical property, hardness, heat resistance and other properties of the tungsten copper alloy are further improved, and the high-strength tungsten copper alloy is prepared.
The high-strength tungsten-copper alloy prepared by the method has the advantages of high hardness, good mechanical property, high heat resistance, good heat conduction performance and good electric conduction performance, the high-strength tungsten-copper alloy obtained by vacuum pressure sintering has compact structure, few gaps, no influence on structural performance, and the mutual dissolution of the tungsten-copper alloy promoted by the doping of Ni and Cr, so that the obtained alloy has greatly improved performance and wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is an SEM image of a graphene-tungsten copper alloy obtained in step S3 of example 1;
fig. 2 is an SEM image of the high strength tungsten copper alloy produced in example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Graphene oxide is commercially available or experimentally obtained by using a modified Hummers method, the method is as follows:
(1) Weighing 10g of natural graphite powder, 4g of potassium persulfate and 10g of phosphorus pentoxide, adding into a three-mouth flask containing 24mL of sulfuric acid under stirring, firstly reacting for 3 hours in a constant-temperature water bath at 60 ℃, then transferring the three-mouth flask into a constant-temperature water bath at 25 ℃ for reacting for 5 hours, carrying out suction filtration, cleaning with clear water to be neutral, and drying to obtain preoxidized graphite;
(2) Weighing lg of preoxidized graphite, adding the preoxidized graphite into a three-neck flask filled with 25mL of sulfuric acid under stirring, placing the three-neck flask into an ice-water bath, adding 3g of potassium permanganate after the preoxidized graphite is completely dissolved, reacting for 2H, then moving the three-neck flask into a constant-temperature water bath at 35 ℃ for reacting for 40min, finally adding deionized water, continuing to react for 1H at 35 ℃, and finally dripping 30wt% of H 2 O 2 So that no more gas is generated, the solution turns bright yellow, is filtered off centrifugally while hot, and is washed to neutrality with 5wt% hydrochloric acid and clear water. The final precipitate was dried at 90℃for 24 hours to give a flaky graphite oxide.
Example 1
The embodiment provides a preparation method of a high-strength tungsten copper alloy, which comprises the following steps:
s1, preparing graphene oxide-tungsten copper oxide: dissolving 1 part by weight of 5.5mol/L concentrated nitric acid and 7 parts by weight of copper nitrate in 100 parts by weight of water to prepare mixed solution A, adding 3 parts by weight of graphene oxide and 17 parts by weight of ammonium tungstate into 100 parts by weight of water, stirring and dissolving to prepare mixed solution B, adding 100 parts by weight of mixed solution A into 170 parts by weight of mixed solution B, stirring and performing coprecipitation reaction for 0.5h, filtering, ball-milling for 1h, and roasting at 200 ℃ for 1h to prepare graphene oxide-tungsten copper oxide;
s2, reduction of graphene oxide: dispersing 100 parts by weight of graphene oxide-tungsten copper oxide prepared in the step S1 in 200 parts by weight of water, adding 3 parts by weight of 25wt% ammonia water and 1 part by weight of hydrazine hydrate, heating to 80 ℃, stirring and reacting for 1h, filtering, washing and drying to obtain graphene-tungsten copper oxide;
s3, preparing graphene-tungsten copper alloy: reducing the graphene-tungsten copper oxide prepared in the step S2 by introducing hydrogen into a strong-drainage breathable tubular furnace at 650 ℃ for 2 hours, wherein the ventilation amount of the hydrogen is 12L/min, and obtaining graphene-tungsten copper alloy; fig. 1 is an SEM image of the prepared graphene-tungsten copper alloy, and the particle size of the graphene-tungsten copper alloy is 700-1500 nm.
S4, pretreatment of chemical plating: adding 10 parts by weight of the graphene-tungsten copper alloy prepared in the step S3 into 100 parts by weight of a mixed solution of 10g/L tin chloride and 0.5mol/L hydrochloric acid, stirring and reacting for 4min, filtering, washing, adding 100 parts by weight of a mixed solution of 0.3g/L palladium chloride and 0.5mol/L hydrochloric acid, stirring and reacting for 30min, and preparing the pretreated graphene-tungsten copper alloy;
s5, preparing an electroless plating solution: dissolving 40 parts by weight of sodium dihydrogen phosphate, 12 parts by weight of potassium dihydrogen phosphate, 10 parts by weight of nickel sulfate, 15 parts by weight of chromium sulfate and 5 parts by weight of EDTA disodium in 1000 parts by weight of water to prepare an electroless plating solution;
s6, chemical plating: adding 30 parts by weight of the pretreated graphene-tungsten copper alloy prepared in the step S4 into 1000 parts by weight of the electroless plating solution prepared in the step S5, heating to 35 ℃, stirring and reacting for 10min, filtering, washing and drying to prepare the Ni-Cr activated graphene-tungsten copper alloy;
s7, preparing high-strength tungsten-copper alloy: adding 100 parts by weight of the Ni-Cr activated graphene-tungsten copper alloy prepared in the step S6 and 15 parts by weight of aluminum isopropoxide into 100 parts by weight of ethanol, dropwise adding 5 parts by weight of water, stirring and reacting for 0.5h, filtering, washing, roasting for 1h at 300 ℃ under the protection of nitrogen, and then carrying out vacuum pressurizing sintering to obtain the high-strength tungsten copper alloy; fig. 2 is an SEM image of the high-strength tungsten-copper alloy, and it is clear that the high-strength tungsten-copper alloy has a compact structure and almost no large gap.
The vacuum pressure sintering conditions are as follows: the sintering time is 40min at room temperature-600 ℃, the pressure is 30MPa, the sintering time is 50min at 600-850 ℃, and the sintering time is 70min at 850-1000 ℃.
Example 2
The embodiment provides a preparation method of a high-strength tungsten copper alloy, which comprises the following steps:
s1, preparing graphene oxide-tungsten copper oxide: dissolving 2 parts by weight of 6mol/L concentrated nitric acid and 10 parts by weight of copper nitrate in 100 parts by weight of water to prepare mixed solution A, adding 5 parts by weight of graphene oxide and 22 parts by weight of ammonium tungstate into 100 parts by weight of water, stirring and dissolving to prepare mixed solution B, adding 100 parts by weight of mixed solution A into 200 parts by weight of mixed solution B, stirring and carrying out coprecipitation reaction for 1h, filtering, ball-milling for 2h, and roasting at 300 ℃ for 3h to prepare graphene oxide-tungsten copper oxide;
s2, reduction of graphene oxide: dispersing 100 parts by weight of graphene oxide-tungsten copper oxide prepared in the step S1 in 200 parts by weight of water, adding 7 parts by weight of 30wt% ammonia water and 3 parts by weight of hydrazine hydrate, heating to 100 ℃, stirring and reacting for 3 hours, filtering, washing and drying to obtain graphene-tungsten copper oxide;
s3, preparing graphene-tungsten copper alloy: introducing hydrogen into the graphene-tungsten copper oxide prepared in the step S2 at 750 ℃ by adopting a strong drainage ventilation type tubular furnace for reduction for 4 hours, wherein the ventilation amount of the hydrogen is 17L/min, so as to obtain graphene-tungsten copper alloy;
s4, pretreatment of chemical plating: adding 10 parts by weight of the graphene-tungsten copper alloy prepared in the step S3 into 100 parts by weight of a mixed solution of 15g/L tin chloride and 1mol/L hydrochloric acid, stirring and reacting for 5min, filtering, washing, adding 100 parts by weight of a mixed solution of 0.5g/L palladium chloride and 1mol/L hydrochloric acid, stirring and reacting for 40min, and preparing the pretreated graphene-tungsten copper alloy;
s5, preparing an electroless plating solution: dissolving 50 parts by weight of sodium dihydrogen phosphate, 15 parts by weight of potassium dihydrogen phosphate, 20 parts by weight of nickel sulfate, 25 parts by weight of chromium sulfate and 10 parts by weight of EDTA disodium in 1000 parts by weight of water to prepare an electroless plating solution;
s6, chemical plating: adding 50 parts by weight of the pretreated graphene-tungsten copper alloy prepared in the step S4 into 1000 parts by weight of the electroless plating solution prepared in the step S5, heating to 40 ℃, stirring and reacting for 20min, filtering, washing and drying to prepare the Ni-Cr activated graphene-tungsten copper alloy;
s7, preparing high-strength tungsten-copper alloy: adding 100 parts by weight of the Ni-Cr activated graphene-tungsten copper alloy prepared in the step S6 and 17 parts by weight of aluminum isopropoxide into 100 parts by weight of ethanol, dropwise adding 10 parts by weight of water, stirring and reacting for 1h, filtering, washing, roasting for 2h at 500 ℃ under the protection of nitrogen, and then carrying out vacuum pressurizing sintering to obtain the high-strength tungsten copper alloy;
the vacuum pressure sintering conditions are as follows: the sintering time is 60min at room temperature-600 ℃, the pressure is 35MPa, the sintering time is 70min at 600-850 ℃, and the sintering time is 90min at 850-1000 ℃.
Example 3
The embodiment provides a preparation method of a high-strength tungsten copper alloy, which comprises the following steps:
s1, preparing graphene oxide-tungsten copper oxide: dissolving 1.5 parts by weight of 5.7mol/L concentrated nitric acid and 8.5 parts by weight of copper nitrate in 100 parts by weight of water to prepare mixed solution A, adding 4 parts by weight of graphene oxide and 20 parts by weight of ammonium tungstate into 100 parts by weight of water, stirring and dissolving to prepare mixed solution B, adding 185 parts by weight of mixed solution A into the mixed solution B, stirring and carrying out coprecipitation reaction for 1h, filtering, ball-milling for 1.5h, and roasting at 250 ℃ for 2h to prepare graphene oxide-tungsten copper oxide;
s2, reduction of graphene oxide: dispersing 100 parts by weight of graphene oxide-tungsten copper oxide prepared in the step S1 in 200 parts by weight of water, adding 5 parts by weight of 27wt% ammonia water and 2 parts by weight of hydrazine hydrate, heating to 90 ℃, stirring and reacting for 2 hours, filtering, washing and drying to obtain graphene-tungsten copper oxide;
s3, preparing graphene-tungsten copper alloy: introducing hydrogen into the graphene-tungsten copper oxide prepared in the step S2 at 700 ℃ for reduction for 3 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 157L/min, and obtaining the graphene-tungsten copper alloy;
s4, pretreatment of chemical plating: adding 10 parts by weight of the graphene-tungsten copper alloy prepared in the step S3 into 100 parts by weight of a mixed solution of 12g/L tin chloride and 0.7mol/L hydrochloric acid, stirring and reacting for 5min, filtering, washing, adding 100 parts by weight of a mixed solution of 0.4g/L palladium chloride and 0.7mol/L hydrochloric acid, stirring and reacting for 35min, and preparing the pretreated graphene-tungsten copper alloy;
s5, preparing an electroless plating solution: 45 parts by weight of sodium dihydrogen phosphate, 13.5 parts by weight of potassium dihydrogen phosphate, 15 parts by weight of nickel sulfate, 20 parts by weight of chromium sulfate and 7 parts by weight of EDTA disodium are dissolved in 1000 parts by weight of water to prepare an electroless plating solution;
s6, chemical plating: adding 40 parts by weight of the pretreated graphene-tungsten copper alloy prepared in the step S4 into 1000 parts by weight of the electroless plating solution prepared in the step S5, heating to 37 ℃, stirring and reacting for 15min, filtering, washing and drying to prepare the Ni-Cr activated graphene-tungsten copper alloy;
s7, preparing high-strength tungsten-copper alloy: adding 100 parts by weight of the Ni-Cr activated graphene-tungsten copper alloy prepared in the step S6 and 16 parts by weight of aluminum isopropoxide into 100 parts by weight of ethanol, dropwise adding 7 parts by weight of water, stirring and reacting for 1h, filtering, washing, roasting for 1.5h at 400 ℃ under the protection of nitrogen, and then carrying out vacuum pressurizing sintering to obtain the high-strength tungsten copper alloy;
the vacuum pressure sintering conditions are as follows: the sintering time is 50min at room temperature-600 ℃, the pressure is 32MPa, the sintering time is 60min at 600-850 ℃, and the sintering time is 80min at 850-1000 ℃.
Comparative example 1
In contrast to example 3, graphene oxide was not added in step S1, and step S2 was not performed.
The method comprises the following steps:
s1, preparing tungsten copper oxide: dissolving 1.5 parts by weight of 5.7mol/L concentrated nitric acid and 8.5 parts by weight of copper nitrate in 100 parts by weight of water to prepare mixed solution A, adding 20 parts by weight of ammonium tungstate into 100 parts by weight of water, stirring and dissolving to prepare mixed solution B, adding 185 parts by weight of mixed solution A into 185 parts by weight of mixed solution B, stirring and carrying out coprecipitation reaction for 1h, filtering, ball-milling for 1.5h, and roasting at 250 ℃ for 2h to prepare tungsten copper oxide;
s2, preparing tungsten-copper alloy: introducing hydrogen into the tungsten copper oxide prepared in the step S1 by adopting a strong drainage ventilation type tubular furnace at 700 ℃ for reduction for 3 hours, wherein the ventilation amount of the hydrogen is 157L/min, and obtaining tungsten copper alloy;
s3, pretreatment of chemical plating: adding 10 parts by weight of the tungsten-copper alloy prepared in the step S2 into 100 parts by weight of a mixed solution of 12g/L tin chloride and 0.7mol/L hydrochloric acid, stirring and reacting for 5min, filtering, washing, adding 100 parts by weight of a mixed solution of 0.4g/L palladium chloride and 0.7mol/L hydrochloric acid, stirring and reacting for 35min, and preparing the pretreated tungsten-copper alloy;
s4, preparing an electroless plating solution: 45 parts by weight of sodium dihydrogen phosphate, 13.5 parts by weight of potassium dihydrogen phosphate, 15 parts by weight of nickel sulfate, 20 parts by weight of chromium sulfate and 7 parts by weight of EDTA disodium are dissolved in 1000 parts by weight of water to prepare an electroless plating solution;
s5, chemical plating: adding 40 parts by weight of the pretreated tungsten-copper alloy prepared in the step S3 into 1000 parts by weight of the electroless plating solution prepared in the step S5, heating to 37 ℃, stirring and reacting for 15min, filtering, washing and drying to prepare the Ni-Cr activated tungsten-copper alloy;
s6, preparing high-strength tungsten-copper alloy: adding 100 parts by weight of the Ni-Cr activated tungsten copper alloy prepared in the step S5 and 16 parts by weight of aluminum isopropoxide into 100 parts by weight of ethanol, dropwise adding 7 parts by weight of water, stirring and reacting for 1h, filtering, washing, roasting for 1.5h at 400 ℃ under the protection of nitrogen, and then carrying out vacuum pressurizing sintering to obtain the high-strength tungsten copper alloy;
the vacuum pressure sintering conditions are as follows: the sintering time is 50min at room temperature-600 ℃, the pressure is 32MPa, the sintering time is 60min at 600-850 ℃, and the sintering time is 80min at 850-1000 ℃.
Comparative example 2
In comparison with example 3, the difference is that step S4 is not performed.
The method comprises the following steps:
s1, preparing graphene oxide-tungsten copper oxide: dissolving 1.5 parts by weight of 5.7mol/L concentrated nitric acid and 8.5 parts by weight of copper nitrate in 100 parts by weight of water to prepare mixed solution A, adding 4 parts by weight of graphene oxide and 20 parts by weight of ammonium tungstate into 100 parts by weight of water, stirring and dissolving to prepare mixed solution B, adding 185 parts by weight of mixed solution A into the mixed solution B, stirring and carrying out coprecipitation reaction for 1h, filtering, ball-milling for 1.5h, and roasting at 250 ℃ for 2h to prepare graphene oxide-tungsten copper oxide;
s2, reduction of graphene oxide: dispersing 100 parts by weight of graphene oxide-tungsten copper oxide prepared in the step S1 in 200 parts by weight of water, adding 5 parts by weight of 27wt% ammonia water and 2 parts by weight of hydrazine hydrate, heating to 90 ℃, stirring and reacting for 2 hours, filtering, washing and drying to obtain graphene-tungsten copper oxide;
s3, preparing graphene-tungsten copper alloy: introducing hydrogen into the graphene-tungsten copper oxide prepared in the step S2 at 700 ℃ for reduction for 3 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 157L/min, and obtaining the graphene-tungsten copper alloy;
s4, preparing an electroless plating solution: 45 parts by weight of sodium dihydrogen phosphate, 13.5 parts by weight of potassium dihydrogen phosphate, 15 parts by weight of nickel sulfate, 20 parts by weight of chromium sulfate and 7 parts by weight of EDTA disodium are dissolved in 1000 parts by weight of water to prepare an electroless plating solution;
s5, chemical plating: adding 40 parts by weight of the graphene-tungsten copper alloy prepared in the step S3 into 1000 parts by weight of the electroless plating solution prepared in the step S5, heating to 37 ℃, stirring and reacting for 15min, filtering, washing and drying to prepare the Ni-Cr activated graphene-tungsten copper alloy;
s6, preparing high-strength tungsten-copper alloy: adding 100 parts by weight of the Ni-Cr activated graphene-tungsten copper alloy prepared in the step S5 and 16 parts by weight of aluminum isopropoxide into 100 parts by weight of ethanol, dropwise adding 7 parts by weight of water, stirring and reacting for 1h, filtering, washing, roasting for 1.5h at 400 ℃ under the protection of nitrogen, and then carrying out vacuum pressurizing sintering to obtain the high-strength tungsten copper alloy;
the vacuum pressure sintering conditions are as follows: the sintering time is 50min at room temperature-600 ℃, the pressure is 32MPa, the sintering time is 60min at 600-850 ℃, and the sintering time is 80min at 850-1000 ℃.
Comparative example 3
The difference from example 3 is that nickel sulfate is not added in step S5.
The method comprises the following steps:
s5, preparing an electroless plating solution: 45 parts by weight of sodium dihydrogen phosphate, 13.5 parts by weight of potassium dihydrogen phosphate, 35 parts by weight of chromium sulfate, and 7 parts by weight of disodium EDTA were dissolved in 1000 parts by weight of water to prepare an electroless plating solution.
Comparative example 4
In comparison with example 3, the difference is that chromium sulfate was not added in step S5.
The method comprises the following steps:
s5, preparing an electroless plating solution: 45 parts by weight of sodium dihydrogen phosphate, 13.5 parts by weight of potassium dihydrogen phosphate, 35 parts by weight of nickel sulfate, and 7 parts by weight of disodium EDTA were dissolved in 1000 parts by weight of water to prepare an electroless plating solution.
Comparative example 5
In comparison with example 3, the difference is that steps S4-S6 are not performed.
The method comprises the following steps:
s1, preparing graphene oxide-tungsten copper oxide: dissolving 1.5 parts by weight of 5.7mol/L concentrated nitric acid and 8.5 parts by weight of copper nitrate in 100 parts by weight of water to prepare mixed solution A, adding 4 parts by weight of graphene oxide and 20 parts by weight of ammonium tungstate into 100 parts by weight of water, stirring and dissolving to prepare mixed solution B, adding 185 parts by weight of mixed solution A into the mixed solution B, stirring and carrying out coprecipitation reaction for 1h, filtering, ball-milling for 1.5h, and roasting at 250 ℃ for 2h to prepare graphene oxide-tungsten copper oxide;
s2, reduction of graphene oxide: dispersing 100 parts by weight of graphene oxide-tungsten copper oxide prepared in the step S1 in 200 parts by weight of water, adding 5 parts by weight of 27wt% ammonia water and 2 parts by weight of hydrazine hydrate, heating to 90 ℃, stirring and reacting for 2 hours, filtering, washing and drying to obtain graphene-tungsten copper oxide;
s3, preparing graphene-tungsten copper alloy: introducing hydrogen into the graphene-tungsten copper oxide prepared in the step S2 at 700 ℃ for reduction for 3 hours by adopting a strong drainage ventilation type tubular furnace, wherein the ventilation amount of the hydrogen is 157L/min, and obtaining the graphene-tungsten copper alloy;
s5, preparing high-strength tungsten-copper alloy: adding 100 parts by weight of the graphene-tungsten copper alloy prepared in the step S3 and 16 parts by weight of aluminum isopropoxide into 100 parts by weight of ethanol, dropwise adding 7 parts by weight of water, stirring and reacting for 1h, filtering, washing, roasting for 1.5h at 400 ℃ under the protection of nitrogen, and then carrying out vacuum pressurizing sintering to obtain the high-strength tungsten copper alloy;
the vacuum pressure sintering conditions are as follows: the sintering time is 50min at room temperature-600 ℃, the pressure is 32MPa, the sintering time is 60min at 600-850 ℃, and the sintering time is 80min at 850-1000 ℃.
Comparative example 6
The difference compared to example 3 is that step S7 is not performed with the addition of aluminum isopropoxide.
The method comprises the following steps:
s7, preparing high-strength tungsten-copper alloy: carrying out vacuum pressurizing sintering on 100 parts by weight of the Ni-Cr activated graphene-tungsten copper alloy prepared in the step S6 to obtain a high-strength tungsten copper alloy;
the vacuum pressure sintering conditions are as follows: the sintering time is 50min at room temperature-600 ℃, the pressure is 32MPa, the sintering time is 60min at 600-850 ℃, and the sintering time is 80min at 850-1000 ℃.
Comparative example 7
In comparison with example 3, the difference is that graphene oxide is not added in step S1, step S2 is not performed, and at the same time, aluminum isopropoxide is not added in step S7.
The method comprises the following steps:
s1, preparing tungsten copper oxide: dissolving 1.5 parts by weight of 5.7mol/L concentrated nitric acid and 8.5 parts by weight of copper nitrate in 100 parts by weight of water to prepare mixed solution A, adding 20 parts by weight of ammonium tungstate into 100 parts by weight of water, stirring and dissolving to prepare mixed solution B, adding 185 parts by weight of mixed solution A into 185 parts by weight of mixed solution B, stirring and carrying out coprecipitation reaction for 1h, filtering, ball-milling for 1.5h, and roasting at 250 ℃ for 2h to prepare tungsten copper oxide;
s2, preparing tungsten-copper alloy: introducing hydrogen into the tungsten copper oxide prepared in the step S1 by adopting a strong drainage ventilation type tubular furnace at 700 ℃ for reduction for 3 hours, wherein the ventilation amount of the hydrogen is 157L/min, and obtaining tungsten copper alloy;
s3, pretreatment of chemical plating: adding 10 parts by weight of the tungsten-copper alloy prepared in the step S2 into 100 parts by weight of a mixed solution of 12g/L tin chloride and 0.7mol/L hydrochloric acid, stirring and reacting for 5min, filtering, washing, adding 100 parts by weight of a mixed solution of 0.4g/L palladium chloride and 0.7mol/L hydrochloric acid, stirring and reacting for 35min, and preparing the pretreated tungsten-copper alloy;
s4, preparing an electroless plating solution: 45 parts by weight of sodium dihydrogen phosphate, 13.5 parts by weight of potassium dihydrogen phosphate, 15 parts by weight of nickel sulfate, 20 parts by weight of chromium sulfate and 7 parts by weight of EDTA disodium are dissolved in 1000 parts by weight of water to prepare an electroless plating solution;
s5, chemical plating: adding 40 parts by weight of the pretreated tungsten-copper alloy prepared in the step S3 into 1000 parts by weight of the electroless plating solution prepared in the step S5, heating to 37 ℃, stirring and reacting for 15min, filtering, washing and drying to prepare the Ni-Cr activated tungsten-copper alloy;
s6, preparing high-strength tungsten-copper alloy: performing vacuum pressurizing sintering on 100 parts by weight of the Ni-Cr activated tungsten copper alloy prepared in the step S6 to obtain a high-strength tungsten copper alloy;
the vacuum pressure sintering conditions are as follows: the sintering time is 50min at room temperature-600 ℃, the pressure is 32MPa, the sintering time is 60min at 600-850 ℃, and the sintering time is 80min at 850-1000 ℃.
Test example 1
The high strength tungsten copper alloy samples prepared in examples 1 to 3 and comparative examples 1 to 7 were tested for porosity using an AutoPore IV 9510 type mercury porosimeter, and the density of the samples was measured by the Archimedes drainage method. The results are shown in Table 1.
TABLE 1
As can be seen from the above table, the high-strength tungsten-copper alloy prepared in the embodiments 1-3 of the present invention has smaller porosity and higher relative density, so that it can be inferred that the prepared high-strength tungsten-copper alloy has high density and almost no larger hole defect, so that the prepared alloy material has higher comprehensive performance.
Test example 2
The high strength tungsten copper alloy samples prepared in examples 1-3 and comparative examples 1-7 were subjected to performance test, and the results are shown in Table 2.
The conductivity of the alloy samples was measured at room temperature using a D60K digital metal conductivity meter.
The hardness of the alloy sample was measured by using a HB-3000 type Brinell hardness tester under conditions of a ram diameter of 5mm, a test load of 750kg, and a dwell time of 30 s.
The thermal conductivity of the alloy specimens was measured with a TCT416 type thermal conductivity meter, and the dimensions of the alloy specimens used were Φ10mm×3mm.
The tensile strength of the alloy sample was measured by AG-100KN material high temperature performance tester at a tensile rate of 1mm/min at room temperature.
TABLE 2
As can be seen from the above table, the high-strength tungsten-copper alloy prepared in the embodiments 1-3 has stronger hardness, better mechanical property and better heat conduction property and electric conduction property.
Test example 3
The high-strength tungsten copper alloy samples prepared in examples 1-3 and comparative examples 1-7 were subjected to high temperature resistance test, and the results are shown in Table 3.
High-temperature tensile test is carried out on an Instron3369 electronic tensile testing machine, nitrogen is adopted as protective atmosphere, the heating rate is 10 ℃/min, the test temperature is 200-800 ℃, the heat preservation time is 20min, and the tensile rate is 1mm/min.
TABLE 3 Table 3
As shown in the table above, the high-strength tungsten-copper alloy prepared in the embodiments 1-3 has better high-temperature resistance and good mechanical property at high temperature.
Comparative example 1 is different from example 3 in that graphene oxide is not added in step S1, and step S2 is not performed. The hardness, mechanical property, thermal conductivity and electrical conductivity are obviously reduced. Comparative example 6 differs from example 3 in that the addition of aluminum isopropoxide is not performed in step S7. The hardness and high temperature resistant mechanical properties are obviously reduced, the relative density is reduced, and the porosity is increased. Comparative example 7 is different from example 3 in that graphene oxide was not added in step S1, step S2 was not performed, and at the same time, aluminum isopropoxide was not added in step S7. The hardness, mechanical property, high temperature resistance mechanical property, thermal conductivity and electric conductivity are obviously reduced, the relative density is reduced, and the porosity is increased. According to the preparation method, firstly, graphene oxide is added when the tungsten copper oxide is prepared by a coprecipitation method, and the graphene oxide can be uniformly distributed on the surface of the tungsten copper oxide by utilizing good solubility of the graphene oxide in an aqueous solution and forming hydrogen bonds, so that the graphene oxide-tungsten copper oxide is prepared, and then, the graphene oxide is reduced by utilizing hydrazine hydrate, and the tungsten copper oxide is reduced by utilizing hydrogen, so that the graphene-tungsten copper alloy is prepared, and the mechanical property, hardness, heat conduction, electric conduction and the like of the tungsten copper alloy are obviously improved. According to the invention, the prepared Ni-Cr activated graphene-tungsten copper alloy is added into an ethanol solution of aluminum isopropoxide, and through dropwise adding of water, sol-gel reaction is carried out, so that aluminum hydroxide is filled in pores of the Ni-Cr activated graphene-tungsten copper alloy, aluminum oxide is generated under the condition of roasting, and the graphene/aluminum oxide modified Ni-Cr activated tungsten copper alloy is prepared, so that the mechanical property, hardness, heat resistance and other properties of the tungsten copper alloy are further improved, and the high-strength tungsten copper alloy is prepared. The presence of graphene and alumina has a synergistic effect.
Comparative example 2 is different from example 3 in that step S4 is not performed. The heat-conducting property, the electric conductivity, the hardness and the mechanical strength are reduced, the relative density is reduced, and the porosity is increased. According to the invention, firstly, graphene-tungsten copper alloy is subjected to a sensitization and activation method, palladium ions and tin ions on the surface undergo a reduction reaction to generate metal Pd which is used as a reaction catalyst for electroless plating, and electroless plating of Ni and Cr is promoted.
Comparative examples 3 and 4 are different from example 3 in that nickel sulfate or chromium sulfate is not added in step S5. Comparative example 5 differs from example 3 in that steps S4 to S6 are not performed. The heat-conducting property, the electric conductivity, the hardness and the mechanical strength are obviously reduced, the relative density is reduced, and the porosity is increased. The activation modification of Ni and Cr has synergistic effect. According to the invention, the activation doping of the graphene-tungsten copper alloy is realized by adding trace activating elements, so that the performance of the tungsten copper alloy is improved, and the uniform and compact tissue structure and the excellent comprehensive performance of the tungsten copper alloy are realized. The tungsten-copper alloy prepared by adopting Ni and Cr as activating elements has improved liquid alumina corrosion resistance, and the existence of the activating elements can enhance an evaporative cooling mechanism in the corrosion process. Cr element is used as a transition element of tungsten and copper phases, has a key effect on the combination of material interfaces, and Cr atoms at the interfaces can diffuse from one end of the Cu-Cr alloy to one end of the W-Cu alloy to form a solid solution of tungsten and chromium, so that the interface strengthening of tungsten and copper is achieved. Under the synergistic effect of Ni and Cr, the heat conducting property, the electric conducting property and the mechanical strength of the tungsten-copper alloy are further improved, so that the performance of the tungsten-copper alloy is enhanced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. The preparation method of the high-strength tungsten-copper alloy is characterized by comprising the following steps of:
s1, preparing graphene oxide-tungsten copper oxide: adding concentrated nitric acid into copper nitrate to prepare mixed solution A, adding graphene oxide into ammonium tungstate solution, stirring and dissolving to prepare mixed solution B, adding the mixed solution A into the mixed solution B, stirring to perform coprecipitation reaction, filtering, ball-milling and roasting to prepare graphene oxide-tungsten copper oxide;
s2, reduction of graphene oxide: dispersing the graphene oxide-tungsten copper oxide prepared in the step S1 in water, adding ammonia water and hydrazine hydrate, heating for reaction, filtering, washing and drying to obtain the graphene-tungsten copper oxide;
s3, preparing graphene-tungsten copper alloy: reducing the graphene-tungsten copper oxide prepared in the step S2 by low-temperature hydrogen to obtain graphene-tungsten copper alloy;
s4, pretreatment of chemical plating: adding the graphene-tungsten copper alloy prepared in the step S3 into a mixed solution of stannic chloride and hydrochloric acid, stirring and reacting for a first time period, filtering, washing, adding the mixed solution of palladium chloride and hydrochloric acid, stirring and reacting for a second time period, and preparing the pretreated graphene-tungsten copper alloy;
s5, preparing an electroless plating solution: dissolving sodium dihydrogen phosphite, potassium dihydrogen phosphate, nickel sulfate, chromium sulfate and EDTA disodium in water to prepare chemical plating solution; the mass ratio of the sodium dihydrogen phosphite to the potassium dihydrogen phosphate to the nickel sulfate to the chromium sulfate to the EDTA disodium to the water is 40-50:12-15:10-20:15-25:5-10:1000;
s6, chemical plating: adding the pretreated graphene-tungsten copper alloy prepared in the step S4 into the chemical plating solution prepared in the step S5, heating, stirring, reacting, filtering, washing and drying to prepare the Ni-Cr activated graphene-tungsten copper alloy;
s7, preparing high-strength tungsten-copper alloy: and (3) adding the Ni-Cr activated graphene-tungsten copper alloy prepared in the step (S6) into an ethanol solution of aluminum isopropoxide, dropwise adding water, stirring for reaction, filtering, washing, roasting under the protection of inert gas, and then performing vacuum pressurizing sintering to obtain the high-strength tungsten copper alloy.
2. The preparation method according to claim 1, wherein in the step S1, the concentration of the concentrated nitric acid is 5.5-6mol/L, the mass ratio of the concentrated nitric acid to the copper nitrate is 1-2:7-10, and the mass ratio of the graphene oxide to the ammonium tungstate is 3-5:17-22, wherein the time of the coprecipitation reaction is 0.5-1h, the roasting temperature is 200-300 ℃, the time is 1-3h, and the time of ball milling is 1-2h.
3. The preparation method according to claim 1, wherein the mass ratio of the graphene oxide-tungsten copper oxide, the ammonia water and the hydrazine hydrate in the step S2 is 100:3-7:1-3, wherein the concentration of the ammonia water is 25-30wt%, the heating temperature is 80-100 ℃, and the reaction time is 1-3h.
4. The preparation method according to claim 1, wherein the low-temperature hydrogen reduction in step S3 is performed by introducing hydrogen at 650-750 ℃ for 2-4 hours using a strongly-draining and breathable tubular furnace, and the hydrogen ventilation is 12-17L/min.
5. The preparation method according to claim 1, wherein the concentration of tin chloride in the mixed solution of tin chloride and hydrochloric acid in step S4 is 10-15g/L, the concentration of hydrochloric acid is 0.5-1mol/L, the concentration of palladium chloride in the mixed solution of palladium chloride and hydrochloric acid is 0.3-0.5g/L, the concentration of hydrochloric acid is 0.5-1mol/L, the first time period is 4-5min, and the second time period is 30-40min.
6. The preparation method according to claim 1, wherein the mass ratio of the pretreated graphene-tungsten copper alloy to the electroless plating solution in the step S6 is 30-50:1000, the temperature of the heating and stirring reaction is 35-40 ℃, and the time is 10-20min.
7. The preparation method according to claim 1, wherein in the step S7, the mass ratio of the Ni-Cr activated graphene-tungsten copper alloy, aluminum isopropoxide and water is 100:15-17:5-10, the stirring reaction time is 0.5-1h, the roasting temperature is 300-500 ℃ and the time is 1-2h, and the vacuum pressure sintering conditions are as follows: the sintering time is 40-60min at room temperature-600 ℃, the pressure is 30-35MPa, the sintering time is 50-70min, the sintering time is 850-1000 ℃ and the sintering time is 70-90min.
8. A high strength tungsten copper alloy made by the method of any one of claims 1-7.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101078068A (en) * | 2007-07-05 | 2007-11-28 | 北京科技大学 | Method for preparing ultra-fine crystal grain tungsten-copper alloy and tungsten-copper alloy |
| WO2016011987A1 (en) * | 2014-07-21 | 2016-01-28 | 中国科学院深圳先进技术研究院 | Graphene thin film and preparation method therefor |
| CN105603231A (en) * | 2015-12-07 | 2016-05-25 | 宁波墨西科技有限公司 | Graphene-modified copper alloy nano-material and preparation method thereof |
| CN106498209A (en) * | 2016-10-28 | 2017-03-15 | 西安理工大学 | A kind of preparation method of doped graphene tungsten-copper alloy |
| CN108893637A (en) * | 2018-07-02 | 2018-11-27 | 西安交通大学 | A kind of preparation method of copper-tungsten doped graphene |
| CN108950279A (en) * | 2018-07-27 | 2018-12-07 | 西北有色金属研究院 | A method of collaboration improves CuW contact material arc erosion performance |
| CN110172632A (en) * | 2019-03-20 | 2019-08-27 | 河南科技大学 | A kind of graphene oxide enhancing dispersion copper tungsten chromium electrical contact material and preparation method thereof |
| CN111979438A (en) * | 2020-08-25 | 2020-11-24 | 西北有色金属研究院 | Method for improving interface bonding strength of graphene copper-based composite material |
| CN112981159A (en) * | 2021-02-09 | 2021-06-18 | 中国科学院电工研究所 | Preparation method of graphene reinforced copper-based composite material |
| CN113020588A (en) * | 2021-02-26 | 2021-06-25 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene oxide doped tungsten-copper core-shell structure material |
| WO2022068812A1 (en) * | 2020-09-30 | 2022-04-07 | 全球能源互联网研究院有限公司 | Copper-tungsten alloy material, preparation method therefor, and application thereof |
| CN115673319A (en) * | 2022-09-06 | 2023-02-03 | 佛山华智新材料有限公司 | Composite material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011159922A2 (en) * | 2010-06-16 | 2011-12-22 | The Research Foundation Of State University Of New York | Graphene films and methods of making thereof |
| JP6793503B2 (en) * | 2016-09-01 | 2020-12-02 | 東京エレクトロン株式会社 | How to generate graphene |
| US11603594B2 (en) * | 2016-10-21 | 2023-03-14 | Nanjing Daimonte Technology Co., Ltd. | Boron doped diamond electrode and preparation method and applications thereof |
-
2023
- 2023-03-31 CN CN202310338044.4A patent/CN116287830B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101078068A (en) * | 2007-07-05 | 2007-11-28 | 北京科技大学 | Method for preparing ultra-fine crystal grain tungsten-copper alloy and tungsten-copper alloy |
| WO2016011987A1 (en) * | 2014-07-21 | 2016-01-28 | 中国科学院深圳先进技术研究院 | Graphene thin film and preparation method therefor |
| CN105603231A (en) * | 2015-12-07 | 2016-05-25 | 宁波墨西科技有限公司 | Graphene-modified copper alloy nano-material and preparation method thereof |
| CN106498209A (en) * | 2016-10-28 | 2017-03-15 | 西安理工大学 | A kind of preparation method of doped graphene tungsten-copper alloy |
| CN108893637A (en) * | 2018-07-02 | 2018-11-27 | 西安交通大学 | A kind of preparation method of copper-tungsten doped graphene |
| CN108950279A (en) * | 2018-07-27 | 2018-12-07 | 西北有色金属研究院 | A method of collaboration improves CuW contact material arc erosion performance |
| CN110172632A (en) * | 2019-03-20 | 2019-08-27 | 河南科技大学 | A kind of graphene oxide enhancing dispersion copper tungsten chromium electrical contact material and preparation method thereof |
| CN111979438A (en) * | 2020-08-25 | 2020-11-24 | 西北有色金属研究院 | Method for improving interface bonding strength of graphene copper-based composite material |
| WO2022068812A1 (en) * | 2020-09-30 | 2022-04-07 | 全球能源互联网研究院有限公司 | Copper-tungsten alloy material, preparation method therefor, and application thereof |
| CN112981159A (en) * | 2021-02-09 | 2021-06-18 | 中国科学院电工研究所 | Preparation method of graphene reinforced copper-based composite material |
| CN113020588A (en) * | 2021-02-26 | 2021-06-25 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene oxide doped tungsten-copper core-shell structure material |
| CN115673319A (en) * | 2022-09-06 | 2023-02-03 | 佛山华智新材料有限公司 | Composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 钨铜合金制备与应用研究;《中国钨业》;第36卷(第05期);第65-77页 * |
| 钨铜合金材料的研究进展及应用;钟远辉;《冶金与材料》;第43卷(第01期);第151-153页 * |
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