CN114131036A - Low-cost preparation method of functionalized micro-nano particle reinforcement - Google Patents
Low-cost preparation method of functionalized micro-nano particle reinforcement Download PDFInfo
- Publication number
- CN114131036A CN114131036A CN202111465734.3A CN202111465734A CN114131036A CN 114131036 A CN114131036 A CN 114131036A CN 202111465734 A CN202111465734 A CN 202111465734A CN 114131036 A CN114131036 A CN 114131036A
- Authority
- CN
- China
- Prior art keywords
- micro
- nano particle
- copper
- particle reinforcement
- reinforcement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000002787 reinforcement Effects 0.000 title claims abstract description 71
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 29
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 28
- 229910001431 copper ion Inorganic materials 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 150000001879 copper Chemical class 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 15
- 239000003381 stabilizer Substances 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 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 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 7
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 7
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 6
- 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 claims description 6
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 claims description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- -1 2' -bipyridine Chemical compound 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 238000001994 activation Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000007747 plating Methods 0.000 abstract description 4
- 206010070834 Sensitisation Diseases 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 3
- 230000008313 sensitization Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Images
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
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- C22C1/10—Alloys containing non-metals
- C22C1/1005—Pretreatment of the non-metallic additives
- C22C1/101—Pretreatment of the non-metallic additives by coating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
- C22C32/0057—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides based on B4C
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
- C22C32/0063—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides based on SiC
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a low-cost preparation method of a functionalized micro-nano particle reinforcement, which is characterized in that the micro-nano particle reinforcement is subjected to ball milling, then in-situ deposition reaction is carried out in a prepared solution, and the reinforcement with the functional copper coating thickness of about 10-200 nm is obtained after filtration, washing, drying and grinding. The method of the invention replaces the chemical coarsening, sensitization and activation processes of the surface of the reinforcing body in the traditional chemical plating process with ball milling, avoids the use of reagents which have high price and pollute the environment, has simple coating process and low cost, and can control the thickness of the copper coating and the like through the design of the proportion of the reaction solution and the reaction conditions. After the method disclosed by the invention is adopted to coat the copper on the micro-nano reinforcement, the dispersibility and the bonding property with a matrix can be improved, the aluminum matrix composite material has the characteristics of high strength and high conductivity, and the development and application of an electric conductor of the aluminum matrix composite material are promoted.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a low-cost preparation method of a functionalized micro-nano particle reinforcement.
Background
The aluminum-based composite material integrates the advantages of low aluminum alloy density, good heat and electric conductivity, high strength modulus of the reinforcement, low coefficient of thermal expansion, wear resistance and the like, and is applied to aerospace vehicle bearing members, automobile parts, precision instruments, electronic device packaging and the like. However, the aluminum alloy has the problem that the strength and the conductivity are improved and restricted, the micro-nano particle reinforcement has poor wettability and high dispersion difficulty with aluminum melt, and the high-temperature interface reaction also causes brittle phase generation, so that the strengthening and toughening effects and the conductivity of the aluminum-based composite material are limited, and the aluminum-based composite material is not beneficial to saving copper by aluminum in the wire and cable industry.
The micro-nano reinforcement surface is coated with a copper layer which is physically and chemically compatible with the aluminum matrix, so that the effective way of improving the wettability, improving the interface bonding property and controlling the interface reaction is provided. For example, patent documents with publication numbers CN106756177A, CN104593752A, CN103805976A, CN106544653A, CN107460458B and CN104451227A, the technical characteristics of the documents are that TiC and B are treated by reaction4C. The micron-sized particles such as SiC and the like, the carbon nano-tubes and the graphene are chemically plated with copper layers on the surfaces, so that the problems of difficult dispersion, poor wettability, low interface bonding strength, interface reaction and the like of the particles in a metal matrix are solved. For another example, patent document No. CN111471943A discloses a high electric and thermal conductivity aluminum-based composite material and a preparation method thereof, which is characterized in that a copper layer is chemically plated on the surface of a SiC particle reinforcement body, thereby improving the electric and thermal conductivity of the aluminum-based composite material.
The references 1 "Effect of coated SiC requirements on micro-structure, mechanical properties and wear of aluminum compositions [ Materials Science and Engineering A,2017,225:012265 ]", 2 "Engineering of structural and manufacturing by interfacial nano-depth-characterization in Carbon nano-depth/aluminum matrix compositions [ Carbon,2020,159: 201" 212] ", and 3" synthetic Engineering and manufacturing of coating of co-coated graphene nano-structures and structural nano-depth composites [ Materials & Engineering Science A, 141661] respectively show that the surface chemical coating of Cu nano-particles can be effectively enhanced by the surface chemical coating method, and that the surface chemical coating of Cu nano-particles can be effectively enhanced by the surface chemical coating method and surface chemical coating method.
In the above-mentioned published documents, the wettability and the interface bonding property with the aluminum matrix of the micro-nano particle reinforcement surface coated with copper are significantly improved, but the modification aims to singly improve the strength or the electric and heat conductivity of the aluminum matrix composite material, and the adverse effect of the reinforcement and the interface on the electric conductivity of the aluminum matrix composite material is not counteracted by designing the thickness of the functional copper coating, so as to achieve the purpose of synergistically improving the mechanical property and the electric conductivity of the aluminum matrix composite material. In addition, in the above-mentioned published documents, the surface of the particle reinforcement needs to be subjected to chemical roughening, sensitizing, activating and other steps before electroless copper plating, and the like, and the above-mentioned processes involve the use of high-cost and environmentally-polluting chemical reagents such as hydrochloric acid, nitric acid, stannous chloride, palladium chloride and the like, and the complicated process also increases the difficulty in controlling the copper coating.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a low-cost preparation method of a functionalized micro-nano particle reinforcement, which utilizes the mechanical force of ball milling to improve the surface activity of the micro-nano reinforcement, improve the interphase reaction capability and the effect of plating a functional copper layer on the surface, omit the processes of chemical coarsening, sensitization and activation, and avoid the use of reagents with high cost and environmental pollution. The functional copper layer inhibits the interface reaction of the reinforcement and the aluminum melt, improves the interface bonding force, can coordinate the mechanics and the conductivity of the aluminum-based composite material by adjusting the thickness of the functional copper layer, and meets the requirement of the high-strength high-conductivity aluminum-based composite material on the functional copper coating micro-nano reinforcement.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a low-cost preparation method of a functionalized micro-nano particle reinforcement comprises the following steps:
1) weighing the micro-nano particle reinforcement and the ceramic balls, and performing ball milling treatment to obtain the treated micro-nano particle reinforcement;
2) preparing a soluble copper salt and a complexing agent into an aqueous solution, mixing and stirring the soluble copper salt and the complexing agent for 20-60 min, dripping a NaOH solution to adjust the pH value of the solution to 9-12.5, and continuously stirring until a precipitate-free solution A is obtained;
3) weighing a stabilizer, dissolving the stabilizer in distilled water, pouring the stabilizer into the solution A prepared in the step 2), and uniformly stirring to obtain a reaction solution B, wherein the concentration of the stabilizer is 5-15 mg/L;
4) placing the reaction solution B in a constant-temperature water bath kettle at 50-75 ℃, and adding the micro-nano particle reinforcement treated in the step 1) under a continuous stirring state to obtain a suspension C with a particle loading of 1-10 g/L;
5) weighing a reducing agent and adding the reducing agent into the suspension C, reducing copper ions of copper salt and depositing the copper ions on the surfaces of the micro-nano particles to form a functional copper coating, reacting for 30-50 min, and simultaneously dropping NaOH solution to keep the pH value of a reaction system at 9-12.5 to obtain a suspension D;
6) standing the suspension D obtained in the step 5) for 30-60 minutes, filtering, washing with distilled water to be neutral, drying, and grinding to obtain the functional micro-nano particle reinforcement with the functional copper coating thickness of 10-200 nm.
Further, in the step 1), the micro-nano particle reinforcement and the ceramic balls are weighed and dried at the temperature of 60-90 ℃, and then the micro-nano particle reinforcement and the ceramic balls are placed in a ball mill for ball milling according to the weight ratio of 1 (10-15), wherein the ball milling speed is 200-500 r/min, and the time is 5-10 hours.
Further, in the step 1), the micro-nano particle reinforcement is TiC, SiC and B with micron size4C particles and at least one of carbon nanotubes and graphene.
Further, in the step 2), the concentration of the copper salt in the aqueous solution is 4-32 g/L, and the molar ratio of the addition amount of the complexing agent to the copper ions is (1-3): 1.
Further, in the step 2), the soluble copper salt is at least one of copper sulfate pentahydrate, copper chloride, copper nitrate, copper tartrate and copper acetate.
Further, in the step 2), the complexing agent is at least one of disodium ethylene diamine tetraacetate, potassium sodium tartrate, triethanolamine, tetrahydroxypropyl ethylenediamine and sodium citrate.
Further, in the step 3), the stabilizer is at least one of thiourea, 2' -bipyridine, o-phenanthroline, sodium thiosulfate and 1, 10-phenanthroline.
In the step 5), the reducing agent is at least one of formaldehyde, ethylenediamine, glyoxylic acid, sodium borohydride and hydrazine hydrate, and the molar ratio of the addition amount of the reducing agent to the copper ions is (0.5-2.5): 1.
A functionalized micro-nano particle reinforcement is prepared by the low-cost preparation method. The functionalized micro-nano particle reinforcement is applied to preparing an aluminum matrix composite.
The invention has the beneficial effects that:
1. the preparation method provided by the invention is scientific and reasonable in design, the micro-nano particle reinforcement is subjected to simple mechanical ball milling activation, the surface of the micro-nano particle reinforcement has catalytic activity, and then the functionalized micro-nano particle reinforcement with the copper coating thickness of 10-200 nm is obtained by designing and proportioning copper salt, a reducing agent, the pH value and the micro-nano reinforcement loading capacity in a reaction solution.
2. The preparation method of the invention omits the coarsening, sensitization and activation processes before the chemical copper plating of the conventional micro-nano particle reinforcement, avoids the use of high-cost and pollution-generating chemical reagents such as hydrochloric acid, nitric acid, stannous chloride, palladium chloride and the like, and has the advantages of simple process, low cost and easy control of the thickness and the shape of the coating copper.
3. The functional micro-nano particle reinforcement prepared by the invention improves the wettability and the dispersibility of the reinforcement in the melt of the stirring casting aluminum matrix, limits the interface reaction of the reinforcement and the melt of the stirring casting aluminum matrix, and improves the bonding property; the functional copper coating not only enhances the transmission of load between the reinforcement and the aluminum matrix, but also can reduce the scattering of electrons by the reinforcement and the interface as an electron transmission channel, so that the aluminum matrix composite has the characteristics of high strength and high conductivity, and the development and application of the aluminum matrix composite light electric conductor are promoted.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD pattern of TiC particles and graphene before and after coating copper in examples 1 and 4;
FIG. 2 is an SEM picture of TiC particles coated with copper in example 1;
fig. 3 is an SEM picture after graphene is coated with copper in example 4;
FIG. 4 is a metallographic photograph of a TiC particle coated with copper and then reinforced aluminum matrix composite material in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
1. A low-cost preparation method of a functionalized micro-nano particle reinforcement is characterized by comprising the following steps:
1) weighing the micro-nano particle reinforcement and the ceramic ball, drying at 60-90 ℃, and then placing the micro-nano particle reinforcement and the ceramic ball into the ball according to the weight ratio of 1 (10-15)Ball milling is carried out in a mill, the ball milling rotating speed is 200-500 r/min, and the time is 5-10 h. The micro-nano particle reinforcement is TiC, SiC and B with micron size4C particles and at least one of carbon nanotubes and graphene.
2) Preparing soluble copper salt and a complexing agent into an aqueous solution, mixing the soluble copper salt and the complexing agent, stirring for 20-60 min, dripping NaOH solution into the aqueous solution to adjust the pH value of the solution to 9-12.5, and continuously stirring until a precipitate-free solution A is obtained. The concentration of copper salt in the solution is 4-32 g/L, and the molar ratio of the addition amount of the complexing agent to copper ions is (1-3): 1. The soluble copper salt is at least one of copper sulfate pentahydrate, copper chloride, copper nitrate, copper tartrate and copper acetate. The complexing agent is at least one of disodium ethylene diamine tetraacetate, potassium sodium tartrate, triethanolamine, tetrahydroxypropyl ethylenediamine and sodium citrate.
3) Weighing a stabilizer, dissolving the stabilizer in distilled water, pouring the stabilizer into the solution A prepared in the step 2), and uniformly stirring to obtain a reaction solution B, wherein the concentration of the stabilizer is 5-15 mg/L; the stabilizer is at least one of thiourea, 2' -bipyridyl, o-phenanthroline, sodium thiosulfate and 1, 10-phenanthroline.
4) And (3) placing the reaction solution B in a constant-temperature water bath kettle at 50-75 ℃, and adding the micro-nano particle reinforcement treated in the step 1) under a continuous stirring state to obtain a suspension C with a particle loading of 1-10 g/L.
5) And weighing a reducing agent, adding the reducing agent into the suspension C, reducing copper ions of copper salt, depositing the copper ions on the surfaces of the micro-nano particles to form a functional copper coating, reacting for 30-50 min, and simultaneously dropping NaOH solution to keep the pH value of a reaction system at 9-12.5 to obtain a suspension D. The reducing agent is at least one of formaldehyde, ethylenediamine, glyoxylic acid, sodium borohydride and hydrazine hydrate, and the molar ratio of the addition amount of the reducing agent to the copper ions is (0.5-2.5): 1.
6) Standing the suspension D obtained in the step 5) for 30-60 min, filtering, washing with distilled water to be neutral, drying, and grinding to obtain the functional micro-nano particle reinforcement with the functional copper coating thickness of 10-200 nm.
The specific embodiment of the invention is as follows:
example 1
A low-cost preparation method of a functionalized micro-nano particle reinforcement comprises the following steps:
1) weighing TiC particles and ceramic balls, drying at 70 ℃, and then placing the TiC particles and the ceramic balls in a ball mill according to the weight ratio of 1:12 for ball milling, wherein the ball milling rotation speed is 400r/min, and the time is 8 h.
2) Preparing aqueous solution of copper sulfate pentahydrate and disodium ethylenediamine tetraacetate, mixing the two solutions, stirring for 30min, then dripping NaOH solution to adjust the pH value to 12.5, and continuously stirring until no precipitate solution A is obtained, wherein the concentration of the copper sulfate pentahydrate is 9.4g/L, the concentration of the disodium ethylenediamine tetraacetate is 14g/L, and the molar ratio of the disodium ethylenediamine tetraacetate to copper ions is 1: 1.
3) Weighing 2,2' -bipyridine, dissolving the 2,2' -bipyridine in distilled water, pouring the solution into the solution A prepared in the step 2), and uniformly stirring to obtain a reaction solution B, wherein the concentration of the 2,2' -bipyridine is 7 mg/L.
4) And (3) placing the reaction solution B in a constant-temperature water bath kettle at 60 ℃, and adding the TiC particles treated in the step 1) under a continuous stirring state to obtain a suspension C with the TiC particle loading of 4 g/L.
5) Weighing a reducing agent formaldehyde and adding the reducing agent formaldehyde into the suspension C, reducing copper ions of the copper sulfate pentahydrate and depositing the copper ions on the active surface of the TiC particles to form a functional copper coating, reacting for 40min, and simultaneously dripping NaOH solution to keep the pH value of the reaction system at 12.5 to obtain a suspension D, wherein the concentration of the formaldehyde is 9.4ml/L, and the molar ratio of the formaldehyde to the copper ions is 2.5: 1.
6) Standing the suspension D obtained in the step 5) for 40min, filtering, washing to be neutral by using distilled water, drying, and grinding to obtain the TiC particle reinforcement with the functional copper coating thickness of about 100 nm.
Example 2
A low-cost preparation method of a functionalized micro-nano particle reinforcement comprises the following steps:
1) weighing B4Drying the C particles and the ceramic balls at 90 ℃, and then pressing B4And (3) placing the C particles and the ceramic balls in a weight ratio of 1:15 into a ball mill for ball milling, wherein the ball milling rotation speed is 500r/min, and the time is 5 h.
2) Preparing copper chloride and potassium sodium tartrate into an aqueous solution, mixing the copper chloride and the potassium sodium tartrate, stirring for 45min, then dripping NaOH solution into the aqueous solution to adjust the pH value to 9, and continuously stirring until a precipitate-free solution A is obtained. The concentration of copper chloride in the reaction solution was 31.4g/L, the concentration of potassium sodium tartrate was 57.8g/L, and the molar ratio of potassium sodium tartrate to copper ions was 1.5: 1.
3) Weighing thiourea, dissolving the thiourea in distilled water, and pouring the thiourea into the solution A prepared in the step 2) to be uniformly stirred to obtain a reaction solution B, wherein the concentration of the thiourea is 5 mg/L.
4) Placing the reaction solution B into a constant-temperature water bath kettle at 50 ℃, and adding the B treated in the step 1) under the condition of continuous stirring4C particles to give B4C suspension C with a particle loading of 10 g/L.
5) Weighing sodium hypophosphite as a reducing agent, adding the sodium hypophosphite into the suspension C, reducing copper ions of copper chloride and depositing the copper ions on the suspension B4C, forming a functional copper coating on the active surface of the particle, reacting for 45min, and simultaneously dropping NaOH solution to keep the pH value of the reaction system at 9 to obtain a suspension D, wherein the concentration of sodium hypophosphite is 34.0g/L, and the molar ratio of sodium hypophosphite to copper ions is 2.1: 1.
6) Standing the suspension D obtained in the step 5) for 30min, filtering, washing with distilled water to neutrality, drying, and grinding to obtain B with a functional copper coating thickness of about 200nm4And C, particle reinforcement.
Example 3
A low-cost preparation method of a functionalized micro-nano particle reinforcement comprises the following steps:
1) weighing carbon nanotubes and ceramic balls, drying at 60 ℃, and then placing the carbon nanotubes and the ceramic balls in a ball mill according to the weight ratio of 1:10 for ball milling at the ball milling rotation speed of 200r/min for 7 h.
2) Preparing aqueous solution of copper tartrate and tetrahydroxypropyl ethylenediamine, mixing the aqueous solution and the aqueous solution, stirring for 50min, adding dropwise NaOH solution to adjust the pH value to 11.5, and continuously stirring until precipitate-free solution A is obtained. The concentration of copper tartrate in the reaction solution was 13.5g/L, the concentration of tetrahydroxypropylethylenediamine was 31.4g/L, and the molar ratio of tetrahydroxypropylethylenediamine to copper ions was 1.7: 1.
3) Weighing sodium thiosulfate and dissolving the sodium thiosulfate in distilled water, pouring the sodium thiosulfate into the solution A prepared in the step 2), and uniformly stirring to obtain a reaction solution B, wherein the concentration of the sodium thiosulfate is 10 mg/L.
4) Putting the reaction solution B into a constant-temperature water bath kettle at 65 ℃, and adding the carbon nano tubes treated in the step 1) under the continuous stirring state to obtain a suspension C with the carbon nano tube loading of 1 g/L.
5) Weighing reducing agent sodium borohydride, adding the reducing agent sodium borohydride into the suspension C, reducing copper ions of the copper tartrate and depositing the copper ions on the active surface of the carbon nano tube to form a functional copper coating, reacting for 45min, and simultaneously dropping NaOH solution to keep the pH value of the reaction system at 11.5 to obtain suspension D, wherein the concentration of the sodium borohydride is 4.8g/L, and the molar ratio of the sodium borohydride to the copper ions is 2: 1.
6) Standing the suspension D obtained in the step 5) for 60min, filtering, washing to be neutral by using distilled water, drying, and grinding to obtain the carbon nano tube reinforcement with the thickness of the functional copper coating being about 10 nm.
Example 4
A low-cost preparation method of a functionalized micro-nano particle reinforcement comprises the following steps:
1) weighing graphene and ceramic balls, drying at 80 ℃, and then placing the graphene and ceramic balls in a ball mill for ball milling at a ball milling rotation speed of 300r/min for 10 hours according to a weight ratio of the graphene to the ceramic balls of 1: 14.
2) Preparing aqueous solution from copper acetate and sodium citrate, mixing the aqueous solution and the aqueous solution, stirring the aqueous solution for 40min, then dripping NaOH solution to adjust the pH value to 11, and continuously stirring the aqueous solution until no precipitate A is obtained, wherein the concentration of the copper acetate in the reaction solution is 10.4g/L, the concentration of the sodium citrate is 40.4g/L, and the molar ratio of the sodium citrate to copper ions is 3: 1.
3) Weighing 1, 10-phenanthroline, dissolving in distilled water, pouring the solution into the solution A prepared in the step 2), and uniformly stirring to obtain a reaction solution B, wherein the concentration of the 1, 10-phenanthroline is 15 mg/L.
4) Putting the reaction solution B into a constant-temperature water bath kettle at 70 ℃, and adding the graphene treated in the step 1) under a continuous stirring state to obtain a suspension C with the graphene loading capacity of 2 g/L.
5) Weighing a reducing agent hydrazine hydrate, adding the reducing agent hydrazine hydrate into the suspension C, reducing copper ions of copper acetate, depositing the copper ions on the active surface of the graphene to form a functional copper coating, reacting for 30 minutes, and simultaneously dropping NaOH solution to keep the pH value of the reaction system at 11 to obtain a suspension D, wherein the concentration of hydrazine hydrate is 1.3ml/L, and the molar ratio of hydrazine hydrate to copper ions is 0.5: 1.
6) Standing the suspension D obtained in the step 5) for 50min, filtering, washing with distilled water to be neutral, drying, and grinding to obtain the graphene reinforcement with the thickness of the functional copper coating being about 110 nm.
The TiC particles of the copper coating obtained in the embodiment 1 of the invention are used as a reinforcement, the tensile strength, the elongation and the conductivity change of the aluminum-based composite material are prepared by a semi-solid stirring casting method, and the room-temperature tensile property of the material is tested according to GB/T228.1-2010. Testing equipment: 50kN electronic universal tester. The length of the sample gauge length is 100mm, and the diameter of the gauge length is 10 mm. The room temperature volume resistivity was measured according to GB/T3048.2-2007, and the conductivity of the composite material was expressed as the percentage of the international annealed copper standard conductivity. Testing equipment: QJ36 digital bridge. The length of the test specimen is 1000mm, and the diameter is 10 mm. The results are shown in table 1:
TABLE 1 comparison of the Properties of TiC particle-reinforced aluminum matrix composites with copper coatings
Note: the results are shown in the table for the 500 ℃ extruded state; '*' means that the performance of the aluminum matrix composite material is enhanced after the graphene functional copper coating in the embodiment 4 of the method is adopted.
As can be seen from table 1, the aluminum matrix composite reinforced by the copper-coated micro-nano particles of the present invention has the characteristics of high strength and good electrical conductivity, which indicates that the micro-nano particle reinforced functional copper-coated aluminum matrix composite is suitable for the electrical conductor of the light high-strength aluminum matrix composite.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A low-cost preparation method of a functionalized micro-nano particle reinforcement is characterized by comprising the following steps:
1) weighing the micro-nano particle reinforcement and the ceramic balls, and performing ball milling treatment on the micro-nano particle reinforcement and the ceramic balls to obtain a treated micro-nano particle reinforcement;
2) preparing a soluble copper salt and a complexing agent into an aqueous solution, mixing and stirring the soluble copper salt and the complexing agent for 20-60 min, dripping a NaOH solution to adjust the pH value of the solution to 9-12.5, and continuously stirring until a precipitate-free solution A is obtained;
3) weighing a stabilizer, dissolving the stabilizer in distilled water, pouring the stabilizer into the solution A prepared in the step 2), and uniformly stirring to obtain a reaction solution B, wherein the concentration of the stabilizer is 5-15 mg/L;
4) placing the reaction solution B in a constant-temperature water bath kettle at 50-75 ℃, and adding the micro-nano particle reinforcement treated in the step 1) under a continuous stirring state to obtain a suspension C with a particle loading of 1-10 g/L;
5) weighing a reducing agent, adding the reducing agent into the suspension C, reducing copper ions of copper salt and depositing the copper ions on the active surface of the micro-nano particles to form a functional copper coating, reacting for 30-50 min, and simultaneously dripping NaOH solution to adjust the pH value of a reaction system to 9-12.5 to obtain a suspension D;
6) standing the suspension D obtained in the step 5) for 30-60 minutes, filtering, washing with distilled water to be neutral, drying, and grinding to obtain the functional micro-nano particle reinforcement with the functional copper coating thickness of 10-200 nm.
2. The low-cost preparation method of the composite material micro-nano reinforcement functional copper coating according to claim 1, characterized in that: in the step 1), the micro-nano particle reinforcement and the ceramic balls are weighed and dried at the temperature of 60-90 ℃, and then the micro-nano particle reinforcement and the ceramic balls are placed in a ball mill for ball milling according to the weight ratio of 1 (10-15), wherein the ball milling speed is 200-500 r/min, and the time is 5-10 h.
3. The low-cost preparation method of the functionalized micro-nano particle reinforcement according to claim 1, is characterized in that: in the step 1), the micro-nano particle reinforcement is micron TiC, SiC and B4C particles and at least one of carbon nanotubes and graphene.
4. The low-cost preparation method of the functionalized micro-nano particle reinforcement according to claim 1, wherein in the step 2), the concentration of copper salt in the aqueous solution is 4-32 g/L, and the molar ratio of the addition amount of the complexing agent to copper ions is (1-3): 1.
5. The low-cost preparation method of the functionalized micro-nano particle reinforcement according to claim 1, is characterized in that: in the step 2), the soluble copper salt is at least one of copper sulfate pentahydrate, copper chloride, copper nitrate, copper tartrate and copper acetate.
6. The low-cost preparation method of the functionalized micro-nano particle reinforcement according to claim 1, is characterized in that: in the step 2), the complexing agent is at least one of disodium ethylene diamine tetraacetate, potassium sodium tartrate, triethanolamine, tetrahydroxypropylethylenediamine and sodium citrate.
7. The low-cost preparation method of the functionalized micro-nano particle reinforcement according to claim 1, is characterized in that: in the step 3), the stabilizer is at least one of thiourea, 2' -bipyridine, o-phenanthroline, sodium thiosulfate and 1, 10-phenanthroline.
8. The low-cost preparation method of the functionalized micro-nano particle reinforcement according to claim 1, is characterized in that: in the step 5), the reducing agent is at least one of formaldehyde, ethylenediamine, glyoxylic acid, sodium borohydride and hydrazine hydrate, and the molar ratio of the addition amount of the reducing agent to the copper ions is (0.5-2.5): 1.
9. A functionalized micro-nano particle reinforcement prepared by the low-cost preparation method of any one of claims 1 to 8.
10. The application of the functionalized micro-nano particle reinforcement body according to claim 9 in the preparation of aluminum matrix composite materials.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111465734.3A CN114131036A (en) | 2021-12-03 | 2021-12-03 | Low-cost preparation method of functionalized micro-nano particle reinforcement |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111465734.3A CN114131036A (en) | 2021-12-03 | 2021-12-03 | Low-cost preparation method of functionalized micro-nano particle reinforcement |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114131036A true CN114131036A (en) | 2022-03-04 |
Family
ID=80387526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111465734.3A Pending CN114131036A (en) | 2021-12-03 | 2021-12-03 | Low-cost preparation method of functionalized micro-nano particle reinforcement |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114131036A (en) |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1442391A (en) * | 2003-04-04 | 2003-09-17 | 中国科学院上海硅酸盐研究所 | Method of preparing nano composite powdered particle using copper enclosed nano silicone carbide particle |
CN101439973A (en) * | 2008-12-23 | 2009-05-27 | 四川大学 | Copper coated silicon carbide composite material and preparation thereof |
CN101559494A (en) * | 2009-06-02 | 2009-10-21 | 四川大学 | Core-shell structure type tungsten carbide-cobalt hard alloy raw material powder and preparation method thereof |
CN101892472A (en) * | 2010-07-13 | 2010-11-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing ceramic-metal copper composite powder material |
CN102172500A (en) * | 2011-02-15 | 2011-09-07 | 江苏大学 | Preparation method for synthesizing graphene/copper composite nanomaterial at one step |
CN102198510A (en) * | 2011-04-27 | 2011-09-28 | 黑龙江大学 | Method for preparing nano copper/carbon nano tube composite powder by liquid phase method |
CN102436862A (en) * | 2011-09-08 | 2012-05-02 | 西北师范大学 | Graphene/nanometer copper electric conducting composite material and preparation thereof |
JP2013067854A (en) * | 2011-09-20 | 2013-04-18 | Pelnox Ltd | Copper composite particle, composite metallic copper particle, method for producing copper composite particle, metallic paste, article having metallic conductor and method for producing article having metallic conductor |
CN103113958A (en) * | 2013-03-05 | 2013-05-22 | 苏州惠丰润滑油有限公司 | Preparation method of graphene alkenyl nano-copper lubricant additive |
CN104479804A (en) * | 2014-11-25 | 2015-04-01 | 华南理工大学 | Nanometer copper/graphene composite material and preparation method and application thereof |
EA201501058A1 (en) * | 2015-09-25 | 2017-03-31 | Научно-Исследовательское Учреждение "Институт Ядерных Проблем" Белорусского Государственного Университета (Нии Яп Бгу) | METHOD FOR OBTAINING COMPOSITION NANOPARTICLES GRAPHEN / COPPER |
CN108103485A (en) * | 2017-12-18 | 2018-06-01 | 西安理工大学 | A kind of preparation method in graphene surface clad copper or nickel |
CN108624775A (en) * | 2018-04-20 | 2018-10-09 | 西安理工大学 | A kind of the graphene enhancing Cu-base composites and preparation method of supported copper |
CN108751176A (en) * | 2018-06-05 | 2018-11-06 | 沈阳建筑大学 | A kind of preparation method of plating copper nano-particle graphene composite material |
CN110125438A (en) * | 2019-05-31 | 2019-08-16 | 湖南工业大学 | A kind of method that liquid-phase reduction prepares ultra-fine cemented carbide composite powder |
CN110624546A (en) * | 2019-10-22 | 2019-12-31 | 特烯(厦门)科技有限公司 | Preparation method of copper/graphene catalyst |
-
2021
- 2021-12-03 CN CN202111465734.3A patent/CN114131036A/en active Pending
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1442391A (en) * | 2003-04-04 | 2003-09-17 | 中国科学院上海硅酸盐研究所 | Method of preparing nano composite powdered particle using copper enclosed nano silicone carbide particle |
CN101439973A (en) * | 2008-12-23 | 2009-05-27 | 四川大学 | Copper coated silicon carbide composite material and preparation thereof |
CN101559494A (en) * | 2009-06-02 | 2009-10-21 | 四川大学 | Core-shell structure type tungsten carbide-cobalt hard alloy raw material powder and preparation method thereof |
CN101892472A (en) * | 2010-07-13 | 2010-11-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing ceramic-metal copper composite powder material |
CN102172500A (en) * | 2011-02-15 | 2011-09-07 | 江苏大学 | Preparation method for synthesizing graphene/copper composite nanomaterial at one step |
CN102198510A (en) * | 2011-04-27 | 2011-09-28 | 黑龙江大学 | Method for preparing nano copper/carbon nano tube composite powder by liquid phase method |
CN102436862A (en) * | 2011-09-08 | 2012-05-02 | 西北师范大学 | Graphene/nanometer copper electric conducting composite material and preparation thereof |
JP2013067854A (en) * | 2011-09-20 | 2013-04-18 | Pelnox Ltd | Copper composite particle, composite metallic copper particle, method for producing copper composite particle, metallic paste, article having metallic conductor and method for producing article having metallic conductor |
CN103113958A (en) * | 2013-03-05 | 2013-05-22 | 苏州惠丰润滑油有限公司 | Preparation method of graphene alkenyl nano-copper lubricant additive |
CN104479804A (en) * | 2014-11-25 | 2015-04-01 | 华南理工大学 | Nanometer copper/graphene composite material and preparation method and application thereof |
EA201501058A1 (en) * | 2015-09-25 | 2017-03-31 | Научно-Исследовательское Учреждение "Институт Ядерных Проблем" Белорусского Государственного Университета (Нии Яп Бгу) | METHOD FOR OBTAINING COMPOSITION NANOPARTICLES GRAPHEN / COPPER |
CN108103485A (en) * | 2017-12-18 | 2018-06-01 | 西安理工大学 | A kind of preparation method in graphene surface clad copper or nickel |
CN108624775A (en) * | 2018-04-20 | 2018-10-09 | 西安理工大学 | A kind of the graphene enhancing Cu-base composites and preparation method of supported copper |
CN108751176A (en) * | 2018-06-05 | 2018-11-06 | 沈阳建筑大学 | A kind of preparation method of plating copper nano-particle graphene composite material |
CN110125438A (en) * | 2019-05-31 | 2019-08-16 | 湖南工业大学 | A kind of method that liquid-phase reduction prepares ultra-fine cemented carbide composite powder |
CN110624546A (en) * | 2019-10-22 | 2019-12-31 | 特烯(厦门)科技有限公司 | Preparation method of copper/graphene catalyst |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ma et al. | Preparation and characterization of monodispersed PS/Ag composite microspheres through modified electroless plating | |
CN109317665B (en) | Copper/carbon composite material and preparation method thereof | |
Varol et al. | The effect of silver coated copper particle content on the properties of novel Cu-Ag alloys prepared by hot pressing method | |
Song et al. | An electroless plating and planetary ball milling process for mechanical properties enhancement of bulk CNTs/Cu composites | |
CN110983211A (en) | Preparation method of carbon nano tube reinforced copper-based composite material | |
CN110578065B (en) | Preparation method of graphene reinforced copper-based composite material | |
CN109554565A (en) | A kind of interface optimization method of carbon nanotube enhanced aluminium-based composite material | |
CN110331318A (en) | A kind of graphene and carbon nanotube enhanced aluminium-based composite material and preparation method thereof | |
US20230193427A1 (en) | Graphene- and in-situ nanoparticle-reinforced aluminum-based composite material and preparation method | |
CN102747240A (en) | Preparation method of carbon-nanotube-enhanced magnesium-based composite material | |
Beygi et al. | An optimization analysis on electroless deposition of Al2O3/Cu core-shell nanostructures | |
CN110699676A (en) | High-strength high-conductivity metal glass composite material and preparation method thereof | |
WO2014029210A1 (en) | Preparation method for electrical contact materials | |
CN109338134A (en) | A kind of preparation method of nickel-plating carbon nanotube reinforced aluminum matrix composites | |
Gao et al. | Study on metallurgically prepared copper-coated carbon fibers reinforced aluminum matrix composites | |
Liu et al. | Optimizing the interface bonding in Cu matrix composites by using functionalized carbon nanotubes and cold rolling | |
CN110828024B (en) | Conducting wire prepared from conductive graphene coated copper and preparation method and application thereof | |
Guo et al. | Effect of reinforcement content on microstructures and mechanical properties of graphene nanoflakes-reinforced titanium alloy matrix composites | |
Zou et al. | Electroless copper plating mechanism of mesophase pitch-based carbon fibers by the grafting modification of silane couple agents | |
CN109265712B (en) | Preparation method of polyacrylic acid composite conductive particles coated with graphene in gradient manner | |
CN114131036A (en) | Low-cost preparation method of functionalized micro-nano particle reinforcement | |
CN110343977B (en) | Preparation method of continuous carbon fiber reinforced aluminum matrix composite | |
CN110295298B (en) | Preparation method of graphene-aluminum composite material | |
Luo et al. | Microstructure and properties of W-Ag matrix composites by designed dual-metal-layer coated powders | |
CN110560698A (en) | preparation method of carbon nano tube reinforced copper-based composite material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |