CN108950615A - A kind of molybdenum/platinum based on surface anodization nanoporous molybdenum/silver layer shape composite material and preparation method thereof - Google Patents
A kind of molybdenum/platinum based on surface anodization nanoporous molybdenum/silver layer shape composite material and preparation method thereof Download PDFInfo
- Publication number
- CN108950615A CN108950615A CN201810726276.6A CN201810726276A CN108950615A CN 108950615 A CN108950615 A CN 108950615A CN 201810726276 A CN201810726276 A CN 201810726276A CN 108950615 A CN108950615 A CN 108950615A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- silver
- solution
- plating
- platinum
- 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 54
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011733 molybdenum Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 38
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 31
- 239000004332 silver Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000002048 anodisation reaction Methods 0.000 title claims abstract description 13
- 238000007747 plating Methods 0.000 claims abstract description 47
- 239000011888 foil Substances 0.000 claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 238000003490 calendering Methods 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 238000009713 electroplating Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 25
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 25
- 239000012498 ultrapure water Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 6
- 229940043349 potassium metabisulfite Drugs 0.000 claims description 6
- 235000010263 potassium metabisulphite Nutrition 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 claims description 3
- 150000003583 thiosemicarbazides Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 230000002457 bidirectional effect Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 238000009849 vacuum degassing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- UCNMJHLMBGAULH-UHFFFAOYSA-L P(=O)(O)([O-])[O-].[Na+].[Na+].S(=O)(=O)(O)O.C(CCCCCCCCCCC)[Na] Chemical compound P(=O)(O)([O-])[O-].[Na+].[Na+].S(=O)(=O)(O)O.C(CCCCCCCCCCC)[Na] UCNMJHLMBGAULH-UHFFFAOYSA-L 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000003466 welding Methods 0.000 abstract description 11
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract description 5
- 238000007872 degassing Methods 0.000 abstract description 5
- 238000007743 anodising Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 24
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 208000025599 Heat Stress disease Diseases 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 241001233242 Lontra Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Molybdenum/platinum/silver laminar composite preparation method based on surface anodization nanoporous molybdenum that the invention discloses a kind of, main includes preparing electrolyte, plating Pt liquid and plating Ag liquid, being formed by anodized on molybdenum foil surface has nanoporous, Mo/Pt plating sample is obtained in the molybdenum foil electroplating surface Pt with nanoporous, Mo/Pt plating sample is cleaned, degasification, calendering and annealing obtain Mo/Pt stratiform sample, it is compound finally to carry out silver metal layer to the Mo/Pt stratiform sample.Nano-porous structure is prepared on the surface Mo by anodizing first, to improve the surface-active of Mo foil, then prepare Mo/Pt/Ag laminar composite.Preparation method of the present invention is a kind of preparation method that can effectively improve Mo/Pt/Ag laminar composite interface bond strength and welding performance.The resistance spot welding of Mo/Pt/Ag laminar composite and space gallium arsenide cells that the present invention obtains, which is stretched bond strength, can satisfy the 160gf index request that national military standard GJB2602-1996 and space flight user propose.
Description
Technical field
The present invention relates to a kind of preparation methods of laminar composite, more particularly to one kind to be based on surface anodization nanometer
Molybdenum/platinum of porous molybdenum/silver layer shape composite material and preparation method thereof.
Background technique
In the spacecraft of earth low orbit operation, such as satellite, airship and space station, energy resource supply is mainly by the sun
Cell array provides, and the service life of solar array mainly by mutually determining in flakes.Traditional solar cell array is mainly adopted
Pure Ag metal is used to will cause as interconnection sheet material since there is elemental oxygens and heat cycle effect in Low earth orbit environment
Metal Ag generation erosion falls off and heat fatigue cracking, and solar array is caused to fail.New material is studied to replace traditional gold
Belong to Ag mutually can effectively improve solar array service life in flakes, have weight to the military service of China's long-life spacecraft
The meaning wanted.
Mo metal has lower thermal expansion coefficient, and the ability for resisting heat fatigue caused by track thermal cycle is very strong, together
When its anti-atomic oxygen erosiveness it is also relatively strong.Therefore, mutually had in flakes using Mo metal as spacecraft solar battery array
Unique advantage.Mo metal as mutually in flakes the shortcomings that be that its solderability is very poor, to solve this problem, can by Mo metal with can
The good Ag metal progress of weldering property is compound to prepare Mo/Ag laminar composite.But since Mo-Ag belongs to non-solid-solution metal,
Reaction heat is positive, and does not spread between each other, and prepared by Mo/Ag laminar composite difficult.
In this research previous work, Mo/Ag laminar composite, institute had once been prepared by irradiation damage alloyage process
The composite material of preparation and gallium arsenide solar cell solder bond are good.But this preparation method is complicated for operation, is not suitable for work
Sparetime university's large-scale production.This research later attempts the lamellar composite that Mo, Ag are solved the problems, such as by using the method for metal intermediate layer,
I.e. using with Pt metal that Mo and Ag can be dissolved as middle layer by Mo, Ag lamellar composite together with, then prepare Mo/Ag
Laminar composite becomes preparation Mo/Pt/Ag laminar composite.Although result of study shows that theoretically Mo and Pt can
Mutually solid solution, but actually since Mo surface inertness is too big, actually Mo combines or extremely difficult with Pt.This causes most
The Mo/Pt/Ag laminar composite bond strength prepared eventually still cannot be met the requirements.
Summary of the invention
For the prior art, a kind of molybdenum/platinum/silver layer shape based on surface anodization nanoporous molybdenum proposed by the present invention
Composite material and preparation method thereof, wherein the method for used anodic oxidation prepares nano porous layer on Mo foil surface, improves Mo
Surface-active, solve the problems, such as the combination of Mo and Pt metal, finally prepare and meet intensity requirement (national military standard GJB2602-
1996) molybdenum/platinum/silver laminar composite.
In order to solve the above-mentioned technical problem, a kind of molybdenum based on surface anodization nanoporous molybdenum proposed by the present invention/
Platinum/silver layer shape composite material and preparation method thereof, comprising the following steps:
Step 1: preparing electrolyte: suitable ammonium fluoride being dissolved in ultrapure water, is stirred with glass bar complete to ammonium fluoride
Dissolution, obtains ammonium fluoride solution, wherein the mass concentration of ammonium fluoride and ultrapure water is 5.475~14.8g/L；By suitable second
Glycol is added in above-mentioned ammonium fluoride solution, wherein the volume ratio of ethylene glycol and ultrapure water is 9:1；Magnetic agitation 4h is uniformly mixed,
It is then allowed to stand 1h and electrolyte is made, it is spare；
Step 2: the container for being contained with electrolyte made from step 1 is placed in water bath, temperature is room temperature, with molybdenum foil
As anode, platinized platinum submerges in the electrolytic solution as cathode, turns on the power switch, under the constant voltage condition of 5~35V
15~20min of anodized is carried out, after anodized, molybdenum foil is taken out and is placed in the container equipped with dehydrated alcohol
Soaking and washing removal surface electrolyte residual is carried out then to hang 6~10h naturally dry, the molybdenum foil after drying is placed on ceramics
It is placed in tube furnace on substrate, is passed through hydrogen atmosphere, be warming up to 650 DEG C with the heating rate of 5~8 DEG C/min, heat preservation 3~5 is small
When, then cool to room temperature with the furnace, the molybdenum foil surface has nano-porous structure；
Step 3: preparing platinum plating solution: disodium hydrogen phosphate being dissolved in ultrapure water for 250~400g/L according to mass-volume concentration
In obtain disodium phosphate soln, be that diammonium hydrogen phosphate is dissolved in ultrapure water by 150~300g/L according to mass-volume concentration
To ammonium dibasic phosphate solution, the platinum acid chloride solution that mass-volume concentration is 8~10g/L is prepared, by above-mentioned suitable phosphoric acid hydrogen two
Dodecyl sodium sulfate is added after sodium solution, ammonium dibasic phosphate solution and platinum acid chloride solution mixing and obtains mixed solution A, the mixing
In solution A, the mass volume ratio of chloroplatinic acid is 0.8~1g/L, and the mass volume ratio of diammonium hydrogen phosphate is 30~60g/L, phosphoric acid
The mass volume ratio of disodium hydrogen is 100~160g/L, and the mass volume ratio of dodecyl sodium sulfate is 0.01~0.02g/L；It is quiet
It sets 4 hours, platinum plating solution is made, the pH of the platinum plating solution is 7.0~7.5；
Step 4: electroplatinizing: the platinum plating solution obtained using step 3 has nanometer as electroplate liquid, with the surface that step 2 obtains
The molybdenum foil of porous structure is as anode, using platinized platinum as anode, is immersed into electrode in electroplate liquid and is electroplated, current density is
2.0~3.0A/dm2, temperature is 80~85 DEG C, and electroplating time is 1~2h, obtains to surface and is coated with the molybdenum foil of platinum, is denoted as Mo/Pt electricity
Plate sample；
Step 5 Mo/Pt plating sample post-processing: the Mo/Pt plating sample that step 4 obtains is cleaned with deionized water,
Then ultrapure water is used, remained on surface electroplate liquid is removed, hangs 6~10h naturally dry, is put into drying in vacuum oven,
Then rolled, pressure is 20~25MPa, and the calendering time is 60min；Later, Mo/Pt plating sample is placed on ceramic substrate
On be placed in tube furnace, be passed through hydrogen, be warming up to 1050 DEG C with the heating rate of 5~8 DEG C/min, keep the temperature 8h, cool to the furnace
Room temperature obtains Mo/Pt stratiform sample；
Step 6: preparing silver plating liquid: it is super to be that sodium thiosulfate is completely dissolved in by 200~250g/L according to mass-volume concentration
It is molten that sodium thiosulfate is obtained in pure water, and silver nitrate is dissolved in ultrapure water for 200~225g/L according to appropriate concentration and obtains nitric acid
Silver-colored solution is that potassium metabisulfite is dissolved in ultrapure water that obtain potassium metabisulfite molten by 200~225g/L according to mass-volume concentration
Liquid；Then pyrosulfurous acid potassium solution is poured into and obtains emulsion in silver nitrate solution, then the emulsion is poured into sodium thiosulfate
Mixed solution B is obtained in solution, in the mixed solution, the mass volume ratio of silver nitrate is 40~45g/L, the matter of sodium thiosulfate
Amount volume ratio is 200~250g/L, and the mass volume ratio of potassium metabisulfite is 40~45g/L；2h is stood, into mixed solution B
It is that thiosemicarbazides is added in 0.6~1.0g/L according to mass-volume concentration, stirs to being completely dissolved, obtain silver plating liquid, the silver plating liquid
Ph be 6.5~8.0；
Step 7: silver metal layer is compound: utilizing silver plating liquid Mo/Pt stratiform sample made from step 5 made from step 6
Silver metal layer in surface recombination, the process of compound silver metal layer are divided into three times, remove every time including double-pulse plating silver, vacuum
Gas, 20MPa calendering process and 930 DEG C of annealings；The electroplating time of electrosilvering is followed successively by 5min, 10min and 15min three times；
Gained is molybdenum/platinum/silver laminar composite after above-mentioned silver metal layer is compound.
Compared with prior art, the beneficial effects of the present invention are:
In the research process of technical solution of the present invention, it is more early period nanometer to be prepared on the surface Mo using the method for de- alloy
Pore structure improves Mo surface-active, compound with Pt again later, to obtain Mo/Pt/Ag laminar composite；The result shows that should
Mo/Pt/Ag laminar composite bond strength is greatly improved.The study found that but if desired using strong acid (such as nitre
Acid) de- alloy is carried out, Mo foil is easy to appear sole mass and loss of strength is excessive.And without using strong in preparation method of the present invention
Acid, and anodic oxidation is used, relatively thin nano porous layer can be prepared on the surface many metals (such as Ti, W etc.), while
It not will lead to parent metal intensity to lose, therefore the method for anodic oxidation of the present invention is prepared on Mo foil surface
Nano porous layer improves the surface-active of Mo, solves the problems, such as the combination of Mo and Pt metal, finally prepares and meet intensity requirement
Molybdenum/platinum/silver the laminar composite of (national military standard GJB2602-1996).
Detailed description of the invention
Fig. 1 is the nano-pore electron scanning micrograph that Mo metal foil surface anodic oxidation obtains in embodiment；
Fig. 2 is the nano-pore obtained after hydrogen atmosphere protection heat treatment reduction after Mo metal foil surface nanosizing in embodiment
Electron scanning micrograph；
Fig. 3 is the Mo metal foil active testing curve in embodiment with nano surface porous structure；
Fig. 4 is the temperature variation curve for Mo/Pt being electroplated in embodiment sample annealing；
Fig. 5 is the electron scanning micrograph of Mo/Pt stratiform annealed sample in embodiment；
Fig. 6 is the EDS constituent analysis spectrogram of Mo/Pt stratiform annealed sample in embodiment；
Fig. 7 is the temperature variation curve for Mo/Pt/Ag being electroplated in embodiment sample annealing；
Fig. 8 is the electron scanning micrograph of Mo/Pt/Ag laminar composite in embodiment；
Fig. 9-1 is the schematic diagram 1 of Mo/Pt/Ag laminar composite resistance spot welding tensile strength test process in embodiment；
Fig. 9-2 is the schematic diagram 2 of Mo/Pt/Ag laminar composite resistance spot welding tensile strength test process in embodiment.
Specific embodiment
Technical solution of the present invention is described in further detail in the following with reference to the drawings and specific embodiments, it is described specific
Embodiment is only explained the present invention, is not intended to limit the invention.
A kind of molybdenum/platinum based on surface anodization nanoporous molybdenum proposed by the present invention/silver laminar composite preparation
Method, main includes preparing electrolyte, plating Pt liquid and plating Ag liquid, and being formed by anodized on molybdenum foil surface has nanometer
It is porous, Mo/Pt plating sample is obtained in the molybdenum foil electroplating surface Pt with nanoporous, Mo/Pt plating sample is cleaned,
Degasification, calendering and annealing obtain Mo/Pt stratiform sample, and it is compound finally to carry out silver metal layer to the Mo/Pt stratiform sample.
In the present invention, nano-porous structure is prepared on the surface Mo by anodizing first, to improve the table of Mo foil
Face activity, then preparation Mo/Pt/Ag laminar composite.The Mo/Pt/Ag laminar composite that the present invention is obtained and space
The resistance spot weldings of gallium arsenide cells stretches that bond strength can satisfy national military standard GJB2602-1996 and space flight user proposes
160gf index request.
Embodiment: molybdenum/platinum/silver laminar composite preparation based on surface anodization nanoporous molybdenum, it is specific to walk
It is rapid as follows:
Step 1: preparing electrolyte: weighing 5.92g NH4F is placed in the beaker equipped with 40mL ultrapure water, is stirred with glass bar
It mixes to NH4F is completely dissolved, and it is above-mentioned dissolved with NH to measure the addition of 360mL ethylene glycol4In the beaker of F, and extremely it is electrolysed with magneton stirring 4h
Liquid is uniformly mixed, and it is spare to be then allowed to stand 1h；
Step 2: by being placed in water bath equipped with the beaker of electrolyte, control temperature at 25 DEG C or so, with surface decontamination,
Cleaned Mo foil sample is submerged in the electrolytic solution as cathode, is turned on the power switch, with 20V's as anode, Pt piece
Anodized 15min is carried out under constant voltage condition, is taken out sample after anodized and is placed in equipped with anhydrous second
Soaking and washing 5min is carried out in the beaker of alcohol, then removal surface electrolyte residual is rinsed processing using dehydrated alcohol, hangs
Naturally dry is hung, molybdenum foil surface is as shown in Figure 1.Molybdenum foil after drying is put and is placed in tube furnace on a ceramic substrate, hydrogen is passed through
Gas atmosphere is warming up to 650 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 3 hours, then cool to room temperature with the furnace, it is more to obtain surface
The molybdenum foil in hole, as shown in Figure 2.
Step 3: preparing plating Pt liquid: measurement 400mL ultrapure water is fitted into the beaker that capacity is 1000mL first, by 140g
Disodium hydrogen phosphate dissolves in wherein.200mL ultrapure water is poured into the beaker that capacity is 500mL again, dissolves in 40g diammonium hydrogen phosphate,
1g chloroplatinic acid 100mL ultrapure water is dissolved, is uniformly mixed in the beaker of the 1000mL before acquired solution is all poured into, finally
The dodecyl sodium sulfate of 0.01g is added, is settled to 1L, stands 4 hours.
Step 4: plating Pt: the solution obtained using step 1 is electroplate liquid, the porous surface molybdenum that is obtained with anodic oxidation
(having a size of 20mm × 20mm × 17 μm) are immersed into electrode in electrolyte using platinum electrode as anode for cathode, and current density is
2.5A/dm2, size of current 200mA, temperature is 85 DEG C, electroplating time 2h, and Mo/Pt plating sample is obtained after plating.
Step 5: Mo/Pt plating sample post-processing: including: cleaning, degasification, calendering and annealing；
Obtained Mo/Pt plating sample: being placed in the beaker equipped with deionized water after the completion of plating and clean 5min by cleaning,
Then cleaning 3 times is rinsed 3min to its surface with ultrapure water further to remove remained on surface electroplate liquid, hangs 6~10h
Naturally dry；Degasification: sample being placed on clean drying box metal otter board, chamber door is closed, under 200 DEG C, 0.1Pa vacuum degree
It is dried 3h；Calendering: pressure 25MPa, calendering time are 60min；It is made annealing treatment as shown in Figure 4: after calendering
Mo/Pt plating sample is put to be placed in tube furnace on a ceramic substrate, is passed through hydrogen atmosphere, is warming up to 5 DEG C of heating rate
1050 DEG C, 8h is kept the temperature, room temperature is then cooled to the furnace, obtains Mo/Pt stratiform sample, as shown in Figure 5.
Step 6: preparing plating Ag liquid: 250g sodium thiosulfate is completely dissolved in the ultrapure water of the 300mL in 1000mL beaker
In.45g silver nitrate is dissolved in the 200mL ultrapure water in 500mL beaker, 45g potassium metabisulfite is dissolved in another 500mL and is burnt
In 200mL ultrapure water in cup.Then pyrosulfurous acid potassium solution is poured into silver nitrate solution, then obtained emulsion is poured into
In hypo solution, 2h is stood, the thiosemicarbazides of 0.8g is added, stirs to being completely dissolved, is settled to 1L.
Step 7: Ag metal layer is compound: the process predominantly Ag metal on Mo/Pt stratiform specimen surface lamellar composite
Layer, for the internal stress for reducing composite material, which completes in three times, in the compound Ag metal layer of Mo/Pt stratiform specimen surface point
It every time include four steps: double-pulse plating Ag, vacuum degassing, calendering process and annealing to carry out three times.
The technological parameter of the bidirectional pulse plating Ag of use are as follows: forward current density 0.4A/dm2, reverse current density
For 0.2A/dm2, positive duty ratio is 20%, and reversed duty ratio is 10%, and forward and reverse power frequency is 1000Hz, three times Ag
The compound electroplating time of metal layer is respectively 5min, 10min, 15min.Each Ag is dried in a vacuum drying oven after being electroplated
3h temperature is 60 DEG C of progress degasification, is then rolled, is annealed.Calendering carries out on press machine (PC-40), pressure 25MPa,
The calendering time is 1h.Anneal after calendering, as shown in fig. 7, annealing in tubular type ambient anneal furnace (OTL1200) into
Row, annealing temperature are 930 DEG C, are warming up to 250 DEG C first with the heating rate of 5 DEG C/min, keep the temperature 10min；Then with 7 DEG C/min
Heating rate is warming up to 930 DEG C, keeps the temperature 6h, and protective atmosphere is hydrogen atmosphere, and furnace cooling is to room temperature after insulating process.
It is multiple that the Mo/Pt/Ag stratiform based on surface anodization nanoporous Mo is finally obtained after the completion of silver metal layer is compound
Condensation material, as shown in Figure 8.
Sample made from above-described embodiment is tested and is characterized:
(1) SEM is tested:
Fig. 5 is the surface topography SEM figure after the Mo/Pt plating sample annealing being prepared in the present embodiment step 4.From
In figure as can be seen that through anodic oxidation and reduced anneal treated nanoporous Mo foil after the electrodeposition Pt by 2h, table
The nano aperture structure in face is completely capped, and Pt layers of plating is more smooth, and macroscopically it can be seen that metallic luster, no hole
Structure exists.
Fig. 8 is the Mo/Pt/Ag stratiform that the present embodiment is prepared using Mo foil after anodic oxidation and hydrogen treat as matrix
Composite material surface pattern SEM figure.As seen from the figure, after being layered repeatedly plating Ag, the smooth pore-free of material surface；On microcosmic
Crystal grain arranges smooth densification, and crystal boundary is in close contact, and surface layer is not easy to adsorb electroplate liquid residue, is easier to clean up.
(2) EDS constituent analysis
Fig. 6 is the EDS constituent analysis map that sample is electroplated in Mo/Pt in the present embodiment step 2, as seen from the figure, by hydrogen
For the Mo foil of reduction treatment after the electrodeposition Pt by 2h, the relative atom content of surface Pt can reach 54.33%, oxygen it is opposite
Atom content drops to 10.12%.
(3) Mo/Pt/Ag laminar composite tensile strength is tested
The test of bond strength needs Mo/Pt/Ag laminar composite being welded to GaAs too by resistance spot weld
On positive energy cell piece, resistance spot weld used is the UNITEKPECO board electric resistance electric arc welder of U.S. UNITEK company production, selection
Different capacity, different welding pressure are come to determine optimum welding process parameter, welding manner be that single-side double-point welds.Such as Fig. 9-1 and 9-2
Shown, 1 is solar battery sheet, 2 for Mo/Pt/Ag laminar composite mutually in flakes, 3 be the silver electrode of cell piece, and 4 be resistance
Weld nugget, 5 be tensile load F, and 6 be fixed station, and 7 be fixing clamp.
Table 1, which is the present embodiment, obtains the Mo/Pt/Ag stratiform of nanoporous Mo foil preparation based on anodic oxidation and hydrogen reducing
Welding tensile strength test results after composite material and the welding of gallium arsenide cells single-side double-point.Specifically as shown in Table 1, in pressure
1.8 pounds, maximum weld tensile strength 428gf can be reached under the conditions of bonding power 85W, and all extension test data are more than
160gf index as defined in national military standard GJB2602-1996 shows that Mo foil carries out after anodized and hydrogen reducing processing
The material that Mo/Pt/Ag lamellar composite is prepared has good binding performance.Optimum welding process parameter is determined simultaneously are as follows:
Pressure is 1.8 pounds, bonding power 85W.
1 Mo/Pt/Ag laminar composite tensile strength test results of table
(4) Fig. 3 is the nano surface porous active layer Mo foil after 650C hydrogen reducing annealing and the test of pure Mo foil
Obtained linear polarisation curves, sweep speed 5mV/s.According to the available electrochemistry in relation to electrode of linear polarisation curves
Matter, the liberation of hydrogen take-off potential of pure Mo foil is higher as seen from Figure 3, about -0.413V, nano surface porous active layer Mo foil
Liberation of hydrogen take-off potential is lower, about -0.322V.Energy needed for reflecting nano surface porous active layer Mo foil progress evolving hydrogen reaction
Consume it is less, that is, illustrate nanoporous active layer Mo foil surface-active be higher than pure Mo foil.The reason is that having nanoporous active layer
Mo foil have bigger specific surface area, effective active point is more.
The foregoing is merely the preferable specific embodiments of the present invention, but scope of protection of the present invention is not limited thereto,
Any person skilled in the art is in the technical scope that the present invention is shown, according to the technical scheme of the invention and its inventive conception
What is converted on an equal basis should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of molybdenum/platinum based on surface anodization nanoporous molybdenum/silver layer shape composite material and preparation method thereof, feature exist
In this method follows the steps below:
Step 1: preparing electrolyte: suitable ammonium fluoride being dissolved in ultrapure water, is stirred with glass bar completely molten to ammonium fluoride
Solution, obtains ammonium fluoride solution, wherein the mass concentration of ammonium fluoride and ultrapure water is 5.475~14.8g/L；By suitable second two
Alcohol is added in above-mentioned ammonium fluoride solution, wherein the volume ratio of ethylene glycol and ultrapure water is 9:1；Magnetic agitation 4h is uniformly mixed, so
1h is stood afterwards, and electrolyte is made, it is spare；
Step 2: the container for being contained with electrolyte made from step 1 is placed in water bath, temperature is room temperature, using molybdenum foil as
Anode, platinized platinum are submerged in the electrolytic solution as cathode, are turned on the power switch, to carry out under the constant voltage condition of 5~35V
15~20min of anodized after anodized, takes out molybdenum foil and is placed in the container equipped with dehydrated alcohol and carries out
Soaking and washing removes surface electrolyte residual, then, hangs 6~10h naturally dry, the molybdenum foil after drying is placed on ceramic substrate
On be placed in tube furnace, be passed through hydrogen atmosphere, be warming up to 650 DEG C with the heating rate of 5~8 DEG C/min, keep the temperature 3~5 hours, so
After cool to room temperature with the furnace, the molybdenum foil surface has nano-porous structure；
Step 3: preparing platinum plating solution: disodium hydrogen phosphate being dissolved in ultrapure water for 250~400g/L according to mass-volume concentration and being obtained
To disodium phosphate soln, diammonium hydrogen phosphate is dissolved in ultrapure water for 150~300g/L according to mass-volume concentration and obtains phosphorus
Sour two ammonium salt solution of hydrogen, the platinum acid chloride solution that preparation mass-volume concentration is 8~10g/L are molten by above-mentioned suitable disodium hydrogen phosphate
Dodecyl sodium sulfate is added after liquid, ammonium dibasic phosphate solution and platinum acid chloride solution mixing and obtains mixed solution A, the mixed solution
In A, the mass volume ratio of chloroplatinic acid is 0.8~1g/L, and the mass volume ratio of diammonium hydrogen phosphate is 30~60g/L, phosphoric acid hydrogen two
The mass volume ratio of sodium is 100~160g/L, and the mass volume ratio of dodecyl sodium sulfate is 0.01~0.02g/L；It is small to stand 4
When, platinum plating solution is made, the pH of the platinum plating solution is 7.0~7.5；
Step 4: electroplatinizing: the platinum plating solution obtained using step 3 has nanoporous as electroplate liquid, with the surface that step 2 obtains
The molybdenum foil of structure is as anode, using platinized platinum as anode, is immersed into electrode in electroplate liquid and is electroplated, current density be 2.0~
3.0A/dm2, size of current 200mA, temperature is 80~85 DEG C, and electroplating time is 1~2h, it obtains to surface and is coated with the molybdenum foil of platinum,
It is denoted as Mo/Pt plating sample；
Step 5 Mo/Pt plating sample post-processing: the Mo/Pt plating sample that step 4 obtains is cleaned with deionized water, then
With ultrapure water, remained on surface electroplate liquid is removed, hangs 6~10h naturally dry, is put into drying in vacuum oven, then
Rolled, pressure is 20~25MPa, and the calendering time is 60min；Later, Mo/Pt plating sample is put and is set on a ceramic substrate
In in tube furnace, it is passed through hydrogen, 1050 DEG C is warming up to the heating rate of 5~8 DEG C/min, keeps the temperature 8h, cool to room temperature with the furnace,
Obtain Mo/Pt stratiform sample；
Step 6: preparing silver plating liquid: sodium thiosulfate being completely dissolved in ultrapure water for 200~250g/L according to mass-volume concentration
In to obtain sodium thiosulfate molten, be that silver nitrate is dissolved in ultrapure water that obtain silver nitrate molten by 200~225g/L according to appropriate concentration
Potassium metabisulfite is dissolved in ultrapure water according to mass-volume concentration for 200~225g/L and obtains pyrosulfurous acid potassium solution by liquid；So
Pyrosulfurous acid potassium solution is poured into afterwards and obtains emulsion in silver nitrate solution, then the emulsion is poured into hypo solution
Mixed solution B is obtained, in the mixed solution, the mass volume ratio of silver nitrate is 40~45g/L, the quality volume of sodium thiosulfate
Than being 40~45g/L for the mass volume ratio of 200~250g/L, potassium metabisulfite；2h is stood, into mixed solution B according to matter
Measuring volumetric concentration is that thiosemicarbazides is added in 0.6~1.0g/L, stirs to being completely dissolved, obtains silver plating liquid, the Ph of the silver plating liquid is
6.5~8.0；
Step 7: silver metal layer is compound: utilizing silver plating liquid Mo/Pt stratiform specimen surface made from step 5 made from step 6
Compound upper silver metal layer, the process of compound silver metal layer are divided into three times, every time include double-pulse plating silver, vacuum degassing, 20
The calendering process of~25MPa and 930 DEG C of annealings；The electroplating time of electrosilvering is followed successively by 5min, 10min and 15min three times；
Gained is molybdenum/platinum/silver laminar composite after above-mentioned silver metal layer is compound.
2. molybdenum/platinum based on surface anodization nanoporous molybdenum/silver laminar composite preparation side according to claim 1
Method, which is characterized in that in step 7, the technological parameter of the bidirectional pulse electrosilvering of use are as follows: forward current density 0.4A/
dm2, reverse current density 0.2A/dm2, positive duty ratio is 20%, and reversed duty ratio is 10%, and forward and reverse power frequency is equal
For 1000Hz, the compound electroplating time of Ag metal layer is respectively 5min, 10min, 15min three times.
3. molybdenum/platinum based on surface anodization nanoporous molybdenum/silver laminar composite preparation side according to claim 1
Method, which is characterized in that in step 7, the vacuum degassed process conditions after silver has been electroplated every time are dry in a vacuum drying oven
Dry 3h temperature is 60 DEG C.
4. molybdenum/platinum based on surface anodization nanoporous molybdenum/silver laminar composite preparation side according to claim 1
Method, which is characterized in that in step 7, the process conditions of 930 DEG C of annealings are: being heated up first with the heating rate of 5 DEG C/min
To 250 DEG C, 10min is kept the temperature；Then 930 DEG C being warming up to 7 DEG C/min heating rate, keeps the temperature 6h, protective atmosphere is hydrogen atmosphere,
Furnace cooling is to room temperature after insulating process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810726276.6A CN108950615A (en) | 2018-07-04 | 2018-07-04 | A kind of molybdenum/platinum based on surface anodization nanoporous molybdenum/silver layer shape composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810726276.6A CN108950615A (en) | 2018-07-04 | 2018-07-04 | A kind of molybdenum/platinum based on surface anodization nanoporous molybdenum/silver layer shape composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108950615A true CN108950615A (en) | 2018-12-07 |
Family
ID=64485671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810726276.6A Pending CN108950615A (en) | 2018-07-04 | 2018-07-04 | A kind of molybdenum/platinum based on surface anodization nanoporous molybdenum/silver layer shape composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108950615A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114197014A (en) * | 2021-12-14 | 2022-03-18 | 合肥工业大学 | Method for realizing surface nanocrystallization of pure titanium part with complex shape |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102995028A (en) * | 2012-11-27 | 2013-03-27 | 天津大学 | Copper/molybdenum/copper composite material based on radiation damage diffusion alloying and preparation method thereof |
| CN103681952A (en) * | 2013-08-20 | 2014-03-26 | 天津大学 | A preparation technique for spacecraft-used molybdenum/platinum/silver/ layered metal matrix composite materials |
| CN103797589A (en) * | 2011-09-14 | 2014-05-14 | 国际商业机器公司 | Photovoltaic devices |
| CN105206850A (en) * | 2015-10-19 | 2015-12-30 | 太原理工大学 | Ti/W/Mo oxide in-situ reinforced platinum/palladium nanostructured composite catalyst and preparation method thereof |
| CN106024975A (en) * | 2016-06-03 | 2016-10-12 | 天津大学 | Preparation method of nano-porous molybdenum foil based molybdenum/platinum/silver laminar composite material |
| CN107904645A (en) * | 2017-10-19 | 2018-04-13 | 天津大学 | A kind of anodized surface processing method for improving metal molybdenum foil surface-active |
-
2018
- 2018-07-04 CN CN201810726276.6A patent/CN108950615A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103797589A (en) * | 2011-09-14 | 2014-05-14 | 国际商业机器公司 | Photovoltaic devices |
| CN102995028A (en) * | 2012-11-27 | 2013-03-27 | 天津大学 | Copper/molybdenum/copper composite material based on radiation damage diffusion alloying and preparation method thereof |
| CN103681952A (en) * | 2013-08-20 | 2014-03-26 | 天津大学 | A preparation technique for spacecraft-used molybdenum/platinum/silver/ layered metal matrix composite materials |
| CN105206850A (en) * | 2015-10-19 | 2015-12-30 | 太原理工大学 | Ti/W/Mo oxide in-situ reinforced platinum/palladium nanostructured composite catalyst and preparation method thereof |
| CN106024975A (en) * | 2016-06-03 | 2016-10-12 | 天津大学 | Preparation method of nano-porous molybdenum foil based molybdenum/platinum/silver laminar composite material |
| CN107904645A (en) * | 2017-10-19 | 2018-04-13 | 天津大学 | A kind of anodized surface processing method for improving metal molybdenum foil surface-active |
Non-Patent Citations (1)
| Title |
|---|
| 吴友明: "钼基互连片材料的制备及电阻焊工艺仿真", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114197014A (en) * | 2021-12-14 | 2022-03-18 | 合肥工业大学 | Method for realizing surface nanocrystallization of pure titanium part with complex shape |
| CN114197014B (en) * | 2021-12-14 | 2023-04-07 | 合肥工业大学 | Method for realizing surface nanocrystallization of pure titanium part with complex shape |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20200373586A1 (en) | Highly corrosion-resistant porous metal body | |
| CN104846397B (en) | One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed | |
| CN102428213B (en) | Method for treating the surface of a metal | |
| JP2012132083A (en) | Metallic porous body having high corrosion resistance, and method for manufacturing therefor | |
| CN104269278B (en) | A kind of self-supporting nanoporous nickel nickel compound electric pole piece and preparation method thereof | |
| CN106757234A (en) | The preparation method of 3D nano porous metal materials | |
| JPWO2015133296A1 (en) | Porous metal body and method for producing porous metal body | |
| CN104611731A (en) | Fence-type aluminum bar lead alloy anode plate for non-ferrous metal electrodeposition and preparation method of fence-type aluminum bar lead alloy anode plate | |
| CN104818503A (en) | Preparation method of porous copper full-impregnated film of three-dimensional network structure | |
| CN105483744A (en) | Porous hydrogen evolution catalyst, preparation method of porous hydrogen evolution catalyst and electrode containing hydrogen evolution catalyst | |
| CN104562094B (en) | A kind of preparation method of non-ferrous metal electrodeposition graded composite anode | |
| CN106024975B (en) | The preparation method of molybdenum/platinum based on nanoporous molybdenum foil/silver-colored laminar composite | |
| CN103681952B (en) | The preparation technology of spacecraft molybdenum/platinum/silver laminar metal matrix composite | |
| CN108950615A (en) | A kind of molybdenum/platinum based on surface anodization nanoporous molybdenum/silver layer shape composite material and preparation method thereof | |
| CN101162778A (en) | Lithium ionic cell cathode ear pole material and method for producing the same | |
| JP4824961B2 (en) | Plated steel sheet for battery container, battery container using the plated steel sheet for battery container, and battery using the battery container | |
| CN105810949A (en) | Preparation method of current collector with high specific surface area | |
| CN106591926A (en) | Method for preparing CNTs-porous nickel/nickel oxide hydrogen evolution reaction catalyst on surface of steel | |
| JP5635382B2 (en) | Method for producing porous metal body having high corrosion resistance | |
| CN114988529A (en) | Preparation method of DSA electrode with titanium suboxide coating on surface | |
| JP4675707B2 (en) | Plated steel sheet for battery container, battery container using the plated steel sheet for battery container, and battery using the battery container | |
| JP2000268783A (en) | Surface treated steel sheet for battery case, manufacture thereof, battery case using surface treated steel sheet for battery case and battery using them | |
| JP2007059087A (en) | Plated steel sheet for battery case, battery case using same, and battery using the battery case | |
| JPWO2019106879A1 (en) | Method for manufacturing metal porous body, fuel cell and metal porous body | |
| Ye et al. | Formation of Nanocrystalline Surface of Cu–Sn Alloy Foam Electrochemically Produced for Li-Ion Battery Electrode |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181207 |