CN103681952A - A preparation technique for spacecraft-used molybdenum/platinum/silver/ layered metal matrix composite materials - Google Patents
A preparation technique for spacecraft-used molybdenum/platinum/silver/ layered metal matrix composite materials Download PDFInfo
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- CN103681952A CN103681952A CN201310369272.4A CN201310369272A CN103681952A CN 103681952 A CN103681952 A CN 103681952A CN 201310369272 A CN201310369272 A CN 201310369272A CN 103681952 A CN103681952 A CN 103681952A
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- molybdenum
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 222
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 118
- 239000011733 molybdenum Substances 0.000 title claims abstract description 118
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 111
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 66
- 239000004332 silver Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000011156 metal matrix composite Substances 0.000 title abstract description 10
- 239000000463 material Substances 0.000 title abstract 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000000137 annealing Methods 0.000 claims abstract description 48
- 238000003466 welding Methods 0.000 claims abstract description 22
- 238000009713 electroplating Methods 0.000 claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims description 41
- 238000005516 engineering process Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000004140 cleaning Methods 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
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 5
- 235000019800 disodium phosphate Nutrition 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 3
- ZMCCBULBRKMZTH-UHFFFAOYSA-N molybdenum platinum Chemical compound [Mo].[Pt] ZMCCBULBRKMZTH-UHFFFAOYSA-N 0.000 claims description 3
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 3
- 229940043349 potassium metabisulfite Drugs 0.000 claims description 3
- 235000010263 potassium metabisulphite Nutrition 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000010946 fine silver Substances 0.000 claims 1
- 210000003041 ligament Anatomy 0.000 claims 1
- 239000011888 foil Substances 0.000 abstract description 7
- 238000000682 scanning probe acoustic microscopy Methods 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000004626 scanning electron microscopy Methods 0.000 description 9
- 238000012876 topography Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 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 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910015797 MoPt Inorganic materials 0.000 description 1
- 101100077717 Mus musculus Morn2 gene Proteins 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a preparation technique for spacecraft-solar-cell-array-interconnection-sheet-used molybdenum/platinum/silver/ layered metal matrix composite materials. The technique comprises the steps of pretreatment of Molybdenum metal foils, platinum plating of molybdenum metal surfaces, molybdenum/platinum electroplating sample annealing, silver electroplating of molybdenum/platinum layered annealing sample surfaces, annealing of molybdenum/platinum/silver electroplating samples, scanning electron microscope observation of molybdenum/platinum/silver layered metal matrix composite material surface morphologies, Auger spectroscopy analysis along the depth and resistor spot welding tensile strength testing. According to the invention, diffusion infiltrating happens in a molybdenum/platinum interface and a platinum/silver interface, so that metallurgical bonding is realized in the molybdenum/platinum interface and the platinum/silver interface, and relatively high interface bonding intensity is realized. The molybdenum/platinum/silver/ layered metal matrix composite materials with the high interface bonding intensity and high welding tensile strength are obtained. The welding tensile strength of the molybdenum/platinum/silver/ layered metal matrix composite materials when in spot welding with a solar cell single spot resistor is 324gf, and a welding strength index prescribed by China military standard GJB2602-1996 is exceeded.
Description
Technical field
The present invention relates to the preparation technology of a kind of spacecraft solar battery array molybdenum/platinum/silver layer shape metal-base composites for sheet of interconnect.
Background technology
The power-supply system of spacecraft (comprising satellite, spaceship and space station etc.) is as energy storage device with the required power control of distribution system, to form as Blast Furnace Top Gas Recovery Turbine Unit (TRT), batteries by usining solar array.Solar array generates electricity between the illumination period of Earth's orbit, for spacecraft by electric loading, provide electric energy, be battery charging simultaneously.
Solar array is comprised of a large amount of solar battery sheets, and these cell pieces in order dress are attached on solar panel, utilize the photoelectric effect of solar cell, convert incident solar radiation to electric energy.Although every very little electric current and the voltage of battery contribution, a large amount of cell pieces carries out suitable series and parallel connections can provide the needed electric current of spacecraft load and voltage, and drawing of these series, parallel and electric current is all to adopt metal interconnected to carry out.
It is in the upper operation of Low Earth Orbit (Low Earth Orbit-LEO, orbit altitude in 200Km between 1000Km) that spacecraft has quite a few.Sheet of interconnect used will stand the impact of elemental oxygen, thermal cycle, micrometeorite and space junk and ultra-violet radiation on this track, wherein especially serious with the impact of elemental oxygen and thermal cycle again.In this space environment, often there is crackle in sheet of interconnect, oxidation is degraded and distortion comes off, and gently solar array power output declines, and heavy battery battle array is thoroughly destroyed, thereby cause spacecraft to lose efficacy.And reliability in-orbit and the life-span that will improve LEO spacecraft, it will be one of key that sheet of interconnect employing has high resistance atomic oxygen erosion ability, low-thermal-expansion amount and high conductive novel Mo/platinum/silver-colored laminar composite.
Chinese patent CN201110008862.5 discloses molybdenum for solar cell interconnect sheet/silver layer shape metal-base composites and preparation technology, mainly to adopt ion implantation, silver ion is injected to the test piece of molybdenum paper tinsel, and then electrosilvering obtains molybdenum/silver layer shape metal-base composites.Though it may be noted that molybdenum/silver layer shape metal-base composites has solved the problems such as sheet of interconnect high interfacial bonding strength, heat-resistant anti-fatigue, good weldability and conductivity, but facts have proved that also must resolve sheet of interconnect possesses the problem that excellent non-oxidizability is born LEO atomic oxygen erosion, between molybdenum-Yin, adding platinum layer to prepare molybdenum/platinum/silver-colored laminar composite can meet.
The technology of preparing of molybdenum/platinum/silver-colored laminar composite has several difficult points:
though molybdenum-platinum is solid solution system, exist phases in the middle of five metals (
phase Mo
6pt,
phase Mo
3pt,
phase Mo
3pt,
phase MoPt,
phase Mo
6pt
2), add that molybdenum foil surface activity is extremely low, obtain bond strength molybdenum/platinum combination interface difficulty high, that plasticity and toughness are good larger;
though platinum-Yin system is solid solution system, academia exists larger dispute to platinum-Yin binary alloy phase diagram up to now, and this makes the formulation of reasonable microstructural confirmation, annealing process exist difficulty;
the thermal expansion coefficient difference of molybdenum, platinum and silver metal is large, and (thermal coefficient of expansion of molybdenum is about 5.2
10
-6/ K
-1, platinum thermal coefficient of expansion be about 9.0
10
-6/ K
-1, silver thermal coefficient of expansion be about 19.2
10
-6/ K
-1), the more difficult control of thermal stress.
Summary of the invention
The object of the present invention is to provide the preparation technology of a kind of spacecraft solar battery array molybdenum/platinum/silver layer shape metal-base composites for sheet of interconnect, to improve the life and reliability in-orbit of LEO spacecraft.Cyanideless electro-plating+repeatedly annealing technology is realized the metallurgical binding at interface between molybdenum/platinum/silver in employing, has finally prepared molybdenum/platinum/silver layer shape metal-base composites, has reached performance requirement.Prepared molybdenum/platinum/silver layer shape metal-base composites can reach with the intensity of space gallium arsenide solar cell resistance spot welding the requirement of the national mark GJB2602-1996 of army.
The preparation technology of solar battery array provided by the invention molybdenum/platinum for sheet of interconnect/silver layer shape metal-base composites mainly comprises the following steps:
1) pre-treatment of molybdenum paper tinsel.The pre-treatment of molybdenum foil is for obtaining high-intensity molybdenum/platinum/silver-colored interface in conjunction with extremely important.Pre-treatment has comprised the steps such as molybdenum foil deoils, cleaning, etching, Ultrasonic Cleaning, its process is: the molybdenum foil cleaning with alcohol is immersed in the liquid that deoils and soaked, take out and immerse soaking and washing in deionized water, the molybdenum foil having cleaned that deoils immerses etching in etching liquid, etching finishes to soak in rear immersion deionized water, then put into deionized water and carry out Ultrasonic Cleaning, after ultrasonic cleaning finishes, dry stand-by.
2) Mo metallic surface electroplatinizing.This step adopts direct current electrode position device electroplatinizing, and temperature of electroplating solution is 80-85 ℃, has electroplated acquisition molybdenum/platinum and has electroplated sample.
Electroplatinizing solution composition and technological parameter are as follows:
Sodium hydrogen phosphate 140g/L pH value 7-7.5
Diammonium hydrogen phosphate 40g/L current density 4-4.5Adm
-2
Chloroplatinic acid 0.5308g/L electroplating time 3.5-4h
Dodecyl sodium sulfate 0.01g/L electroplating temperature 80-85
3) molybdenum/platinum is electroplated sample annealing (atmosphere protection annealing for the first time).This step is mainly previous step is obtained to molybdenum electroplatinizing sample 900-950 under argon shield
anneal 3.5 ~ 4 hours, after annealing, obtained molybdenum/platinum layer shape annealing sample.
4) molybdenum/platinum layer shape annealing specimen surface electrosilvering.This step adopts direct current electrode position device electrosilvering, has electroplated acquisition molybdenum/platinum/silver and has electroplated sample.
Plating silver solution composition and technological parameter are:
Sodium thiosulfate 250g/L pH value 6.5 ~ 8
Potassium metabisulfite 45g/L current density 0.40-0.45Adm
-2
Ammonium acetate 150g/L electroplating time 20-25min
Silver nitrate 45g/L electroplating temperature 18～35
Thiosemicarbazide 0.8g/L
5) molybdenum/platinum/silver is electroplated the annealing (atmosphere protection annealing for the second time) of sample.
This step is mainly electroplates sample under argon shield 700 ~ 750 by molybdenum/platinum that previous step obtains/silver
anneal 4 ~ 4.5 hours, after annealing, finally obtained molybdenum/platinum/silver layer shape metal-base composites.
The present invention carries out following test:
1) after the platinum plating of molybdenum surface electrical, obtain surface topography scanning electron microscopy (SEM) observation that molybdenum/platinum is electroplated sample;
2) the surface topography SEM observation of institute's molybdenum/platinum layer shape that obtains annealing sample after the annealing of atmosphere protection for the first time after the platinum plating of molybdenum surface electrical;
3) the surface topography SEM of molybdenum/platinum/silver layer shape metal-base composites observes;
4) molybdenum/platinum/silver layer shape metal-base composites is analyzed along the composition Auger spectroscopy (AES) of the degree of depth;
5) resistance spot welding of molybdenum/platinum/silver layer shape metal-base composites and space gallium arsenide solar cell sheet welding hot strength test.
Molybdenum/platinum of the present invention/silver-colored laminar composite be take molybdenum as matrix, silver metal as top layer, platinum as intermediate layer, three realizes layer structure advanced composite material prepared by metallurgical binding on interface.Wherein, molybdenum is high temperature resistant, at high temperature can keep higher intensity.Meanwhile, low thermal coefficient of expansion makes molybdenum have good thermal shock resistance, and conductivity and resistance to wear are also good; Silver metal has good weldability (solderability of molybdenum is relatively poor) and conductivity; Platinum except can be used as intermediate layer realize compound to the stratiform of not solid solution molybdenum, silver metal mutually, also can utilize its excellent non-oxidizability to bear atomic oxygen erosion simultaneously.Therefore, molybdenum/platinum/silver-colored laminar composite has possessed the features such as heat shock resistance, good conductivity and welding performance simultaneously, and anti-atomic oxygen corrodes, and does not have ferromagnetism, is very suitable for bearing the LEO spacecraft of alternation thermal force and atomic oxygen erosion.
The invention provides the preparation technology of a kind of spacecraft solar battery array molybdenum/platinum/silver layer shape metal-base composites for sheet of interconnect.Adopt the annealing of Mo metallic surface electroplatinizing+atmosphere protection, molybdenum/platinum surface electrical silver-plated+technology such as atmosphere protection annealing make respectively molybdenum/platinum, platinum/silver-colored interface diffusion occur and infiltrate; thereby realize metallurgical binding on molybdenum/platinum, platinum/silver-colored interface; obtained there is high interfacial bonding strength, molybdenum/platinum/silver layer shape metal-base composites of high welding hot strength; welding hot strength when itself and the resistance spot welding of solar battery sheet single-point is 324 gram forces (gf), has surpassed the 150gf weld strength index of GJB GJB2602-1996 regulation.
Accompanying drawing explanation
Fig. 1: the schematic diagram of molybdenum/platinum in the present invention/silver layer shape metal matrix composite structures.
Fig. 2: the schematic diagram of electroplatinizing device in the present invention.
Fig. 3: the schematic diagram of electrosilvering device in the present invention.
Fig. 4: the molybdenum that obtains after the platinum plating of molybdenum surface electrical in the present invention/platinum is electroplated the surface topography of sample and observed SEM figure.
Fig. 5: in the present invention, after the platinum plating of molybdenum surface electrical, the surface topography of institute's molybdenum/platinum layer shape that obtains annealing sample is observed SEM and schemed after the annealing of atmosphere protection for the first time.
Fig. 6: the surface topography of molybdenum/platinum in the present invention/silver layer shape metal-base composites is observed SEM figure.
Fig. 7: molybdenum/platinum/silver layer shape metal-base composites is along the composition AES spectrogram of the degree of depth.
Fig. 8: molybdenum/platinum in the present invention/silver layer shape metal-base composites weld strength test schematic diagram.
Fig. 9: the test curve of molybdenum/platinum in the present invention/silver layer shape metal-base composites and space gallium arsenide solar cell resistance spot welding welding hot strength.
Embodiment
The present invention in conjunction with the embodiments with accompanying drawing to being described in detail.
Fig. 1 is the schematic diagram of molybdenum/platinum/silver layer shape metal matrix composite structures, and wherein, 1-parent metal, is molybdenum, and thickness is 12
m; 2-metallic intermediate layer, is platinum, and thickness is 0.5
m; 3-top layer metal, is silver, and thickness is 5
m.
Concrete implementation step is as follows:
1, Mo metallic surface deoils, cleans
By the wide 120mm of long 180mm cleaning with alcohol
the molybdenum paper tinsel of thick 15 μ m immerses 1L completely and deoils the middle immersion of liquid (37% concentrated hydrochloric acid 50mL+98% concentrated sulfuric acid 50mL+distilled water) after 3 minutes, takes out to immerse in deionized water and soaks and clean for 5 minutes, cleans and carries out 3 times.
2, Mo metallic surface etching
Above-mentioned process is deoiled and processed and use the molybdenum foil of washed with de-ionized water to be immersed in the middle etching of 1L etching liquid (37% concentrated hydrochloric acid 150mL+98% concentrated sulfuric acid 150mL+ distilled water+80g chromium trioxide) 10 minutes, take out to immerse in deionized water and soak 15 minutes, then take out and be immersed in deionized water for ultrasonic ripple and clean that (supersonic frequency 50Hz, temperature was 30 in 25 minutes
), after Ultrasonic Cleaning, taking-up is dried stand-by.
3, the preparation of electroplatinizing solution
First 140g sodium hydrogen phosphate is dissolved in the deionized water of 200mL, stirs and make it all be dissolved into disodium phosphate soln; Then 40g diammonium hydrogen phosphate is become to Diammonium phosphate (DAP) solution with the deionized water dissolving of 500mL; 0.5308g chloroplatinic acid (platiniferous 0.2g altogether) is become to platinum acid chloride solution with 100mL deionized water dissolving.
The disodium phosphate soln preparing and ammonium dibasic phosphate solution are mixed, platinum acid chloride solution is added to stir it is mixed; Then add 0.01g dodecyl sodium sulfate, make its whole dissolvings finally add deionized water to 1L.
4, Mo metallic surface electroplatinizing
Adopt the direct current electrode position device shown in Fig. 2 to electroplate.In figure, 4-DC power supply, 5-miliammeter, 6-silver metal plate anode, the test piece of 7-molybdenum, 8-coating bath (being made by transparent inorganic glass), 9-plating solution, 10-constant temperature water bath.
Platinum electrode (anode) area is 1cm
1cm, with the distance of electroplating sample be 3.5cm.Electroplating current density is 4Adm
-2, electroplating time is 3.5 hours, temperature of electroplating solution is controlled at 85 ℃ with constant temperature water bath.
After plating finishes, obtained molybdenum/platinum and electroplated sample, with deionized water immersion, after 15 minutes, with filter paper, blotted, hung and dry in the air 12 hours, inserted in vacuum drying oven 60
temperature, 10
-1under Pa vacuum degree, dry 90 minutes.
5, atmosphere protection annealing for the first time
By above-mentioned molybdenum/platinum electroplate sample in annealing furnace 900 ℃ carry out argon shield annealing 4 hours.Annealing process is: with 5 ℃ of heating rates per minute, rise to 250 ℃, 250 ℃ of insulations 10 minutes, then with 6.5 ℃ of heating rates per minute, rise to 900 ℃, at 900 ℃, be incubated 4 hours, after insulation finishes, start cooling, cooling method is cooling with stove.
After annealing finishes, obtain molybdenum/platinum layer shape annealing sample.
6, molybdenum/platinum layer shape annealing specimen surface electrosilvering
(1) preparation of plating silver solution
First 250g sodium thiosulfate is dissolved in the deionized water of 300mL, stirs and make it all be dissolved into hypo solution; Then 45g silver nitrate is become to liquor argenti nitratis ophthalmicus and pyrosulfurous acid potassium solution with the deionized water dissolving of 250mL respectively with 45g potassium metabisulfite, under the condition stirring, pyrosulfurous acid potassium solution is poured in liquor argenti nitratis ophthalmicus, generate after pyrosulfurous acid silver turbid solution, immediately solution is added in hypo solution lentamente, silver ion is combined with sodium thiosulfate, generates micro-yellow clarified solution;
Again ammonium acetate 150g is added in above-mentioned micro-glistening yellow clear liquid, standing after, then add thiosemicarbazide 0.8g, it is all dissolved, finally with deionized water, be settled to 1L.The silver plating liquid pH value making is between 6.5 ~ 8.
(2) electrosilvering
Adopt the direct current electrode position device shown in Fig. 3 to carry out electrosilvering to molybdenum/platinum layer shape annealing specimen surface.In figure, 11-DC power supply, 12-miliammeter, 13-silver metal plate anode, 14-molybdenum/platinum layer shape annealing sample, 15-coating bath (being made by transparent inorganic glass), 16-plating solution.
The area of silver electrode (anode) is 10cm
10cm, silver electrode test coupon (negative electrode) 5.5cm.Electroplating current density is 0.45Adm
-2, electroplating time is 25min, electroplating temperature is 25
.
After plating finishes, obtain molybdenum/platinum/silver and electroplate sample, with deionized water immersion, after 15 minutes, with filter paper, blot, hang and dry in the air 12 hours, insert in vacuum drying oven 60
temperature, 10
-1under Pa vacuum degree, dry 90 minutes.
7, atmosphere protection annealing for the second time
By above-mentioned molybdenum/platinum/silver electroplate sample in annealing furnace 700 ℃ carry out argon shield annealing 4 hours.Annealing process is: with 5 ℃ of heating rates per minute, rise to 250 ℃, 250 ℃ of insulations 10 minutes, then with 6.5 ℃ of heating rates per minute, rise to 700 ℃, at 700 ℃, be incubated 4 hours, after insulation finishes, start cooling, cooling method is cooling with stove.
Annealing finishes rear final acquisition molybdenum/platinum/silver layer shape metal-base composites.
8, the SEM of molybdenum/platinum layer shape annealing specimen surface pattern observes
Fig. 4 is the surface topography map that molybdenum/platinum is electroplated sample, has plated the fine and close platinum layer uniformly of one deck as can be seen from Figure 4 at Mo metallic surface; Fig. 5 obtains the surface topography map of molybdenum/platinum layer shape annealing samples for 4 hours 900 ℃ of annealing after electroplatinizing, can find out that platinum layer uniform crystal particles after annealing grows up, and the surfacing of platinum plating layer is fine and close.
9, the SEM of molybdenum/platinum/silver layer shape film on metal matrix composite surface pattern observes
Fig. 6 is the SEM figure of molybdenum/platinum/silver layer shape film on metal matrix composite surface pattern, as can be seen from Figure 6 surface coverage the silver layer of one deck even compact, composite material has formed an integral body.
10, molybdenum/platinum/silver layer shape metal-base composites is analyzed along the composition AES of the degree of depth
Fig. 7 be molybdenum/platinum/silver layer shape metal-base composites along the composition AES spectrogram of the degree of depth, can molybdenum-platinum and platinum-Yin interface all there is diffusion, formed metallurgical binding.
11, molybdenum/platinum/silver layer shape metal-base composites welding hot strength test
Welding hot strength test process is shown in accompanying drawing 8, detailed process is for adopting resistance spot welding single spot welding to be connected on the gallium arsenide solar cell sheet of space the test piece of molybdenum/platinum/silver layer shape metal-base composites, then be stretched to it and come off from solar battery sheet, tensile load becomes 45 with sample
.
According to the feature of molybdenum/platinum/silver layer shape metal matrix composite structures (referring to accompanying drawing 1), the extension test result that composite layer argent and space gallium arsenide solar cell sheet weld together has not only reflected the soldering tip intensity between composite material and solar battery sheet, has also reflected the boundary strength between molybdenum/platinum/silver.
Accompanying drawing 9 is test result.When result shows single-point resistance spot welding, its welding (interface) intensity is 324 gram forces (gf), (GJB GJB2602-1996 set quota is 150gf, meets the requirement of spacecraft to have reached the index request that GJB and space flight user propose.
Claims (10)
1. a preparation technology for solar battery array molybdenum/platinum/silver layer shape metal-base composites for sheet of interconnect, comprises the following steps:
1) to molybdenum paper tinsel deoil, the pre-treatment of cleaning, etching, Ultrasonic Cleaning;
2) adopt direct current electrode position device to Mo metallic surface electroplatinizing, obtain molybdenum/platinum and electroplate sample;
3) previous step being obtained to molybdenum electroplatinizing sample carries out for the first time annealing under inert atmosphere protection and has obtained molybdenum/platinum layer shape annealing sample;
4) adopt direct current electrode position device to molybdenum/platinum layer shape annealing specimen surface electrosilvering, obtain molybdenum/platinum/silver and electroplate sample;
5) molybdenum/platinum that previous step obtains/silver is electroplated to sample and carried out inert atmosphere protection annealing for the second time, finally obtained molybdenum/platinum/silver layer shape metal-base composites.
2. a preparation technology for solar battery array molybdenum/platinum/silver layer shape metal-base composites for sheet of interconnect, comprises the following steps:
1) to the deoiling of molybdenum paper tinsel, cleaning, etching and Ultrasonic Cleaning pre-treatment, it is characterized in that:
2) adopt direct current electrode position device, use platinum electrode,, obtains molybdenum/platinum and electroplates sample at Mo metallic surface electroplatinizing as negative electrode as anode, molybdenum;
3) 900-950 under argon shield
molybdenum/platinum is electroplated to sample and carry out atmosphere protection annealing for the first time 3.5 ~ 4 hours, after annealing, obtain molybdenum/platinum layer shape annealing sample;
4) adopt direct current electrode position device, with fine silver plate, as anode, molybdenum/platinum layer shape, anneal sample as negative electrode, carry out electrosilvering, obtain molybdenum/platinum/silver and electroplate sample;
5) molybdenum/platinum/silver is electroplated to sample 700-750 under argon shield
carry out atmosphere protection annealing for the second time 4 ~ 4.5 hours, final molybdenum/platinum/silver layer shape metal-base composites that obtains after annealing.
3. according to the preparation technology described in claim 1 or 2, the layer structure that the structure that it is characterized in that described composite material is silver-platinum-molybdenum-platinum-Yin, platinum is the intermediate metal layer between molybdenum and silver; On molybdenum-platinum and platinum-Yin interface, all diffuse to form metallurgical binding.
4. according to the preparation technology described in claim 1 or 2, it is characterized in that in described composite material, molybdenum matrix ligament thickness is 12
m, platinum middle layer thickness is 0.5
m, silver-colored skin depth is 5
m.
5. according to the preparation technology described in claim 1 or 2, it is characterized in that described electroplatinizing solution composition and technological parameter are as follows:
Sodium hydrogen phosphate 140g/L pH value 7-7.5
Diammonium hydrogen phosphate 40g/L current density 4-4.5Adm
-2
Chloroplatinic acid 0.5308g/L electroplating time 3.5-4h
Dodecyl sodium sulfate 0.01g/L electroplating temperature 80-85
.
6. according to the preparation technology described in claim 1 or 2, it is characterized in that described plating silver solution composition and technological parameter are:
Sodium thiosulfate 250g/L pH value 6.5 ~ 8
Potassium metabisulfite 45g/L current density 0.40-0.45Adm
-2
Ammonium acetate 150g/L electroplating time 20-25min
Silver nitrate 45g/L electroplating temperature 18～35
Thiosemicarbazide 0.8g/L.
7. according to preparation technology claimed in claim 2, it is characterized in that described in step 3) that annealing process is: with 5 ℃ of heating rates per minute, rise to 250 ℃, 250 ℃ of insulations 10 minutes, then with 6.5 ℃ of heating rates per minute, rise to 900 ℃, at 900 ℃, be incubated 4 hours, after insulation finishes, start cooling, cooling method is cooling with stove.
8. according to preparation technology claimed in claim 2, it is characterized in that described in step 5) that annealing process is: with 5 ℃ of heating rates per minute, rise to 250 ℃, 250 ℃ of insulations 10 minutes, then with 6.5 ℃ of heating rates per minute, rise to 700 ℃, at 700 ℃, be incubated 4 hours, after insulation finishes, start cooling, cooling method is cooling with stove.
9. the solar battery array that the arbitrary preparation technology described in claim 1 or 2 obtains is molybdenum/platinum/silver layer shape metal-base composites for sheet of interconnect.
10. according to solar battery array claimed in claim 9 molybdenum/platinum/silver layer shape metal-base composites for sheet of interconnect, it is characterized in that this composite material and the welding hot strength of space gallium arsenide solar cell sheet when carrying out single-point resistance spot welding are 324 gram forces.
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| 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 |
| CN106711262A (en) * | 2015-11-16 | 2017-05-24 | 上海空间电源研究所 | Molybdenum/titanium/silver metal layered composite material used for space and preparation method thereof |
| CN108950615A (en) * | 2018-07-04 | 2018-12-07 | 天津大学 | A kind of molybdenum/platinum based on surface anodization nanoporous molybdenum/silver layer shape composite material and preparation method thereof |
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| CN102169912A (en) * | 2011-01-17 | 2011-08-31 | 天津大学 | Mo/Ag laminated metal matrix composite for solar cell interconnected sheet and preparation process thereof |
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| CN105112954A (en) * | 2015-09-21 | 2015-12-02 | 无锡清杨机械制造有限公司 | Platinum electroplating liquid of potassium platinum (IV) chloride and electroplating method of platinum electroplating liquid |
| CN106711262A (en) * | 2015-11-16 | 2017-05-24 | 上海空间电源研究所 | Molybdenum/titanium/silver metal layered composite material used for space and preparation method thereof |
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| CN109400178A (en) * | 2018-11-27 | 2019-03-01 | 上海安费诺永亿通讯电子有限公司 | A kind of chip ceramic antenna and preparation method thereof |
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