CN103681952B - The preparation technology of spacecraft molybdenum/platinum/silver laminar metal matrix composite - Google Patents
The preparation technology of spacecraft molybdenum/platinum/silver laminar metal matrix composite Download PDFInfo
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- CN103681952B CN103681952B CN201310369272.4A CN201310369272A CN103681952B CN 103681952 B CN103681952 B CN 103681952B CN 201310369272 A CN201310369272 A CN 201310369272A CN 103681952 B CN103681952 B CN 103681952B
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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 218
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 117
- 239000011733 molybdenum Substances 0.000 title claims abstract description 117
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 109
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 62
- 239000004332 silver Substances 0.000 title claims abstract description 62
- 239000011156 metal matrix composite Substances 0.000 title claims abstract description 39
- 238000005516 engineering process Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 34
- 238000007747 plating Methods 0.000 claims abstract description 34
- 238000003466 welding Methods 0.000 claims abstract description 19
- 238000002203 pretreatment Methods 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 63
- 238000009713 electroplating Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 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
- 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
- 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate 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
- 239000010946 fine silver Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000012876 topography Methods 0.000 abstract description 12
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 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
- 238000005530 etching Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000003756 stirring Methods 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
- 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
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005468 ion implantation Methods 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
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 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
- 238000004140 cleaning Methods 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
- 238000000605 extraction 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
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 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
- 238000005476 soldering Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of preparation technology of spacecraft solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite.Step is the pre-treatment of molybdenum paper tinsel, Mo metallic surface electroplatinizing, molybdenum/platinum plating sample annealing, molybdenum/platinum layer shape annealed sample surface electrical are silver-plated and the annealing of molybdenum/platinum/silver plating sample, molybdenum/platinum/silver laminar metal matrix composite surface topography scanning electron microscopic observation, test along the Auger spectroscopy analysis of the degree of depth and resistance spot welding hot strength.The invention enables molybdenum/platinum, platinum/silver-colored interface that diffusion occurs to infiltrate, thus metallurgical binding is realized on molybdenum/platinum, platinum/silver-colored interface, obtain the molybdenum/platinum/silver laminar metal matrix composite with high interfacial bonding strength, high welding hot strength, hot strength of welding when itself and the resistance spot welding of solar battery sheet single-point is 324 gram forces (gf), has exceeded the weld strength index that GJB GJB2602-1996 specifies.
Description
Technical field
The present invention relates to a kind of preparation technology of spacecraft solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite.
Background technology
The power-supply system of spacecraft (comprising satellite, spaceship and space station etc.) be by using solar array as Blast Furnace Top Gas Recovery Turbine Unit (TRT), batteries formed as energy storage device with the power control needed for distribution system.Solar array generates electricity between the illumination period of Earth's orbit, provides electric energy for spacecraft by electric loading, is battery charging simultaneously.
Solar array is made up of a large amount of solar battery sheet, and these cell pieces fill in order and are attached on solar panel, utilize the photoelectric effect of solar cell, convert incident solar radiation to electric energy.Although every sheet battery very little electric current of contribution and voltage, a large amount of cell pieces carries out suitable series and parallel connections then can provide electric current required for spacecraft load and voltage, and the extraction of these series, parallel and electric current is all adopt metal interconnected to carry out.
Spacecraft has quite a few to be in the upper operation of Low Earth Orbit (LowEarthOrbit-LEO, orbit altitude is between 200Km to 1000Km).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 then solar array power output declines, and heavy then cell array is thoroughly destroyed, thus causes spacecraft to lose efficacy.And reliability in-orbit and the life-span of LEO spacecraft will be improved, 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 solar cell interconnect sheet molybdenum/silver laminar metal matrix composite and preparation technology, mainly adopt ion implantation, by in the test piece of silver ion implantation molybdenum paper tinsel, then electrosilvering obtains molybdenum/silver laminar metal matrix composite.Though it may be noted that molybdenum/silver laminar metal matrix composite solves the problems such as sheet of interconnect high interfacial bonding strength, heat-resistant anti-fatigue, excellent weldability and conductivity, but facts have proved that also must resolve sheet of interconnect possesses excellent non-oxidizability to bear the problem of LEO atomic oxygen erosion, adds platinum metal layer and can meet to prepare molybdenum/platinum/silver-colored laminar composite between molybdenum-Yin.
The technology of preparing of molybdenum/platinum/silver-colored laminar composite has several difficult point:
though molybdenum-platinum is solid solution system, also exist five metal mesophase spherule (
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 high, that plasticity and toughness the are good molybdenum/platinum combination interface difficulty of bond strength larger;
though platinum-Yin system is solid solution system, academia also exists larger dispute to platinum-Yin binary alloy phase diagram up to now, and this makes reasonable microstructural confirmation, the formulation of annealing process also exists difficulty;
(thermal coefficient of expansion of molybdenum is about 5.2 to the thermal expansion coefficient difference of molybdenum, platinum and silver metal comparatively greatly
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 a kind of preparation technology of spacecraft solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite, to improve the life and reliability in-orbit of LEO spacecraft.Adopt the annealing technology of cyanideless electro-plating+repeatedly to realize the metallurgical binding at interface between molybdenum/platinum/silver, finally prepared molybdenum/platinum/silver laminar metal matrix composite, reached performance requirement.Prepared molybdenum/platinum/silver laminar metal matrix composite can reach with the intensity of space gallium arsenide solar cell resistance spot welding the requirement that GJB2602-1996 marks in national army.
The preparation technology of solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite provided by the invention mainly comprises the following steps:
1) pre-treatment of molybdenum paper tinsel.The pre-treatment of molybdenum foil is extremely important for the molybdenum/platinum/silver-colored interface cohesion obtaining high strength.Pre-treatment includes the steps such as molybdenum foil deoils, cleans, etches, Ultrasonic Cleaning, its process is: immersed in the liquid that deoils by the molybdenum foil crossed with alcohol washes and soak, take out and immerse soaking and washing in deionized water, the molybdenum foil that cleaned of deoiling immerses in etching liquid and etches, etching terminates to soak in rear immersion deionized water, then put into deionized water and carry out Ultrasonic Cleaning, dry stand-by after ultrasonic cleaning terminates.
2) Mo metallic surface electroplatinizing.This step adopts direct current electrode position device electroplatinizing, and temperature of electroplating solution is 80-85 DEG C, has electroplated acquisition molybdenum/platinum plating sample.
Electroplatinizing solution composition and technological parameter as follows:
Sodium hydrogen phosphate 140g/LpH 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 plating sample annealing (first time atmosphere protection annealing).This step is mainly and previous step is obtained molybdenum electroplatinizing sample 900-950 under argon shield
carry out annealing 3.5 ~ 4 hours, after annealing, obtain molybdenum/platinum layer shape annealed sample.
4) molybdenum/platinum layer shape annealed sample surface electrical is silver-plated.This step adopts direct current electrode position device electrosilvering, has electroplated acquisition molybdenum/platinum/silver plating sample.
Plating silver solution composition and technological parameter are:
Sodium thiosulfate 250g/LpH 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) annealing (annealing of second time atmosphere protection) of molybdenum/platinum/silver plating sample.
This step is mainly and previous step is obtained molybdenum/platinum/silver plating sample under argon shield 700 ~ 750
carry out annealing 4 ~ 4.5 hours, after annealing, finally obtain molybdenum/platinum/silver laminar metal matrix composite.
The present invention carries out following test:
1) the surface topography scanning electron microscopy (SEM) obtaining molybdenum/platinum plating sample after the platinum plating of molybdenum surface electrical is observed;
2) after the platinum plating of molybdenum surface electrical after first time atmosphere protection annealing obtain molybdenum/platinum layer shape annealed sample surface topography SEM observe;
3) the surface topography SEM of molybdenum/platinum/silver laminar metal matrix composite observes;
4) molybdenum/platinum/silver laminar metal matrix composite is analyzed along the composition Auger spectroscopy (AES) of the degree of depth;
5) molybdenum/platinum/silver laminar metal matrix composite is welded hot strength with the resistance spot welding of space gallium arsenide solar cell sheet and is tested.
The layer structure advanced composite material that molybdenum/platinum of the present invention/silver-colored laminar composite is take molybdenum as matrix, silver metal is top layer, platinum is intermediate layer, three realizes metallurgical binding and prepares 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 is then except can realize, except the lamellar composite to mutual not solid solution molybdenum, silver metal, the non-oxidizability of its excellence also can being utilized to bear atomic oxygen erosion as intermediate layer 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 the LEO spacecraft bearing alternation thermal force and atomic oxygen erosion.
The invention provides a kind of preparation technology of spacecraft solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite.Adopt Mo metallic surface electroplatinizing+atmosphere protection annealing, molybdenum/platinum surface electrical silver-plated+technology such as atmosphere protection annealing makes molybdenum/platinum, platinum/silver-colored interface that diffusion occurs to infiltrate respectively; thus metallurgical binding is realized on molybdenum/platinum, platinum/silver-colored interface; obtain the molybdenum/platinum/silver laminar metal matrix composite with high interfacial bonding strength, high welding hot strength; hot strength of welding when itself and the resistance spot welding of solar battery sheet single-point is 324 gram forces (gf), has exceeded the 150gf weld strength index that GJB GJB2602-1996 specifies.
Accompanying drawing explanation
Fig. 1: the schematic diagram of molybdenum/platinum/silver laminar metal matrix composite structure in the present invention.
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: in the present invention after the platinum plating of molybdenum surface electrical obtain molybdenum/platinum plating sample surface topography observe SEM figure.
Fig. 5: in the present invention after the platinum plating of molybdenum surface electrical first time atmosphere protection annealing after institute obtain molybdenum/platinum layer shape annealed sample surface topography observe SEM scheme.
Fig. 6: in the present invention, the surface topography of molybdenum/platinum/silver laminar metal matrix composite observes SEM figure.
Fig. 7: molybdenum/platinum/silver laminar metal matrix composite is along the composition AES spectrogram of the degree of depth.
Fig. 8: molybdenum/platinum/silver laminar metal matrix composite weld strength test schematic diagram in the present invention.
Fig. 9: in the present invention, molybdenum/platinum/silver laminar metal matrix composite welds the test curve of hot strength with space gallium arsenide solar cell resistance spot welding.
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 laminar metal matrix composite structure, and wherein, 1-parent metal is molybdenum, and thickness is 12
; 2-metallic intermediate layer is platinum, and thickness is 0.5
; 3-coating metal is silver, and thickness is 5
.
Concrete implementation step is as follows:
1, Mo metallic surface deoils, cleans
By the long 180mm crossed with alcohol washes
wide 120mm
the molybdenum paper tinsel of thick 15 μm 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, and take out to immerse in deionized water to soak and clean for 5 minutes, cleaning carries out 3 times.
2, Mo metallic surface etching
Above-mentioned process is deoiled process and use the molybdenum foil of washed with de-ionized water to be immersed in 1L etching liquid (37% concentrated hydrochloric acid 150mL+98% concentrated sulfuric acid 150mL+ distilled water+80g chromium trioxide) and etch 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 25 minutes (supersonic frequency 50Hz, temperature is 30
), 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 the deionized water dissolving of 40g diammonium hydrogen phosphate 500mL is become ammonium dibasic phosphate solution; 0.5308g chloroplatinic acid (altogether platiniferous 0.2g) is become platinum acid chloride solution with 100mL deionized water dissolving.
The disodium phosphate soln prepared and ammonium dibasic phosphate solution are mixed, platinum acid chloride solution is added stirring and make it mix; Then add 0.01g dodecyl sodium sulfate, make its whole dissolving finally add deionized water to 1L.
4, Mo metallic surface electroplatinizing
The direct current electrode position device shown in Fig. 2 is adopted to electroplate.In figure, 4-DC power supply, 5-miliammeter, 6-platinum plate anode, the test piece of 7-molybdenum, 8-coating bath (being made up of transparent inorganic glass), 9-plating solution, 10-constant temperature water bath.
Platinum electrode (anode) area is 1cm
1cm is 3.5cm with the distance of plating sample.Electroplating current density is 4Adm
-2, electroplating time is 3.5 hours, and temperature of electroplating solution constant temperature water bath controls at 85 DEG C.
After plating terminates, obtain molybdenum/platinum plating sample, blot with filter paper after soaking 15 minutes with deionized water, hang and dry in the air 12 hours, insert in vacuum drying oven 60
temperature, 10
-1dry 90 minutes under Pa vacuum degree.
5, first time atmosphere protection annealing
By above-mentioned molybdenum/platinum plating sample in annealing furnace 900 DEG C carry out argon shield and anneal 4 hours.Annealing process is: rise to 250 DEG C with 5 DEG C of heating rates per minute, and 250 DEG C of insulations 10 minutes, then rise to 900 DEG C with 6.5 DEG C of heating rates per minute, at 900 DEG C, be incubated 4 hours, start cooling after insulation terminates, cooling method was cool with stove.
After annealing terminates, obtain molybdenum/platinum layer shape annealed sample.
6, molybdenum/platinum layer shape annealed sample surface electrical is silver-plated
(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 liquor argenti nitratis ophthalmicus and pyrosulfurous acid potassium solution with the deionized water dissolving of 250mL respectively with 45g potassium metabisulfite, under the condition stirred, pyrosulfurous acid potassium solution is poured in liquor argenti nitratis ophthalmicus, after generating 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, after leaving standstill, then add thiosemicarbazide 0.8g, make it all dissolve, be finally settled to 1L with deionized water.The silver plating liquid pH value made is between 6.5 ~ 8.
(2) electrosilvering
The direct current electrode position device shown in Fig. 3 is adopted to carry out electrosilvering to molybdenum/platinum layer shape annealed sample surface.In figure, 11-DC power supply, 12-miliammeter, 13-silver metal plate anode, 14-molybdenum/platinum layer shape annealed sample, 15-coating bath (being made up of 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, and electroplating temperature is 25
.
After plating terminates, obtain molybdenum/platinum/silver plating sample, blot with filter paper after soaking 15 minutes with deionized water, hang and dry in the air 12 hours, insert in vacuum drying oven 60
temperature, 10
-1dry 90 minutes under Pa vacuum degree.
7, second time atmosphere protection annealing
By above-mentioned molybdenum/platinum/silver plating sample in annealing furnace 700 DEG C carry out argon shield and anneal 4 hours.Annealing process is: rise to 250 DEG C with 5 DEG C of heating rates per minute, and 250 DEG C of insulations 10 minutes, then rise to 700 DEG C with 6.5 DEG C of heating rates per minute, at 700 DEG C, be incubated 4 hours, start cooling after insulation terminates, cooling method was cool with stove.
Annealing terminates rear final acquisition molybdenum/platinum/silver laminar metal matrix composite.
The SEM of 8, molybdenum/platinum layer shape annealed sample surface topography observes
Fig. 4 is the surface topography map of molybdenum/platinum plating sample, has plated the platinum layer of one deck dense uniform as can be seen from Figure 4 at Mo metallic surface; Fig. 5 obtains the surface topography map of molybdenum/platinum layer shape annealed sample in 4 hours 900 DEG C of annealing after electroplatinizing, can find out platinum layer after annealing uniform crystal particles grow up, the surfacing of platinum plating layer is fine and close.
9, the SEM of molybdenum/platinum/silver laminar metal matrix composite surface topography observes
Fig. 6 is the SEM figure of molybdenum/platinum/silver laminar metal matrix composite surface topography, and the surface coverage silver layer of one deck even compact as can be seen from Figure 6, composite material defines an entirety.
10, molybdenum/platinum/silver laminar metal matrix composite is analyzed along the composition AES of the degree of depth
Fig. 7 is the composition AES spectrogram of molybdenum/platinum/silver laminar metal matrix composite along the degree of depth, molybdenum-platinum and platinum-Yin interface all can there occurs diffusion, define metallurgical binding.
11, molybdenum/platinum/silver laminar metal matrix composite 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 molybdenum/platinum/silver laminar metal matrix composite test piece, then be stretched to it to come off from solar battery sheet, tensile load becomes 45 with sample
.
According to the feature (see accompanying drawing 1) of molybdenum/platinum/silver laminar metal matrix composite structure, the extension test result that composite layer argent and space gallium arsenide solar cell sheet weld together not only reflects the soldering tip intensity between composite material and solar battery sheet, also reflects 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 reach the index request that GJB and space flight user propose.
Claims (10)
1. a preparation technology for solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite, comprises the following steps:
1) molybdenum paper tinsel deoiled, clean, etch, the pre-treatment of Ultrasonic Cleaning;
2) adopt direct current electrode position device to Mo metallic surface electroplatinizing, obtain molybdenum/platinum plating sample;
3) previous step is obtained molybdenum electroplatinizing sample to carry out annealing under first time inert atmosphere protection and obtain molybdenum/platinum layer shape annealed sample;
4) adopt direct current electrode position device silver-plated to molybdenum/platinum layer shape annealed sample surface electrical, obtain molybdenum/platinum/silver plating sample;
5) previous step is obtained molybdenum/platinum/silver plating sample to carry out the annealing of second time inert atmosphere protection, finally obtain molybdenum/platinum/silver laminar metal matrix composite.
2. a preparation technology for solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite, comprises the following steps:
1) the carrying out of molybdenum paper tinsel deoiled, clean, etch and Ultrasonic Cleaning pre-treatment, it is characterized in that:
2) adopt direct current electrode position device, with platinum electrode as anode, molybdenum as negative electrode, at Mo metallic surface electroplatinizing, obtain molybdenum/platinum plating sample;
3) 900-950 under argon shield
molybdenum/platinum plating sample is carried out to first time atmosphere protection annealing 3.5 ~ 4 hours, obtains molybdenum/platinum layer shape annealed sample after annealing;
4) adopt direct current electrode position device, with fine silver plate as anode, molybdenum/platinum layer shape annealed sample as negative electrode, carry out electrosilvering, obtain molybdenum/platinum/silver and electroplate sample;
5) by molybdenum/platinum/silver plating sample 700-750 under argon shield
carry out second time atmosphere protection annealing 4 ~ 4.5 hours, after annealing, finally obtain molybdenum/platinum/silver laminar metal matrix composite.
3., according to the preparation technology described in claim 1 or 2, it is characterized in that the structure of described composite material is the layer structure of silver-platinum-molybdenum-platinum-Yin, platinum is the intermediate metal layer between molybdenum and silver; 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, Mo substrate layer thickness is 12
, platinum middle layer thickness is 0.5
, silver-colored skin depth is 5
.
5. according to the preparation technology described in claim 1 or 2, it is characterized in that described electroplatinizing solution composition and technological parameter as follows:
Sodium hydrogen phosphate 140g/LpH 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/LpH 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 according to claim 2, it is characterized in that annealing process described in step 3) is: rise to 250 DEG C with 5 DEG C of heating rates per minute, 250 DEG C of insulations 10 minutes, then 900 DEG C are risen to 6.5 DEG C of heating rates per minute, 4 hours are incubated at 900 DEG C, start cooling after insulation terminates, cooling method is cool with stove.
8. according to preparation technology according to claim 2, it is characterized in that annealing process described in step 5) is: rise to 250 DEG C with 5 DEG C of heating rates per minute, 250 DEG C of insulations 10 minutes, then 700 DEG C are risen to 6.5 DEG C of heating rates per minute, 4 hours are incubated at 700 DEG C, start cooling after insulation terminates, cooling method is cool with stove.
9. solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite that the preparation technology described in claim 1 or 2 obtains.
10., according to solar battery array sheet of interconnect molybdenum/platinum/silver laminar metal matrix composite according to claim 9, it is characterized in that this composite material and the space gallium arsenide solar cell sheet hot strength of welding when carrying out single-point resistance spot welding is 324 gram forces.
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