CN102021632A - Method for preparing protective film on copper alloy surface - Google Patents
Method for preparing protective film on copper alloy surface Download PDFInfo
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- CN102021632A CN102021632A CN 201010587697 CN201010587697A CN102021632A CN 102021632 A CN102021632 A CN 102021632A CN 201010587697 CN201010587697 CN 201010587697 CN 201010587697 A CN201010587697 A CN 201010587697A CN 102021632 A CN102021632 A CN 102021632A
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- copper alloy
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000001681 protective effect Effects 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 28
- 239000012528 membrane Substances 0.000 claims description 26
- 239000008151 electrolyte solution Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910017090 AlO 2 Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001952 rubidium oxide Inorganic materials 0.000 claims description 3
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 claims description 3
- 229940071182 stannate Drugs 0.000 claims description 3
- 125000005402 stannate group Chemical group 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229940037003 alum Drugs 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 abstract description 9
- 238000004381 surface treatment Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003961 penetration enhancing agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a method for preparing a protective film on a copper alloy surface and relates to copper alloy surface treatment, in particular to a method for performing microarc oxidation on the surface of the copper alloy and a method for composite surface treatment based on the microarc oxidation method. The method for preparing the protective film on the copper alloy surface is characterized in that a layer of oxide protective film is formed on the surface of the copper alloy by using the copper alloy as an anode and by performing microarc oxidation treatment in electrolyte in a treatment process. In the invention, the drawbacks of complex process, expensive equipment, thinner protective film with lower bonding force with a substrate, environmental pollution and the like of copper alloy surface treatment methods are overcome. A layer of microarc oxide film or microarc oxide composite film is formed on the surface of the copper alloy by microarc oxidation technology with or without adding additive into the electrolyte. The film is thick and has a compact structure and high corrosion resistance, high-temperature oxidization resistance and frictional wear resistance. The process is stable, simple, environmentally-friendly and suitable for industrial production.
Description
Technical field
A kind of preparation method of copper alloy surface protective membrane relates to a kind of copper alloy surface and handles, and particularly carries out differential arc oxidation and based on the composite surface treatment method of differential arc oxidation method at copper alloy surface.
Background technology
Copper alloy has many valuable physics-chem characteristics, and for example its thermal conductivity and specific conductivity are all very high, and chemical stability is strong, and tensile strength is big, easily welding, and corrosion stability is good, plasticity and extension excellent performance.It has obtained using widely in the national economic development as important base mateiral and functional materials, is the second largest consumption non-ferrous metal that consumption is only second to aluminium alloy in China.But the copper alloy corrosion resistance, especially the corrosion resistance in alkaline condition or high temperature oxygen environment is relatively poor, and hardness is general, and wear resistance is relatively poor, and it can be lost efficacy rapidly in than rugged environment.It is higher to add the copper alloy price, further improves its performance, it is protected just seem necessary more.
Fact proved, prevent that metallic material corrosion, effective, the easiest method of wearing and tearing from being that it is carried out surface treatment.At present a large amount of work has been done in the surface treatment of copper alloy both at home and abroad.As patent CA1075570A1, utilize the acid solution of the hydrogen peroxide that contains methyl-cyclohexanol or hexalin that copper alloy is carried out surface treatment, obtain one deck passive film.Patent US4049481A at first utilizes electrodip process at copper alloy surface deposition one deck binary Zinc-tin alloy, copper alloy is heat-treated afterwards again, makes to form transition layer between coating and the copper alloy to improve the coating bonding properties.And patent CN1431335 in conjunction with bottom, and then sprays the nickel-based self-fluxing alloy coating thereon in the controlled copper of temperature or copper alloy matrix surface preparation, spraying, obtains two-layer composite coating of the present invention.Patent CN1560319, the surperficial sulfurize permeating agent and the technology thereof of having invented a kind of copper or copper alloy part are packed the oven dry of penetration enhancer powder, dehydration, mixing back into and are oozed case with copper or copper alloy part, obtain infiltration layer through Overheating Treatment in oozing case.Patent CN1920090 carries out the method that electric spark deposition is handled at copper or copper alloy surface, adopts corresponding electrode to carry out depositing treatment, under protection of inert gas, uses electrical spark equipment to carry out depositing treatment.But these surface protection films or with substrate caking power a little less than, rete is thinner, protective capability is limited; Perhaps need heat in the preparation process, can destroy the mechanical property of copper alloy itself in various degree; Perhaps apparatus expensive, complex process can't be accomplished scale production.
Differential arc oxidation (MAO) technology is a kind of process for treating surface that grows up on the basis of common anode oxidation.Using this technology can be at metallic surface growth in situ one deck ceramic membranes such as Al, Mg, Ti.By technological process is controlled, can make the ceramic membrane of generation have excellent wear-resisting and corrosion resisting property, higher hardness and insulation resistance.Similar technology with other is compared, and the over-all properties of rete improves a lot, and technology is simple, and is easy to operate, the processing efficiency height.But this Study on Technology mainly concentrates on the light metal field, and auxiliary without other surface treatment methods directly at home and abroad do not appear in the newspapers in the document as yet to the treatment process that copper alloy carries out differential arc oxidation.Simultaneously, micro-arc oxidation films is as a kind of vesicular ceramic film, because its porous pattern also can reduce its protective capability to base material.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art; provide a kind of and can effectively solve present copper alloy surface treatment process or rete protective capability deficiency; the perhaps defective of apparatus expensive complex process; technology is simple; material cost is cheap, and rete is thicker and the preparation method of the compact copper alloy surface protective membrane in base.
The objective of the invention is to be achieved through the following technical solutions.
A kind of preparation method of copper alloy surface protective membrane, it is characterized in that its preparation process be with copper alloy as anode, in electrolytic solution, carry out differential arc oxidation and handle, form one deck oxide film at copper alloy surface.
The preparation method of a kind of copper alloy surface protective membrane of the present invention is characterized in that the basic electrolyte of described differential arc oxidation treating processes is the phosphoric acid system, contains Na in the electrolytic solution
3PO
48-12g/L, NaH
2PO
41-5g/L.
The preparation method of a kind of copper alloy surface protective membrane of the present invention is characterized in that the basic electrolyte of described differential arc oxidation treating processes is the aluminic acid system, contains Na in the electrolytic solution
2AlO
28-12g/L and, NaH
2PO
41-5g/L.
The preparation method of a kind of copper alloy surface protective membrane of the present invention is characterized in that the basic electrolyte of described differential arc oxidation treating processes is a silicate systems, contains Na in the electrolytic solution
2SiO
38-12g/L, NaH
2PO
41-5g/L.
The preparation method of a kind of copper alloy surface protective membrane of the present invention is characterized in that the basic electrolyte of described differential arc oxidation treating processes is the boric acid system, contains Na in the electrolytic solution
2B
4O
78-12g/L, NaH
2PO
41-5g/L.
The preparation method of a kind of copper alloy surface protective membrane of the present invention is characterized in that differential arc oxidation treating processes use bipolar pulse power supply, and Cu alloy material is as anode, and the stainless steel electrolytic pond is as negative electrode; The frequency of bipolar pulse power supply is at 120～1200 Hz, and dutycycle is 30%～80%, and constant current density is at 4-10A/dm in the oxidising process
2, electrolyte temperature maintains about 35 ℃, and oxidization time 10～60 minutes after oxidation is finished, dries naturally.
The preparation method of a kind of copper alloy surface protective membrane of the present invention is characterized in that being incorporated as chromic salt, stannate, tungstate, manganate high-valency metal oxysalt in basic electrolyte, its content in electrolytic solution is 2-10g/L.
The preparation method of a kind of copper alloy surface protective membrane of the present invention is characterized in that adding volume ratio in basic electrolyte is the suspension of 0.5%-2%, makes composite electrolytic solution; Suspension is handled through tensio-active agent by graphite, molybdenumdisulphide, wolfram varbide, aluminum oxide, cerium oxide, lanthanum trioxide, Praseodymium trioxide, the rubidium oxide of particle diameter below 500nm, is scattered in the water to make.
The preparation method of a kind of copper alloy surface protective membrane of the present invention is characterized in that the high-valency metal oxysalt that adds is (tungstate, alum salts, manganate etc.) in basic electrolyte.
The preparation method of a kind of copper alloy surface protective membrane of the present invention, technology is simple, easy handling, with low cost, and environmental friendliness, is fit to carry out large-scale production, is easy to industrialization; The rete that obtains combines closely with substrate, and rete is thicker, and copper alloy is had good provide protection, can greatly improve anticorrosive, the wear resistance of copper alloy.Method of the present invention, basic electrolyte is improved, obtain differential arc oxidation compound film by adding high-valency metal oxysalt and nanoscale solids particle, under the prerequisite of the basic mechanical performance that has kept the copper alloy micro-arc oxidation films, further improved the performance such as hardness, erosion resistance, frictional wear of micro-arc oxidation films.
Embodiment
A kind of preparation method of copper alloy surface protective membrane, its preparation process be with copper alloy as anode, in electrolytic solution, carry out differential arc oxidation and handle, form one deck oxide film at copper alloy surface.
1) differential arc oxidation is handled:
Basic electrolyte is phosphoric acid system (Na
3PO
48-12g/L and NaH
2PO4 1-5g/L), aluminic acid system (Na
2AlO
28-12g/L and NaH
2PO4 1-5g/L), silicate systems (Na
2SiO
38-12g/L and NaH
2PO
41-5g/L) with boric acid system (Na
2B
4O
78-12g/L and NaH
2PO4 1-5g/L).
With the bipolar pulse power unit copper alloy is handled, will be through conventional pretreated copper alloy sample as anode, the stainless steel electrolytic pond is as negative electrode.Bipolar pulse power settings frequency is that dutycycle is set in 30～80% at 120～1200 Hz, and constant current density in the oxidising process is controlled at 4 ~ 10A/dm2, and electrolyte temperature remains on about 35 ℃ in the oxidising process, oxidization time 10～60 minutes.After oxidation is finished, dry naturally and can obtain the oxide white protective membrane on the Cu alloy material surface.
2) differential arc oxidation Combined Processing
1) in add the high-valency metal oxysalt in the basic electrolyte mentioned, comprise chromic salt, stannate, tungstate, manganate etc., its composition in electrolytic solution is 2 ~ 10g/L.Then copper alloy is handled its electrical parameter, temperature, treatment time and 1 with the bipolar pulse power supply) in identical.
2) differential arc oxidation Combined Processing
With particle diameter at 500nm with interior solia particle suspension as additive, solia particle comprises: solid lubricant (graphite, MoS
2Deng), hard ceramic particles (WC, Al
2O
3Deng), rare-earth oxide (cerium oxide, lanthanum trioxide, Praseodymium trioxide, rubidium oxide etc.).With tensio-active agent solid particulate is dispersed in and makes suspension in the aqueous solution, afterwards 1) in to add volume ratio in the basic electrolyte mentioned be 0.5 ~ 2% suspension, make composite electrolytic solution.
With the bipolar pulse power unit copper alloy is handled, will be through conventional pretreated copper alloy sample as anode, the stainless steel electrolytic pond is as negative electrode.Bipolar pulse power settings frequency is that dutycycle is set in 30～80% at 120～1200 Hz, and constant current density in the oxidising process is controlled at 4 ~ 10A/dm2, and temperature remains on about 35 ℃ in the oxidising process, oxidization time 10～60 minutes.After oxidation is finished, dry naturally and get final product.
Other features of copper alloy differential arc oxidation treatment method of the present invention are partly done further to replenish at embodiment and are described.
Embodiment 1
Handling sample is the c6300 copper alloy, and size is the sheet of 20 mm * 36 mm * 2 mm, and its concrete operations step is:
1, sample pretreatment: polish sample surfaces successively to its roughness Ra ≈ 0.16 μ m with the waterproof abrasive paper of 500～1000#.Adopt common washing composition that the back sample surfaces of polishing is cleaned,, use distilled water flushing then to remove greasy dirt.
2, differential arc oxidation is handled: bath composition is Na
3PO
48 ~ 12g/L and NaH
2PO
41 ~ 5g/L.To immerse through the copper alloy sample of pre-treatment in the above-mentioned electrolytic solution, adopt and stir and refrigerating unit, the control solution temperature is about 35 ℃, use the bipolar pulse power supply, the positive pulse electric current, the frequency setting frequency is 120 ~ 1200 Hz, dutycycle 30 ~ 80%, and constant current density is at 4 ~ 10A/dm in the oxidising process
2Oxidization time is 10 ~ 60 min.After oxide treatment is finished, with tap water that sample wash is clean, dry naturally and get final product.
Embodiment 2
1, sample pretreatment is identical with embodiment 1.
2, compound differential arc oxidation is handled: bath composition is Na
3PO
48-12g/L, NaH
2PO
41-5g/L, and Na
2WO
42-10g/L is identical with embodiment 1 to the processing of copper alloy sample afterwards.
Embodiment 3
Handling sample is 6300 copper alloys, and size is the sheet of 20 mm * 36 mm * 2 mm, and its concrete operations step is:
1, sample pretreatment is identical with embodiment 1.
2, compound differential arc oxidation is handled: the basic electrolyte composition is Na
3PO
48-12g/L and NaH
2PO
41-5g/L, adding volume ratio then in basic electrolyte is the MoS of 0.5-2%
2Suspension (MoS
2Particle diameter is below 500nm), make composite electrolytic solution.To immerse through the copper alloy sample of pre-treatment in the above-mentioned composite electrolytic solution, adopt and stir and refrigerating unit, the control solution temperature is about 35 ℃, use the bipolar pulse power supply, the positive pulse electric current, the frequency setting frequency is 120-1200 Hz, dutycycle 30 ~ 80%, and constant current density is at 4-10A/dm2 in the oxidising process.Oxidization time is 10-60 min.After oxide treatment is finished, with tap water that sample wash is clean, dry naturally and get final product.
Embodiment 4
Copper alloy after the micro-arc oxidation films protection that obtains among copper alloy and the embodiment 1 is carried out the high-temperature oxidation resistant property testing at 850 ℃, and oxidization time was at 200-300 hour, and the result shows that the oxidation weight gain speed of this copper alloy is 0.015 mg/cm
2H is lower than 0.005mg/cm through the copper alloy oxidation weight gain rate after the differential arc oxidation film layer protection
2H, the copper alloy rate of body weight gain after the differential arc oxidation compound film protection of adding sodium wolframate is lower than 0.003mg/ cm
2H.
Embodiment 5
To 6300 copper alloy samples, the compound differential arc oxidation copper alloy that obtains among differential arc oxidation copper alloy that embodiment 1 obtains and the embodiment 3 carries out the friction and wear behavior test, adopts the mode that reciprocatingly slides, and reciprocating frequence is 5Hz, antithesis is a Φ 3mmGCr15 steel ball, load 2N.Copper alloy frictional coefficient about 0.4, wear rate are 3 * 10
-5Mm
3/ Nm; Arc cupric oxide alloy friction is about 0.6, and loss rate is 8 * 10
-6Mm
3/ Nm; Close differential arc oxidation copper alloy frictional coefficient and be lower than 0.2, wear rate is then crossed shallow owing to polishing scratch and can't be recorded.
Claims (9)
1. the preparation method of a copper alloy surface protective membrane, it is characterized in that its preparation process be with copper alloy as anode, in electrolytic solution, carry out differential arc oxidation and handle, form one deck oxide film at copper alloy surface.
2. the preparation method of a kind of copper alloy surface protective membrane according to claim 1 is characterized in that the basic electrolyte of described differential arc oxidation treating processes is the phosphoric acid system, contains Na in the electrolytic solution
3PO
48-12g/L, NaH
2PO
41-5g/L.
3. the preparation method of a kind of copper alloy surface protective membrane according to claim 1 is characterized in that the basic electrolyte of described differential arc oxidation treating processes is the aluminic acid system, contains Na in the electrolytic solution
2AlO
28-12g/L and, NaH
2PO
41-5g/L.
4. the preparation method of a kind of copper alloy surface protective membrane according to claim 1 is characterized in that the basic electrolyte of described differential arc oxidation treating processes is a silicate systems, contains Na in the electrolytic solution
2SiO
38-12g/L, NaH
2PO
41-5g/L.
5. the preparation method of a kind of copper alloy surface protective membrane according to claim 1 is characterized in that the basic electrolyte of described differential arc oxidation treating processes is the boric acid system, contains Na in the electrolytic solution
2B
4O
78-12g/L, NaH
2PO
41-5g/L.
6. the preparation method of a kind of copper alloy surface protective membrane according to claim 1 is characterized in that differential arc oxidation treating processes use bipolar pulse power supply, and Cu alloy material is as anode, and the stainless steel electrolytic pond is as negative electrode; The frequency of bipolar pulse power supply is at 120～1200 Hz, and dutycycle is 30%～80%, and constant current density is at 4-10A/dm2 in the oxidising process, and electrolyte temperature remains on 35 ℃, and oxidization time 10～60 minutes after oxidation is finished, dries naturally.
7. according to the preparation method of claim 2,3,4,5 described a kind of copper alloy surface protective membranes; it is characterized in that being incorporated as in basic electrolyte chromic salt, stannate, tungstate, manganate high-valency metal oxysalt, its content in electrolytic solution is 2-10g/L.
8. according to the preparation method of claim 2,3,4,5 described a kind of copper alloy surface protective membranes, it is characterized in that adding volume ratio in basic electrolyte is the suspension of 0.5%-2%, makes composite electrolytic solution; Suspension is handled through tensio-active agent by graphite, molybdenumdisulphide, wolfram varbide, aluminum oxide, cerium oxide, lanthanum trioxide, Praseodymium trioxide, the rubidium oxide of particle diameter below 500nm, is scattered in the water to make.
9. according to the preparation method of claim 2,3,4,5 described a kind of copper alloy surface protective membranes, it is characterized in that the high-valency metal oxysalt that adds is tungstate, alum salts or manganate in basic electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010587697 CN102021632A (en) | 2010-12-15 | 2010-12-15 | Method for preparing protective film on copper alloy surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010587697 CN102021632A (en) | 2010-12-15 | 2010-12-15 | Method for preparing protective film on copper alloy surface |
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| Publication Number | Publication Date |
|---|---|
| CN102021632A true CN102021632A (en) | 2011-04-20 |
Family
ID=43863397
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
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Cited By (10)
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| CN102528376A (en) * | 2012-03-02 | 2012-07-04 | 台州学院 | Electric spark precision repairing method for plastic mould |
| CN107236978A (en) * | 2016-07-09 | 2017-10-10 | 平顶山市美伊金属制品有限公司 | The enclosure method of the packing material and pore of closing oxidation rear substrate surface pore |
| CN107502939A (en) * | 2017-06-26 | 2017-12-22 | 安徽雷萨重工机械有限公司 | A kind of anti-friction bearing rolling element |
| CN108468075A (en) * | 2018-03-27 | 2018-08-31 | 杭州电子科技大学 | A kind of electrolyte and its application process of differential arc oxidation self-lubricating composite ceramic coating |
| CN110016708A (en) * | 2019-04-16 | 2019-07-16 | 湖南大学 | Suitable for copper and its micro-arc oxidization surface processing method and product of alloy |
| CN111155160A (en) * | 2020-02-24 | 2020-05-15 | 北京大学 | Method for reducing oxidation speed of metal product |
| CN111254476A (en) * | 2020-02-27 | 2020-06-09 | 江苏大学 | Preparation method of pure copper surface corrosion-resistant black micro-arc oxidation film |
| CN111394771A (en) * | 2020-04-22 | 2020-07-10 | 哈尔滨工业大学 | Method for preparing coating on surface of copper and copper alloy and copper product |
| CN112680692A (en) * | 2020-12-21 | 2021-04-20 | 米巴精密零部件（中国）有限公司 | Method for improving resistance of copper alloy to active sulfur corrosion |
| CN114164475A (en) * | 2021-11-25 | 2022-03-11 | 攀枝花学院 | Method for electrochemically treating magnesium or magnesium alloy surface |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260555A (en) * | 2008-04-18 | 2008-09-10 | 哈尔滨工业大学 | Plasma liquid phase electrolysis method for ceramic film deposited on surface of copper and alloy thereof |
-
2010
- 2010-12-15 CN CN 201010587697 patent/CN102021632A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260555A (en) * | 2008-04-18 | 2008-09-10 | 哈尔滨工业大学 | Plasma liquid phase electrolysis method for ceramic film deposited on surface of copper and alloy thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《中国陶瓷》 20091031 彭家志等 等离子体电解氧化电解液配方研究进展 12-15 2,7-9 第45卷, 第10期 2 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102528376A (en) * | 2012-03-02 | 2012-07-04 | 台州学院 | Electric spark precision repairing method for plastic mould |
| CN107236978A (en) * | 2016-07-09 | 2017-10-10 | 平顶山市美伊金属制品有限公司 | The enclosure method of the packing material and pore of closing oxidation rear substrate surface pore |
| CN107502939A (en) * | 2017-06-26 | 2017-12-22 | 安徽雷萨重工机械有限公司 | A kind of anti-friction bearing rolling element |
| CN108468075A (en) * | 2018-03-27 | 2018-08-31 | 杭州电子科技大学 | A kind of electrolyte and its application process of differential arc oxidation self-lubricating composite ceramic coating |
| CN110016708B (en) * | 2019-04-16 | 2021-02-23 | 湖南大学 | Micro-arc oxidation surface treatment method suitable for copper and copper alloy and product |
| CN110016708A (en) * | 2019-04-16 | 2019-07-16 | 湖南大学 | Suitable for copper and its micro-arc oxidization surface processing method and product of alloy |
| CN111155160A (en) * | 2020-02-24 | 2020-05-15 | 北京大学 | Method for reducing oxidation speed of metal product |
| CN111254476A (en) * | 2020-02-27 | 2020-06-09 | 江苏大学 | Preparation method of pure copper surface corrosion-resistant black micro-arc oxidation film |
| CN111394771A (en) * | 2020-04-22 | 2020-07-10 | 哈尔滨工业大学 | Method for preparing coating on surface of copper and copper alloy and copper product |
| CN111394771B (en) * | 2020-04-22 | 2021-05-04 | 哈尔滨工业大学 | Method for preparing coating on surface of copper and copper alloy and copper product |
| CN112680692A (en) * | 2020-12-21 | 2021-04-20 | 米巴精密零部件（中国）有限公司 | Method for improving resistance of copper alloy to active sulfur corrosion |
| CN114164475A (en) * | 2021-11-25 | 2022-03-11 | 攀枝花学院 | Method for electrochemically treating magnesium or magnesium alloy surface |
| CN114164475B (en) * | 2021-11-25 | 2024-03-15 | 攀枝花学院 | Electrochemical treatment method for magnesium or magnesium alloy surface |
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Application publication date: 20110420 |