CN116445901A - Copper alloy surface black passivation method - Google Patents
Copper alloy surface black passivation method Download PDFInfo
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- CN116445901A CN116445901A CN202310433215.1A CN202310433215A CN116445901A CN 116445901 A CN116445901 A CN 116445901A CN 202310433215 A CN202310433215 A CN 202310433215A CN 116445901 A CN116445901 A CN 116445901A
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- 238000002161 passivation Methods 0.000 title claims abstract description 84
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000005498 polishing Methods 0.000 claims abstract description 45
- -1 rare earth salt Chemical class 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 9
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000467 phytic acid Substances 0.000 claims abstract description 9
- 229940068041 phytic acid Drugs 0.000 claims abstract description 9
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 239000008399 tap water Substances 0.000 claims description 12
- 235000020679 tap water Nutrition 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002603 lanthanum Chemical class 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005282 brightening Methods 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 30
- 238000005260 corrosion Methods 0.000 abstract description 30
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 8
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000012964 benzotriazole Substances 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ZJHIEQGQFJJLBM-UHFFFAOYSA-N [Co].[Sn].[Cu] Chemical compound [Co].[Sn].[Cu] ZJHIEQGQFJJLBM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a black passivation method for a copper alloy surface in the technical field of metal surface treatment, which comprises the steps of preparing polishing solution and passivation solution, firstly placing a copper alloy sheet with the purity of 99.5% into the polishing solution for polishing, and then placing the copper alloy sheet into the passivation solution for passivation. In the passivation method, BTA, nickel salt and rare earth salt are used for preparing the passivation solution of the copper alloy, the preparation method is simple, the passivation solution is nontoxic and harmless, and meanwhile, the corrosion inhibition aids such as triethanolamine borate, phytic acid and the like are added for optimizing the film forming quality of the copper alloy, so that the corrosion resistance of the copper alloy is improved. The passivation method provided by the invention is simple and remarkable in effect, and is beneficial to popularization and application of the passivation method for the copper alloy surface.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a black passivation method for a copper alloy surface.
Background
The copper and copper alloy products are widely applied to various industrial fields such as instruments, decorations and the like, and passivation is an indispensable process for various copper products, so that oxidation and color loss on the surfaces of parts can be avoided, and the appearance and quality of the parts are prevented from being influenced.
BTA (benzotriazole) is widely used as a water treatment agent, a metal rust inhibitor and a corrosion inhibitor in a gas-phase corrosion inhibitor and a lubricating oil additive of copper and copper alloy, and a film formed by passivating single BTA is very thin, so that acid resistance is very poor, other organic and inorganic additives are required to be added into passivation solution to serve as auxiliary materials, and the synergistic effect of rare earth salt and BTA can form a denser and complete passivation film on the surface of the copper material, so that the bonding force between the film and a matrix is promoted. Tests show that the addition amount of the rare earth salt is proper, otherwise, the corrosion resistance of the passivation film is reduced, and the action mechanism of the passivation film is still to be further researched.
At present, most of copper passivation is a traditional process containing hexavalent chromium, and although the passivation effect is good, hexavalent chromium is harmful to human health and has a cancerogenic risk, so the development of a novel copper passivation process without hexavalent chromium is a problem which needs to be solved urgently at present.
A brass passivation solution is published in a Chinese patent database, and the publication number is as follows: CN 110760829A, bulletin day 2020, 2 months and 7 days, wherein the solute of the brass passivating solution is sulfuric acid, potassium dichromate and sodium fluoride, the volume ratio of sulfuric acid to water is 5-10:1, the unit is gram/liter, the volume ratio of potassium dichromate to water is 90-150:1, the unit is gram/liter, and the volume ratio of sodium fluoride to water is 3-5:1, the unit is gram/liter; the Chinese patent database discloses a purple tin cobalt copper passivation coloring of a galvanized layer, and the publication number is as follows: CN 106756966A, publication date 2017, 5 and 31, the passivation solution is prepared by deionized water according to the concentration of thiourea of 8-60 g/L, the concentration of an auxiliary complexing agent of 5-30 g/L, the concentration of cuprous chloride of 3-12 g/L and the concentration of cobalt sulfate of 5-30 g/L; an environment-friendly efficient brass passivation treatment process is disclosed in a Chinese patent database, and the publication number is as follows: CN 104294266A, 21 days of publication 2015, the passivating solution mainly comprises 0.02-50 g/L of mercaptobenzothiazole salt, 0.5-20 g/L of sodium fatty alcohol polyoxyethylene ether sulfate and 0.5-500 ml/L of sulfonated castor oil. The passivation solution is not good in passivation film forming effect and corrosion-resistant, and a large amount of toxic solvents are used.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a black passivation method for the surface of a copper alloy, which uses BTA and rare earth salt as main raw materials of passivation solution, has wide sources of raw materials, is nontoxic and harmless, has good film forming effect, and is favorable for realizing large-scale popularization and application.
The purpose of the invention is realized in the following way: a black passivation method for a copper alloy surface comprises the following steps:
step 1: polishing: firstly preparing polishing solution, placing a copper alloy sheet with the purity of 99.5% into the polishing solution for polishing, controlling the polishing temperature and the polishing time, respectively flushing the surface of the copper alloy by using tap water and deionized water after polishing is finished, and then drying;
step 2: passivation: firstly preparing passivation solution, placing the copper alloy sheet polished in the step 1 into the passivation solution, controlling the passivation temperature and time, respectively using tap water and deionized water to wash the surface of the copper alloy after passivation, and then drying.
The preparation method of the passivation solution in the invention comprises the following steps: the passivation solution for the copper alloy is prepared by using BTA, rare earth salt and nickel salt, the preparation method is simple and nontoxic, citric acid, triethanolamine borate and phytic acid are added as corrosion inhibition auxiliary agents to optimize the film forming quality of the copper alloy, the corrosion resistance of the copper alloy is improved, the BTA and the emulsifier OP-10 show good corrosion inhibition synergistic effect after being compounded, and the two units in the molecule interact to increase the charge transfer and transfer of the BTA, so that the BTA is easier to adsorb on the surface of the copper alloy.
Compared with the prior art, the invention has the beneficial effects that:
firstly, BTA is used as a main raw material of the passivation solution, the raw material sources are widely and easily available, the test cost is reduced, and compared with the passivation solution containing chromium in the prior art, the chromium-free passivation is cleaner and more environment-friendly and is non-toxic;
secondly, rare earth salt is used as auxiliary materials, so that the quality of film formation is enhanced, the film formation is more uniform and more compact, the corrosion resistance is strong, the film formation is also nontoxic and harmless, the production is simple, and the film formation is safe and environment-friendly.
Further, the polishing solution in step 1 includes sulfuric acid, hydrogen peroxide, ethylene glycol, EDTA (brightening agent), nitric acid, surfactant LAS, surfactant 6501 and phytic acid, wherein each liter of polishing solution contains 50 mL, 350 mL hydrogen peroxide, 300 mL ethylene glycol, 45 mL nitric acid, 1.5 g surfactant EDTA, 1.6 g surfactant 6501 and 2.5 g phytic acid.
Further, the polishing temperature in the step 1 is 30-50 ℃, and the polishing time is 30-60 s.
Further, the passivation solution in the step 2 comprises 5-15 g/L of BTA, 5-15 g/L of citric acid, 15-25 g/L of sulfosalicylic acid, 1-3 g/L of emulsifying agent, 0-3 g/L of amine triacetate borate, 0-3 g/L of rare earth salt and 0-3 g/L of nickel salt.
Further, the emulsifier is one of OP-10, triethanolamine, LAO and 6501.
Further, the rare earth salt is lithium nitrate or lanthanum salt.
Further, the nickel salt is one of nickel nitrate, nickel carbonate and nickel sulfate.
Further, in the step 2, the passivation temperature is 30-90 ℃, the passivation time is 3-8 min, tap water is used for washing until no greasy feeling is caused to the touch after passivation is finished, deionized water is used for washing for 2-3 times, and then drying is performed.
Drawings
FIG. 1 shows the effect of different amounts of emulsifier OP-10 on the open circuit voltage.
Fig. 2 is a tafel plot of copper alloy sheets of examples 1-3.
Description of the embodiments
Examples
A black passivation method for a copper alloy surface comprises the following steps:
step 1: polishing: firstly preparing polishing solution, adding 50 ml/L sulfuric acid into 500 mL deionized water, adding 350 ml/L hydrogen peroxide 1 mL, 300 ml/L ethylene glycol 1 mL, 45 ml/L nitric acid 50 mL, 1.5 g/L EDTA 1.5 g, 1.5 g/L surfactant LAS 1g, 1.6 g/L surfactant 6501 g and 2.5 mL/L phytic acid 2 mL, uniformly mixing to obtain polishing solution, and placing copper alloy sheets into the prepared polishing solution, wherein the polishing temperature is controlled to be 50 ℃ and the polishing time is controlled to be 20 s; after the end, tap water and deionized water are respectively used for flushing the surface of the copper alloy, and then the copper alloy is dried.
Step 2: passivation: firstly preparing passivation solution, uniformly mixing BTA with the concentration of 5 g/L, citric acid with the concentration of 10 g/L, sulfosalicylic acid with the concentration of 15 g/L, OP-10 with the concentration of 2 g/L, amine triacetate borate with the concentration of 1.25 g/L, lithium nitrate with the concentration of 0.5 g/L and nickel sulfate with the concentration of 0.5 g/L to obtain the passivation solution, soaking the copper alloy sheet polished in the step 1 in the passivation solution, controlling the passivation temperature to be 60 ℃ for 5min, washing the copper alloy sheet with tap water until no greasy feeling is caused by hand touch after passivation, washing for 2-3 times with deionized water, and finally drying by using an electric hair drier.
Examples
A black passivation method for a copper alloy surface comprises the following steps:
step 1: polishing: firstly preparing polishing solution, adding 50 ml/L sulfuric acid into 500 mL deionized water, adding 350 ml/L hydrogen peroxide 1 mL, 300 ml/L ethylene glycol 1 mL, 45 ml/L nitric acid 50 mL, 1.5 g/L EDTA 1.5 g, 1.5 g/L surfactant LAS 1g, 1.6 g/L surfactant 6501 g and 2.5 mL/L phytic acid 2 mL, uniformly mixing to obtain polishing solution, and placing copper alloy sheets into the prepared polishing solution, wherein the polishing temperature is controlled to be 50 ℃ and the polishing time is controlled to be 20 s; after the end, tap water and deionized water are respectively used for flushing the surface of the copper alloy, and then the copper alloy is dried.
Step 2: passivation: firstly preparing passivation solution, uniformly mixing BTA with the concentration of 15 g/L, citric acid with the concentration of 15 g/L, sulfosalicylic acid with the concentration of 18 g/L, OP-10 with the concentration of 1 g/L, amine triacetate borate with the concentration of 1.75 g/L, lithium nitrate with the concentration of 1 g/L and nickel sulfate with the concentration of 1.5 g/L to obtain the passivation solution, soaking the copper alloy sheet polished in the step 1 in the passivation solution, controlling the passivation temperature to be 60 ℃ for 5min, washing the copper alloy sheet with tap water until no greasy feeling is caused by hand touch after passivation, washing for 2-3 times with deionized water, and finally drying by using an electric hair drier.
Examples
A black passivation method for a copper alloy surface comprises the following steps:
step 1: polishing: firstly preparing polishing solution, adding 50 ml/L sulfuric acid into 500 mL deionized water, adding 350 ml/L hydrogen peroxide 1 mL, 300 ml/L ethylene glycol 1 mL, 45 ml/L nitric acid 50 mL, 1.5 g/L EDTA 1.5 g, 1.5 g/L surfactant LAS 1g, 1.6 g/L surfactant 6501 g and 2.5 mL/L phytic acid 2 mL, uniformly mixing to obtain polishing solution, and placing copper alloy sheets into the prepared polishing solution, wherein the polishing temperature is controlled to be 50 ℃ and the polishing time is controlled to be 20 s; after the end, tap water and deionized water are respectively used for flushing the surface of the copper alloy, and then the copper alloy is dried.
Step 2: passivation: firstly preparing passivation solution, uniformly mixing BTA with the concentration of 10 g/L, citric acid with the concentration of 20 g/L, sulfosalicylic acid with the concentration of 12 g/L, OP-10 with the concentration of 2 g/L, amine triacetate borate with the concentration of 0.75 g/L, lithium nitrate with the concentration of 1.5 g/L and nickel sulfate with the concentration of 0.5 g/L to obtain the passivation solution, soaking the copper alloy sheet polished in the step 1 in the passivation solution, controlling the passivation temperature to be 60 ℃ for 5min, washing the copper alloy sheet with tap water until no greasy feeling is caused by hand touch after passivation, washing for 2-3 times with deionized water, and finally drying by using an electric hair drier.
FIG. 1 shows the effect of the emulsifier OP-10 content on the open circuit potential, which tends to shift positively as the OP-10 content increases. When the OP-10 content is at the first level of 0.75%, the open circuit potential is at a minimum value of-0.178V; at a second level of 1.25% OP-10 content, the open circuit potential increases to-0.155. 0.155V; when the OP-10 content increases to a third level of 1.75%, the open circuit potential increases to-0.153 and V. Thus, at a first level of 0.75% OP-10, the open circuit potential is minimal and the corrosion resistance of the film is best.
Fig. 2 is a Tafel graph of the copper alloy sheet test of examples 1 to 3, wherein the corrosion resistance potential of example 1 is-0.154 and V, the corrosion resistance potential of example 2 is-0.098 and V, the corrosion resistance potential of example 3 is-0.126 and V, the corrosion resistance potential of example 2 is larger, and the passivation solution has better corrosion resistance. Namely, the passivation effect of the copper alloy is best when the BTA content is 15 g/L, the citric acid content is 15 g/L, the sulfosalicylic acid content is 8 g/L, OP-10 content is 1 g/L, the amine triacetate borate content is 1.75 g/L, the lithium nitrate content is 1 g/L, and the nickel sulfate content is 1.5 g/L.
Comparative example 1:
selection of an emulsifier: firstly, polishing a copper alloy sheet, wherein the specific step of polishing is the same as that of example 2, placing the polished copper alloy sheet in a passivation solution for passivation, and the specific step of passivation is the same as that of example 2, using different emulsifying agents, and testing the influence of the different emulsifying agents on corrosion resistance voltage:
| type of emulsifier | Corrosion resistant potential/V |
| OP-10 | -0.153 V |
| Triethanolamine salt | -0.178 V |
| LAO | -0.207 V |
| 6501 | -0.212 V |
From the comparison, the passivation solution prepared by using the emulsifier OP-10 has the greatest corrosion resistance potential when the copper alloy sheet is passivated, and the corrosion resistance of the film is the best.
Comparative example 2:
rare earth salt selection:
| rare earth salt species | Open circuit potential/V |
| Lithium nitrate | -0.185 V |
| Lanthanum salt | -0.252 V |
From comparison, the passivation solution prepared by using lithium nitrate has the greatest corrosion resistance potential when passivating the copper alloy sheet, and the film has the best corrosion resistance.
Comparative example 3:
selection of nickel salt:
| type of nickel salt | Open circuit potential/V |
| Nickel nitrate | -0.178 V |
| Nickel carbonate | -0.252 V |
| Nickel sulfate | -0.321 V |
From the comparison, the passivation solution prepared by using nickel nitrate has the greatest corrosion resistance potential when the copper alloy sheet is passivated, and the corrosion resistance of the film is the best.
Comparative example 4:
effect of BTA concentration on open circuit potential:
| BTA concentration (g/L) | Open circuit potential/V |
| 5 | -0.176 V |
| 8 | -0.167 V |
| 10 | -0.165 V |
| 13 | -0.152 V |
| 15 | -0.145 V |
| 18 | -0.159 V |
| 20 | -0.178 V |
As is clear from comparison, the passivation solution prepared by BTA with the concentration of 15 g/L has the highest corrosion resistance potential when passivating the copper alloy sheet, and the corrosion resistance of the film is best, and when the BTA concentration is too high or too low, the corrosion resistance potential is lowered instead, so that the corrosion resistance of the film is lowered.
Comparative example 5:
influence of triethanolamine borate concentration on open circuit potential:
| triethanolamine borate concentration (g/L) | Open circuit potential/V |
| 0 | -0.178 V |
| 1 | -0.163 V |
| 1.75 | -0.153 V |
| 2 | -0.154 V |
| 2.5 | -0.155 V |
| 3 | -0.162 V |
| 4 | -0.169 V |
| 5 | -0.172 V |
As is clear from the comparison, the passivation solution prepared by using triethanolamine borate with the concentration of 1.75. 1.75 g/L has the greatest corrosion resistance potential when the copper alloy sheet is passivated, and the corrosion resistance of the film is the best.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (8)
1. The black passivation method for the surface of the copper alloy is characterized by comprising the following steps of:
step 1: polishing: firstly preparing polishing solution, placing a copper alloy sheet with the purity of 99.5% into the polishing solution for polishing, controlling the polishing temperature and the polishing time, respectively flushing the surface of the copper alloy by using tap water and deionized water after polishing is finished, and then drying;
step 2: passivation: firstly preparing passivation solution, placing the copper alloy sheet polished in the step 1 into the passivation solution, controlling the passivation temperature and time, respectively using tap water and deionized water to wash the surface of the copper alloy after passivation, and then drying.
2. The method for passivating the surface of a copper alloy in black according to claim 1, wherein the method comprises the following steps: the polishing solution in the step 1 comprises sulfuric acid, hydrogen peroxide, ethylene glycol, EDTA (brightening agent), nitric acid, surfactant LAS, surfactant 6501 and phytic acid, wherein 50 mL, 350 mL hydrogen peroxide, 300 mL ethylene glycol, 45 mL nitric acid, 1.5 g surfactant EDTA, 1.6 g surfactant 6501 and 2.5 g phytic acid are contained in each liter of the polishing solution.
3. The method for passivating the surface of a copper alloy in black according to claim 1, wherein the method comprises the following steps: the polishing temperature in the step 1 is 30-50 ℃, and the polishing time is 30-60 s.
4. The method for passivating the surface of a copper alloy in black according to claim 1, wherein the method comprises the following steps: the passivation solution in the step 2 comprises 5-15 g/L of BTA, 5-15 g/L of citric acid, 15-25 g/L of sulfosalicylic acid, 1-3 g/L of emulsifying agent, 0-3 g/L of amine triacetate borate, 0-3 g/L of rare earth salt and 0-3 g/L of nickel salt.
5. The method for passivating the surface of a copper alloy in black according to claim 4, wherein the method comprises the following steps: the emulsifier is one of OP-10, triethanolamine, LAO and 6501.
6. The method for passivating the surface of a copper alloy in black according to claim 4, wherein the method comprises the following steps: the rare earth salt is lithium nitrate or lanthanum salt.
7. The method for passivating the surface of a copper alloy in black according to claim 4, wherein the method comprises the following steps: the nickel salt is one of nickel nitrate, nickel carbonate and nickel sulfate.
8. The method for passivating the surface of a copper alloy in black according to claim 1, wherein the method comprises the following steps: and in the step 2, the passivation temperature is 30-90 ℃, the passivation time is 3-8 min, tap water is used for washing until no greasy feeling is caused to the touch after passivation is finished, deionized water is used for washing for 2-3 times, and then drying is performed.
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