CN102312232B - Environment-friendly copper and copper alloy surface passivation treatment fluid and passivation treatment method - Google Patents
Environment-friendly copper and copper alloy surface passivation treatment fluid and passivation treatment method Download PDFInfo
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- CN102312232B CN102312232B CN2011102120555A CN201110212055A CN102312232B CN 102312232 B CN102312232 B CN 102312232B CN 2011102120555 A CN2011102120555 A CN 2011102120555A CN 201110212055 A CN201110212055 A CN 201110212055A CN 102312232 B CN102312232 B CN 102312232B
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- 238000002161 passivation Methods 0.000 title claims abstract description 121
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- 239000010949 copper Substances 0.000 title claims abstract description 64
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 55
- 239000012530 fluid Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 heterocycle compound Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 39
- 238000004140 cleaning Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 17
- 229960003540 oxyquinoline Drugs 0.000 claims description 17
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 17
- 238000005498 polishing Methods 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 3
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 10
- 235000011180 diphosphates Nutrition 0.000 abstract description 6
- 230000036541 health Effects 0.000 abstract description 6
- 238000001338 self-assembly Methods 0.000 abstract description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 abstract 2
- 239000012964 benzotriazole Substances 0.000 description 21
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 19
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 18
- 238000002791 soaking Methods 0.000 description 15
- 229910001369 Brass Inorganic materials 0.000 description 13
- 239000010951 brass Substances 0.000 description 13
- 235000019260 propionic acid Nutrition 0.000 description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 9
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 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 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000002949 phytic acid Nutrition 0.000 description 4
- 229940068041 phytic acid Drugs 0.000 description 4
- 239000000467 phytic acid Substances 0.000 description 4
- 229940048084 pyrophosphate Drugs 0.000 description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 229910017849 NH2—NH2 Inorganic materials 0.000 description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- RRUDCFGSUDOHDG-UHFFFAOYSA-N acetohydroxamic acid Chemical compound CC(O)=NO RRUDCFGSUDOHDG-UHFFFAOYSA-N 0.000 description 1
- 229960001171 acetohydroxamic acid Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- HYYHQASRTSDPOD-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.OP(O)(O)=O HYYHQASRTSDPOD-UHFFFAOYSA-N 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses an environment-friendly copper and copper alloy surface passivation treatment fluid and its passivation treatment method. Water or ethanol is used as a solvent of the passivation treatment fluid and its solute contains an N-C heterocycle compound; when the solvent is water, the solute also contains at least one component selected from a carboxylic acid compound and pyrophosphate; and when the solvent is ethanol, the solute also contains at least one component selected from a thio-alcohol compound, a carboxylic acid compound and pyrophosphate. In comparison with the prior art, by the principle of combining large molecular weight solute molecules and small molecular weight solute molecules together for self assembly on the surface of copper and copper alloy, the passivation treatment fluid provided by the invention has a much better passivation effect than a passivation treatment fluid, the solute of which is a single N-C heterocyclic compound, contains no substances of polluting the environment and influencing the health of human body, is convenient to use, requires low price, and has a good application prospect in the market.
Description
Technical Field
The invention relates to the technical field of surface treatment of metal materials, in particular to an environment-friendly passivation treating fluid for copper and copper alloy surfaces and a passivation treating method thereof.
Background
The processing amount of Chinese copper and copper alloy is about 1000 ten thousand tons per year, and the annual output value is more than 6000 million yuan. Generally, after machining copper and copper alloy workpieces, passivation is required to improve the discoloration resistance and corrosion resistance of the workpieces. At present, the passivation of copper and copper alloy products is mainly carried out by cleaning treatment liquid such as chromic acid or the mixture thereof, but the waste water after the cleaning and passivation treatment by using the treatment liquid contains hexavalent chromium ions, which seriously pollutes the environment and affects the body health of operators. Therefore, how to eliminate hexavalent chromium ions in the passivated wastewater is a key problem to be solved by the copper and copper alloy surface treatment technology.
At present, environmental protection methods for passivating copper and copper alloy surfaces are reported, for example, the invention patent with application number CN86103910.6 adopts benzotriazole and polyvinyl alcohol as passivating agents, but the patent still uses a small amount of chromic acid; the invention patent with application number of CN200810187682.6 adopts mixed solution of 5-8g/l benzotriazole, 2-4g/l 1-phenyl-5 mercapto tetrazole, 14-18g/l tartaric acid (or citric acid), 2-4g/l sodium molybdate (or sodium tungstate) and 0.5-1g/l sodium dodecyl sulfate to passivate brass, but the passivating solution has complex components and uses expensive sodium molybdate or sodium tungstate; the invention with the application number of CN201010217372.1 adopts phytic acid as a passivating agent, but the process is carried out under a certain external voltage; the invention with the application number of CN201010595972.1 adopts mixed liquid of phytic acid, hydrogen peroxide, boric acid, polyethylene glycol and the like to passivate brass, but the method has the same complicated components, and the phytic acid (phytic acid) has high phosphorus content, which can increase the Chemical Oxygen Demand (COD) in the wastewater.
Disclosure of Invention
The technical purpose of the invention is to provide an environment-friendly passivation treatment solution for the surfaces of copper and copper alloys and a passivation treatment method for the surfaces of copper and copper alloys by using the passivation treatment solution, aiming at the technical current situation, the passivation treatment solution has the advantages of no substances which pollute the environment and influence the human health, good passivation effect, convenient use, low price and the like.
The technical scheme adopted by the invention for realizing the technical purpose is as follows: the environment friendly passivating treatment liquid for copper and copper alloy surface has solvent of water or ethanol and solute containing N-C heterocyclic compound, and features that: when the solvent is water, the solute also comprises at least one of carboxylic acid compounds and pyrophosphate; when the solvent is ethanol, the solute also comprises at least one of thiol compounds and carboxylic acid compounds.
In the above technical scheme:
the N-C heterocyclic compound is preferably at least one of benzotriazole and 8-hydroxyquinoline;
the thiol compound is preferably at least one of 1, 2-ethanedithiol, n-propyl mercaptan and dodecyl mercaptan;
the carboxylic acid compound is preferably at least one of formic acid, acetic acid, oxalic acid, propionic acid, butyric acid, formate, acetate, oxalate, propionate and butyrate;
the pH value range of the passivation treatment liquid is preferably 2-7.
In the passivation treatment liquid, when the solvent is water, the concentration range of the benzotriazole is preferably 1g/l to the saturation concentration of the benzotriazole, and more preferably 10g/l to 19 g/l; the concentration range of the carboxylic acid compounds is 1g/l to 20g/l, and more preferably 5g/l to 15 g/l; the concentration of pyrophosphate is in the range of 1g/l to 20g/l, more preferably 1g/l to 5 g/l.
In the passivation treatment liquid, when the solvent is ethanol, the concentration range of 8-hydroxyquinoline is 0.1g/l to the saturated concentration, and more preferably 1g/l to 5 g/l; the concentration of the thiol compound is 0.1 to 1g/l, and more preferably 0.5 to 1 g/l.
The method for treating the surfaces of copper and copper alloy by using the passivation treating fluid comprises the following steps:
step 1, preparation of passivation treatment liquid:
dissolving solute containing N-C heterocyclic compounds in water, and then adding carboxylic acid compounds and/or pyrophosphate to obtain passivation treatment solution; or,
dissolving solute containing N-C heterocyclic compounds in an ethanol solvent, and then adding thiol compounds and/or carboxylic acid compounds to obtain passivation treatment solution;
step 2, degreasing the surfaces of copper and copper alloy:
adding a proper amount of sodium dodecyl sulfate into NaOH solution with the mass percentage concentration of 5-20% or KOH solution with the mass percentage concentration of 5-20% to obtain mixed solution, putting copper or copper alloy into the mixed solution, and cleaning for 3-10 minutes at the cleaning temperature of 40-70 ℃;
wherein, the concentration of the sodium dodecyl sulfate in the mixed solution is preferably 0.5g/l to 10g/l, and more preferably 2 g/l; the cleaning temperature is preferably 60-70 ℃;
step 3, surface oxidation film removal treatment of copper and copper alloy:
performing surface oxide film removal treatment on copper or copper alloy by using mechanical polishing, chemical polishing or the method described in the patent application No. CN 201110108791.6;
in the patent application No. CN201110108791.6, the treatment method for removing copper and the oxide film on the surface of copper alloy by reduction with the treatment solution specifically comprises the following steps:
(1) preparation of treatment liquid: adding a reducing agent into water to form a treatment solution, wherein the reducing agent is one or a mixture of more of ascorbic acid, hypophosphite, glucose, hydrazine and derivatives thereof, and hydroxylamine and derivatives thereof, and adjusting the pH value of the treatment solution to 2-13;
(2) surface reduction treatment of copper and copper alloy: and (3) soaking the copper and the copper alloy which are deoiled in the step (2) in the treatment solution at the temperature of normal temperature to 90 ℃, taking out the copper and the copper alloy after the surfaces are reduced to the natural colors of the copper and the copper alloy, and then cleaning and drying the copper and the copper alloy.
The hydrazine and derivatives thereof described in (1) above include, but are not limited to, NH2-NH2、NH2-NH2·H2O, phenylhydrazine, R1R2N-NR1R2(R represents a hydrocarbon group); the hydroxylamine and its derivatives include but are not limited to N, N-diethylhydroxylamine, N-dimethylhydroxylamine, hydroxylamine phosphate, acetohydroxamic acid, hydroxylamine sulfate, hydroxylamine chloride.
Step 4, passivating the surfaces of copper and copper alloy:
and (3) putting the copper or the copper alloy treated in the step (3) into the passivation treatment liquid prepared in the step (1) for surface passivation treatment.
The environment-friendly passivation treating fluid for the surfaces of copper and copper alloys is an aqueous solution or an ethanol solution, wherein the solution can perform self-assembly reaction with the copper and the copper alloys to self-assemble a compact monolayer film on the surfaces of the copper and the copper alloys, thereby realizing the passivation effect on the surfaces of the copper and the copper alloys. The invention is characterized in that the solute not only contains N-C heterocyclic compounds, but also contains at least one of carboxylic acid compounds, thiol compounds and pyrophosphate. Because the molecular weights of all solutes are different, the self-assembly capacities of the solutes on the surfaces of copper and copper alloys are different, and the compactness of the formed self-assembled monolayer film is also different, so that the synergistic effect is realized, and the passivation effect of the surfaces of copper and copper alloys is integrally improved. Especially, when the molecular weight of each solute in the passivation solution is relatively large, the solute with the relatively large molecular weight self-assembles a monolayer film with the relatively large molecular weight on the surface of the copper and the copper alloy, the monolayer film has relatively long molecular chains, so that small gaps are inevitable between molecules, and the solute with the relatively small molecular weight can be assembled in the gaps to fill the small gaps, thereby forming a compact monolayer film on the surface of the copper and the copper alloy, isolating the copper and the copper alloy from outside air and water, and improving the effects of surface passivation and corrosion resistance of the copper and the copper alloy.
When copper is oxidized, the color changes obviously, brass becomes dark, and red copper becomes black. Experiments prove that:
at present, the luster of brass subjected to acid pickling and polishing treatment disappears in humid air for about half a month, while the color of red copper changes in three days, especially in an environment with high humidity and high temperature, the color disintegration speed is higher, for example, under the conditions that the humidity is 80% and the temperature is 70-90 ℃, the color retention time of brass is less than 5 hours, and the color retention time of red copper is less than 2 hours;
at present, after acid cleaning and polishing treatment, brass treated by a passivation treatment solution with a single solute of an N-C heterocyclic compound disappears after about 1 month in humid air, while red copper changes its color after a week, and especially under an environment with high humidity and high temperature, the color-changing speed of red copper is faster, for example, under the conditions of humidity of 80% and temperature of 70-90 ℃, the color-keeping time of brass is less than 50 hours, and the color-keeping time of red copper is less than 5 hours;
however, in the present invention, the copper and copper alloy after acid cleaning and polishing and then after passivation treatment by the passivation treatment solution of the present invention have the following effects:
(1) in humid air, brass does not change color for half a year, and red copper does not change color for three months;
(2) under the conditions that the humidity is 80% and the temperature is 70-90 ℃: the color of the brass can be kept for more than 100 hours, and the color of the red copper can be kept for more than 50 hours.
Therefore, compared with the prior art, the passivation treating fluid for the surfaces of copper and copper alloys provided by the invention adopts the principle that solute molecules with large molecular weight are combined with solute molecules with small molecular weight to be self-assembled on the surfaces of copper and copper alloys together, and has the following advantages:
(1) the passivation effect is far better than that of a passivation treatment liquid with a solute of a single N-C heterocyclic compound;
(2) the chromium-free passivation solution does not contain substances which pollute the environment and influence the health of human bodies, is an environment-friendly passivation solution, and avoids the problems of environment pollution, human body health pollution and the like caused by a large amount of hexavalent chromium generated during passivation treatment;
(3) the use is convenient, the passivation solution is directly dried without cleaning, and the water is saved;
(4) the price is low, the dosage is small and the effect is good;
(5) the application range is wide, the copper alloy passivation agent not only can passivate copper alloy, but also has good passivation effect on red copper (pure copper).
Therefore, the passivation treating fluid and the passivation treating method for the surfaces of copper and copper alloys have the advantages of low cost, convenience in use, rapidness in treatment, remarkable effect, environmental friendliness, health and the like, and have good market application prospects.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to facilitate the understanding of the invention and are not intended to be limiting in any way.
The following passivation samples were a copper alloy spray gun equipped with a red copper cutting tip and a brass spray gun equipped with a brass cutting tip.
Comparative example 1:
in this comparative example, only the surface cleaning and the oxide film removal treatment were performed on the passivation treatment sample, and the passivation treatment was performed without using the passivation solution, for comparison with example 1 described below. The method comprises the following specific steps:
(1) adding 2g/l of sodium dodecyl sulfate into a NaOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution, putting a passivation sample into the mixed solution, and cleaning for 5 minutes at the cleaning temperature of 60 ℃;
(2) and (3) carrying out surface oxide film removal treatment on the passivation treatment sample treated in the step (2) by using mechanical polishing.
Comparative example 2:
for further comparison with example 1 below, the formulation of the passivation solution in this comparative example is: the solvent is water, the solute is benzotriazole, and the mass concentration of the benzotriazole is 10 g/l.
The specific steps of passivating the surface of a passivated sample by using the passivating treatment liquid are as follows:
(1) dissolving a proper amount of benzotriazole in water to ensure that the mass concentration of the benzotriazole is 10g/l, thereby obtaining passivation treatment liquid;
(2) adding 2g/l of sodium dodecyl sulfate into a NaOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution, putting a passivation sample into the mixed solution, and cleaning for 5 minutes at the cleaning temperature of 60 ℃;
(3) carrying out surface oxide film removal treatment on the passivation treatment sample treated in the step (2) by using mechanical polishing;
(4) and (3) soaking the passivation treatment sample treated in the step (3) into the passivation treatment liquid prepared in the step (1) for passivation treatment, keeping the temperature of the passivation treatment liquid at 60 ℃, soaking for 5 minutes, and drying for 5 minutes at 60 ℃ after treatment.
Example 1:
in this embodiment:
the formula of the passivation treating fluid is as follows: the solvent is water, and the solutes are benzotriazole and propionic acid, wherein the mass concentration of the benzotriazole is 10g/l, and the mass concentration of the propionic acid is 10 g/l.
The specific steps of passivating the surface of a passivated sample by using the passivating treatment liquid are as follows:
(1) dissolving a proper amount of benzotriazole in water, and then adding a proper amount of propionic acid to ensure that the mass concentration of the benzotriazole is 10g/l and the mass concentration of the propionic acid is 10g/l so as to obtain passivation treatment solution;
(2) adding 2g/l of sodium dodecyl sulfate into a NaOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution, putting a passivation sample into the mixed solution, and cleaning for 5 minutes at the cleaning temperature of 60 ℃;
(3) carrying out surface oxide film removal treatment on the passivation treatment sample treated in the step (2) by using mechanical polishing;
(4) and (3) soaking the passivation treatment sample treated in the step (3) into the passivation treatment liquid prepared in the step (1) for passivation treatment, keeping the temperature of the passivation treatment liquid at 60 ℃, soaking for 5 minutes, and drying for 5 minutes at 60 ℃ after treatment.
Example 2:
in this embodiment:
the formula of the passivation treating fluid is as follows: the solvent is ethanol, and the solute is benzotriazole and dodecyl mercaptan, wherein the mass concentration of the benzotriazole is 10g/l, and the mass concentration of the dodecyl mercaptan is 1 g/l.
The specific steps of passivating the surface of a passivated sample by using the passivating treatment liquid are as follows:
(1) dissolving a proper amount of benzotriazole into ethanol, and then adding a proper amount of dodecyl mercaptan so that the mass concentration of the benzotriazole is 10g/l and the mass concentration of the dodecyl mercaptan is 1g/l to obtain passivation treatment liquid;
(2) adding 2g/l of sodium dodecyl sulfate into a NaOH solution with the mass percentage concentration of 5-20%, putting a passivation treatment sample into the mixed solution, and cleaning for 10 minutes at the cleaning temperature of 40 ℃;
(3) carrying out surface oxide film removal treatment on the passivation treatment sample treated in the step (2) by using chemical polishing;
(4) and (3) soaking the passivation treatment sample treated in the step (3) into the passivation treatment liquid prepared in the step (1) for passivation treatment, keeping the temperature of the passivation treatment liquid at 60 ℃, soaking for 5 minutes, and drying for 5 minutes at 60 ℃ after treatment.
Example 3:
in this embodiment:
the formula of the passivation treating fluid is as follows: the solvent is water, and the solutes are benzotriazole and pyrophosphoric acid, wherein the mass concentration of the benzotriazole is 10g/l, and the mass concentration of the pyrophosphoric acid is 5 g/l.
The specific steps of passivating the surface of a passivated sample by using the passivating treatment liquid are as follows:
(1) dissolving a proper amount of benzotriazole into ethanol, and then adding a proper amount of pyrophosphoric acid to ensure that the mass concentration of the benzotriazole is 10g/l and the mass concentration of the pyrophosphoric acid is 5g/l so as to obtain passivation treatment solution;
(2) adding 2g/l of sodium dodecyl sulfate into a NaOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution, putting a passivation sample into the mixed solution, and cleaning for 3 minutes at the cleaning temperature of 70 ℃;
(3) carrying out surface oxide film removal treatment on the passivated sample by using the method described in the patent application No. CN 201110108791.6;
(4) and (3) soaking the passivation treatment sample treated in the step (3) into the passivation treatment liquid prepared in the step (1) for passivation treatment, keeping the temperature of the passivation treatment liquid at 60 ℃, soaking for 5 minutes, and drying for 5 minutes at 60 ℃ after treatment.
Comparative example 3:
for comparison with example 4 below, the passivation solution formulation in this comparative example was: the solvent is ethanol, the solute is 8-hydroxyquinoline, and the mass concentration of the 8-hydroxyquinoline is 2 g/l.
The specific steps of passivating the surface of a passivated sample by using the passivating treatment liquid are as follows:
(1) dissolving a proper amount of 8-hydroxyquinoline in water to ensure that the mass concentration of the 8-hydroxyquinoline is 2g/l, thereby obtaining passivation treatment liquid;
(2) adding 2g/l of sodium dodecyl sulfate into a KOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution, putting a passivation sample into the mixed solution, and cleaning for 5 minutes at the cleaning temperature of 60 ℃;
(3) carrying out surface oxide film removal treatment on the passivation treatment sample treated in the step (2) by using mechanical polishing;
(4) and (3) soaking the passivation treatment sample treated in the step (3) into the passivation treatment liquid prepared in the step (1) for passivation treatment, keeping the temperature of the passivation treatment liquid at 60 ℃, soaking for 5 minutes, and drying for 5 minutes at 60 ℃ after treatment.
Example 4:
in this embodiment:
the formula of the passivation treating fluid is as follows: the solvent is ethanol, and the solute is 8-hydroxyquinoline and propionic acid, wherein the mass concentration of the 8-hydroxyquinoline is 2g/l, and the mass concentration of the propionic acid is 10 g/l.
The specific steps of passivating the surface of a passivated sample by using the passivating treatment liquid are as follows:
(1) dissolving a proper amount of 8-hydroxyquinoline in water, and then adding a proper amount of propionic acid to ensure that the mass concentration of the 8-hydroxyquinoline is 2g/l and the mass concentration of the propionic acid is 10g/l so as to obtain passivation treatment solution;
(2) adding 2g/l of sodium dodecyl sulfate into a KOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution, putting a passivation sample into the mixed solution, and cleaning for 5 minutes at the cleaning temperature of 60 ℃;
(3) carrying out surface oxide film removal treatment on the passivation treatment sample treated in the step (2) by using mechanical polishing;
(4) and (3) soaking the passivation treatment sample treated in the step (3) into the passivation treatment liquid prepared in the step (1) for passivation treatment, keeping the temperature of the passivation treatment liquid at 60 ℃, soaking for 5 minutes, and drying for 5 minutes at 60 ℃ after treatment.
Example 5:
in this embodiment:
the formula of the passivation treating fluid is as follows: the solvent is ethanol, and the solute is 8-hydroxyquinoline and dodecyl mercaptan, wherein the mass concentration of 8-hydroxyquinoline is 2g/l, and the mass concentration of dodecyl mercaptan is 1 g/l.
The specific steps of passivating the surface of a passivated sample by using the passivating treatment liquid are as follows:
(1) dissolving a proper amount of 8-hydroxyquinoline in water, and then adding a proper amount of dodecyl mercaptan so that the mass concentration of the 8-hydroxyquinoline is 2g/l and the mass concentration of the dodecyl mercaptan is 10g/l to obtain passivation treatment liquid;
(2) adding 2g/l of sodium dodecyl sulfate into a KOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution, putting a passivation sample into the mixed solution, and cleaning for 5 minutes at the cleaning temperature of 60 ℃;
(3) carrying out surface oxide film removal treatment on the passivation treatment sample treated in the step (2) by using mechanical polishing;
(4) and (3) soaking the passivation treatment sample treated in the step (3) into the passivation treatment liquid prepared in the step (1) for passivation treatment, keeping the temperature of the passivation treatment liquid at 60 ℃, soaking for 5 minutes, and drying for 5 minutes at 60 ℃ after treatment.
The passivated samples treated in the above examples were tested at a humidity of 80% and a temperature of 90 ℃ to obtain the results shown in the following table:
the samples passivated in the above examples were baked in an oven at a humidity of 80% and a temperature of 70 ℃ and the time required for the passivated samples, i.e., the copper alloy lance equipped with the red copper cutting tip and the brass lance equipped with the brass cutting tip to start discoloring was observed to obtain the results shown in the following table.
The above embodiments are described in detail to explain the technical solutions and advantages of the present invention, and it should be understood that the above embodiments are only specific examples of the present invention and are not intended to limit the present invention, and any modifications and improvements made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The environment-friendly passivation treating fluid for the surfaces of copper and copper alloys has the following characteristics that the solvent is ethanol, and the solute comprises N-C heterocyclic compounds: the solute also contains thiol compounds; the N-C heterocyclic compound is 8-hydroxyquinoline, the concentration range of the 8-hydroxyquinoline in the passivation treatment liquid is 0.1g/l to the saturation concentration, and the concentration of the thiol compound is 0.1g/l to 1 g/l.
2. The environment-friendly passivation treating fluid for copper and copper alloy surfaces as claimed in claim 1, wherein: the thiol compound is at least one of 1, 2-ethanedithiol, n-propyl thiol and dodecyl thiol.
3. The environment-friendly passivation treating fluid for copper and copper alloy surfaces as claimed in claim 1, wherein: the pH value range of the passivation treatment liquid is 2-7.
4. The environment-friendly passivation treating fluid for copper and copper alloy surfaces as claimed in claim 1, wherein: in the passivation treatment liquid, the concentration range of 8-hydroxyquinoline is 1g/l to 5g/l, and the concentration of thiol compounds is 0.5g/l to 1 g/l.
5. A method for treating copper and copper alloy surfaces with the passivation solution of any one of claims 1 to 4, characterized by: the method comprises the following steps:
step 1, preparation of passivation treatment liquid:
dissolving solute containing N-C heterocyclic compounds in an ethanol solvent, and then adding thiol compounds to obtain passivation treatment solution;
step 2, degreasing the surfaces of copper and copper alloy:
adding a proper amount of sodium dodecyl sulfate into NaOH solution with the mass percentage concentration of 5-20% or KOH solution with the mass percentage concentration of 5-20% to obtain mixed solution, putting copper or copper alloy into the mixed solution, and cleaning for 3-10 minutes at the temperature of 40-70 ℃;
step 3, surface oxidation film removal treatment of copper and copper alloy:
carrying out oxide film removal treatment on copper and copper alloy by using mechanical polishing or chemical polishing;
step 4, passivating the surfaces of copper and copper alloy:
and (3) putting the copper or the copper alloy treated in the step (3) into the passivation treatment liquid prepared in the step (1) for surface passivation treatment.
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| CN2011102120555A CN102312232B (en) | 2011-07-27 | 2011-07-27 | Environment-friendly copper and copper alloy surface passivation treatment fluid and passivation treatment method |
| CN201310534594.XA CN103556142B (en) | 2011-07-27 | 2011-07-27 | The inactivating treatment liquid of environment-friendly type copper and copper alloy surface and deactivating process for the treatment of thereof |
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| CN103194744A (en) * | 2013-04-22 | 2013-07-10 | 江西铜业股份有限公司 | Copper foil surface passivation liquid and treatment method thereof, and treated copper foil |
| CN104625481A (en) * | 2014-12-31 | 2015-05-20 | 芜湖协诚金属制品有限公司 | Protective agent for welding spot in metal welding |
| CN104818480B (en) * | 2015-04-28 | 2018-05-11 | 太仓市林源电线电缆有限公司 | A kind of proof copper-wire braided line protective agent |
| CN104911575A (en) * | 2015-06-13 | 2015-09-16 | 周彩球 | Environment-friendly copper part passivating agent |
| CN105024081A (en) * | 2015-07-07 | 2015-11-04 | 安徽铜冠铜箔有限公司 | Novel anti-oxidation liquid for copper foil of lithium ion battery |
| CN107124829A (en) * | 2016-02-25 | 2017-09-01 | 东莞新科技术研究开发有限公司 | Pcb surface processing method |
| CN105839093B (en) * | 2016-05-31 | 2019-02-26 | 太原工业学院 | A kind of electro-coppering room temperature chromium-free passivation liquid and its passivation technology |
| CN107022756B (en) * | 2017-05-18 | 2018-03-20 | 依波精品（深圳）有限公司 | The passivation technology of silver or silver alloy |
| CN107365989B (en) * | 2017-07-11 | 2019-08-09 | 东莞市富默克化工有限公司 | A kind of metal surface treating method and its metal protective film obtained |
| CN107475723B (en) * | 2017-08-28 | 2019-11-01 | 厦门大学 | A kind of preparation method of corrosion-resistant copper electric wire |
| CN107475700B (en) * | 2017-08-28 | 2019-11-01 | 厦门大学 | A kind of corrosion resistant copper alloy surface processing method |
| WO2019042159A1 (en) * | 2017-08-28 | 2019-03-07 | 厦门大学 | Anticorrosion treatment method for copper-containing material |
| CN110195222A (en) * | 2019-06-04 | 2019-09-03 | 深圳市瑞世兴科技有限公司 | A kind of RTR subtracts copper post-processing copper foil surface passivator and its use and preparation method |
| CN112342534A (en) * | 2020-11-11 | 2021-02-09 | 桂林漓佳金属有限责任公司 | Passivating agent for passivating copper alloy surface |
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| CN101368273A (en) * | 2007-08-15 | 2009-02-18 | 江苏海迅实业集团股份有限公司 | Copper alloy antirust agent |
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-
2011
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Non-Patent Citations (2)
| Title |
|---|
| 李锋等.铜及其合金表面钝化新工艺的研究.《电镀与涂饰》.2005,第24卷(第2期),第15-17页. |
| 铜及其合金表面钝化新工艺的研究;李锋等;《电镀与涂饰》;20051231;第24卷(第2期);第15-17页 * |
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