CN116575020A - Film forming liquid for passivation film on surface of copper alloy and application thereof - Google Patents
Film forming liquid for passivation film on surface of copper alloy and application thereof Download PDFInfo
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- CN116575020A CN116575020A CN202310367836.4A CN202310367836A CN116575020A CN 116575020 A CN116575020 A CN 116575020A CN 202310367836 A CN202310367836 A CN 202310367836A CN 116575020 A CN116575020 A CN 116575020A
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- Prior art keywords
- copper alloy
- passivation
- film forming
- passivation film
- forming liquid
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- 238000002161 passivation Methods 0.000 title claims abstract description 102
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 70
- 239000007788 liquid Substances 0.000 title claims abstract description 26
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 claims abstract description 8
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 11
- 239000012964 benzotriazole Substances 0.000 claims description 11
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-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
- 239000002253 acid Substances 0.000 claims description 7
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 11
- 230000007935 neutral effect Effects 0.000 abstract description 11
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000711 cancerogenic effect Effects 0.000 abstract description 2
- 231100000315 carcinogenic Toxicity 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012756 surface treatment agent Substances 0.000 abstract description 2
- 229910001369 Brass Inorganic materials 0.000 description 26
- 239000010951 brass Substances 0.000 description 26
- 229910045601 alloy Inorganic materials 0.000 description 25
- 239000000956 alloy Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 238000005260 corrosion Methods 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 20
- 239000007921 spray Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006388 chemical passivation reaction Methods 0.000 description 3
- HBGGBCVEFUPUNY-UHFFFAOYSA-N cyclododecanamine Chemical compound NC1CCCCCCCCCCC1 HBGGBCVEFUPUNY-UHFFFAOYSA-N 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 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
- 239000002351 wastewater Substances 0.000 description 2
- 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 description 1
- 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 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 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 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XTOQOJJNGPEPMM-UHFFFAOYSA-N o-(2-oxo-1,3,2$l^{5}-dioxaphosphinan-2-yl)hydroxylamine Chemical compound NOP1(=O)OCCCO1 XTOQOJJNGPEPMM-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C23C22/05—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 using aqueous solutions
- C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
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 application discloses a film forming liquid for a passivation film on a copper alloy surface and application thereof, belonging to the technical field of metal surface treatment agents; the mixture ratio is as follows: 1.0g/L to 5.0g/L of nitrogen-containing heterocyclic compound; alkylamine 0.05g/L-0.5g/L; 5.0mL/L to 50mL/L of organic alcohol; 1.0g/L to 5.0g/L of imidazoles; glucose 2.0g/L-5.0g/L; the balance of water. The components of the film forming liquid of the passivation film on the surface of the copper alloy are organic matters, and the film forming liquid does not contain inorganic cancerogenic matters such as chromates and the like and other substances polluting the environment and damaging the health of human bodies; the use is convenient, the process is simple, the passivation effect is excellent, the passivated copper alloy can be kept unchanged for 12 months in humid air, and the neutral salt fog resistant time is more than 120 hours.
Description
Technical Field
The application relates to a film forming liquid for a passivation film on a copper alloy surface and application thereof, belonging to the technical field of metal surface treatment agents; the prepared film forming liquid for the passivation film on the surface of the copper alloy is organic, does not contain inorganic matters such as phosphate, chromate and the like, can generate an anti-corrosion film layer with uniform and attractive appearance and good corrosion resistance on the surface of the copper alloy, has a simple process, and is an environment-friendly film forming liquid for the passivation film on the surface of the copper alloy.
Background
The copper alloy has excellent conductivity, corrosion resistance and beautiful color, and is widely used for electronic materials, building materials, packaging materials, imitation gold ornaments, imitation gold artworks, copper words, copper labels, copper coins, large sculptures and the like.
The current research work is mainly focused on polishing, anti-discoloration treatment and other aspects, and a plurality of methods for inhibiting the surface discoloration of the copper material, such as a chromium and ultra-low chromium passivation method, a benzotriazole and sulfosalicylic acid solution passivation method, a coating method and the like, are researched. However, the requirements of the process manufacturers are still not met. The existing chromic acid passivation technology has large chromate consumption, excessive toxic substances contained and large wastewater treatment burden. In recent years, as the use of chromates and wastewater discharge are strictly restricted by the state in environmental regulations, it is very necessary to develop new environmental protection chromium-free passivation technologies for replacing chromate passivation.
At present, in many chromium-free passivation technologies of copper alloys, nitrogen-containing heterocyclic compounds and derivatives thereof are still mainly focused, and as passivation film layers formed by single nitrogen-containing heterocyclic compounds still have many defects, technologies of compound passivation by using nitrogen-containing heterocyclic compounds and other organic and inorganic additives have been developed.
Regarding the technology of complex passivation of nitrogen-containing heterocyclic compounds and other organic and inorganic additives of copper alloys, there are many reports, for example, the patent application of the application with the application number of CN201310273023.5, in which mixed solutions of other compounds such as trialcohole, phytic acid, aminotrimethylene phosphoric acid and the like are adopted to passivate the copper alloys, the components of the passivation solution are complex, and organic phosphorus is contained, so that water eutrophication is caused. The application patent application with the application number of CN200810187682.6 adopts benzotriazole, sodium molybdate or sodium tungstate compound passivation solution to passivate brass, and the passivation solution is expensive because of containing 2-4g/L of sodium molybdate or sodium tungstate. The application patent application with the application number of CN201310534594.5 adopts benzotriazole and pyrophosphate compound passivation solution to passivate copper and copper alloy, and the passivation solution also contains phosphate, so that discharged wastewater can cause eutrophication.
Although the technology of the patent improves the technology of composite passivation of the nitrogenous heterocyclic compound and other organic and inorganic additives of the copper alloy, the corrosion resistance of the surface of the copper alloy is greatly improved, and the problems of environmental protection, economy and the like still exist.
Therefore, developing a passivation film forming solution for copper alloy surface and application thereof, wherein the passivation film prepared by the film forming solution is uniform and attractive, has good corrosion resistance, is phosphorus-free, chromium-free, green and environment-friendly, and has simple process, thus becoming a technical problem to be solved in the technical field.
Disclosure of Invention
Aiming at the defects or shortcomings in the background technology, the application aims to provide the film forming liquid for the passivation film on the surface of the copper alloy and the application thereof, and the passivation film prepared by the film forming liquid is uniform and attractive, has good corrosion resistance, is phosphorus-free and chromium-free, is environment-friendly, has a simple process and has industrial application and popularization prospects.
In order to achieve the above purpose, the application adopts the following technical scheme:
a film forming solution for a passivation film on the surface of a copper alloy comprises the following components in parts by weight: 1.0g/L to 5.0g/L of nitrogen-containing heterocyclic compound; alkylamine 0.05g/L-0.5g/L; 5.0mL/L to 50mL/L of organic alcohol; 1.0g/L to 5.0g/L of imidazoles; glucose 2.0g/L-5.0g/L; the balance of water.
Preferably, the film forming liquid for the passivation film on the surface of the copper alloy comprises the following components in parts by weight: 1.5g/L to 4.0g/L of nitrogen-containing heterocyclic compound; alkylamine 0.1g/L-0.35g/L; organic alcohol 10.0mL/L-25.0mL/L; 1.5g/L to 3.8g/L of imidazoles; glucose 2.5g/L-3.6g/L; the balance of water.
Preferably, the nitrogen-containing heterocyclic compound is at least one of benzotriazole and hydroxybenzotriazole or a mixture of more than two of benzotriazole and hydroxybenzotriazole in any proportion.
Preferably, the alkylamine is at least one of laurylamine or cyclododecylamine.
Preferably, the organic alcohol is at least one of ethanol, ethylene glycol or n-butanol.
Preferably, the imidazole is at least one of imidazole, 2-methylimidazole or 2-mercaptobenzimidazole.
The application of the film forming solution for the passivation film on the surface of the copper alloy comprises the following steps:
1) Firstly, carrying out acid degreasing and rust removal on the surface of the copper alloy, and then carrying out deionized water cleaning;
2) Adopting a film forming solution of a passivation film on the surface of the copper alloy to carry out chromium-free passivation treatment: firstly, regulating the pH value of a passivation film forming solution on the surface of the copper alloy to 4.5-6.0 by using non-reducing acid, wherein the passivation temperature is 20-80 ℃ and the passivation time is 5-20 min;
3) And (3) cleaning the passivated copper alloy with deionized water, and drying to obtain the passivation film.
Preferably, in the step 2), the pH value of the passivation film forming solution on the surface of the copper alloy is adjusted to 5.0-5.7 by non-reducing acid, the passivation temperature is 60-80 ℃, and the passivation time is 10-15 min.
Preferably, the non-reducing acid is dilute nitric acid or dilute sulfuric acid.
The beneficial effects are that:
the components of the film forming liquid of the passivation film on the surface of the copper alloy are organic matters, and the film forming liquid does not contain inorganic cancerogenic matters such as chromates and the like and other substances polluting the environment and damaging the health of human bodies; the use is convenient, the process is simple, the passivation effect is excellent, the passivated copper alloy can be kept unchanged for 12 months in humid air, and the neutral salt fog resistant time is more than 120 hours.
In order to further explain the beneficial effects of the passivation film forming solution for copper alloy surface and the application method thereof, the corresponding drawings are provided, and it should be noted that the drawings provided in the present application are only selected as individual examples in all the drawings, and are not intended to limit the claims, and all other corresponding patterns obtained through the drawings provided in the present application should be considered as being within the scope of the present application.
Drawings
FIG. 1 is a graph showing the corrosion resistance after the surface passivation treatment of the copper alloy according to example 1 of the present application.
Fig. 2 is a graph showing the corrosion resistance of the salt spray for 120 hours after the surface passivation treatment of the copper alloy according to example 1 of the present application.
Fig. 3 is a graph showing the corrosion resistance after the surface passivation treatment for copper alloy according to example 2 of the present application.
Fig. 4 is a graph showing the corrosion resistance of the salt spray for 72 hours after the surface passivation treatment of the copper alloy according to example 2 of the present application.
Fig. 5 is a graph showing the corrosion resistance after the surface passivation treatment for copper alloy according to example 3 of the present application.
FIG. 6 is a graph showing the corrosion resistance of the copper alloy surface passivation treatment according to example 3 of the present application after 96 hours of salt spray.
Detailed Description
The present application will be described in further detail with reference to the following examples, which are not intended to limit the scope of the application.
Unless otherwise indicated, the starting materials in the following examples of the present application were all commercially available, and the test methods used were all conventional in the art.
Example 1
Brass alloy plate surface passivation film forming liquid and application thereof
(1) Preparation of passivation film forming liquid for brass alloy plate surface
2.0g of benzotriazole, 2.0g of hydroxybenzotriazole, 10.0mL of absolute ethyl alcohol, 0.2g of cyclododecylamine, 2.0g of 2-mercaptobenzimidazole and 3.0g of glucose are weighed, deionized water is added to 1 liter, and stirring is carried out until dissolution is carried out, thus obtaining a copper alloy surface passivation film forming solution 1;
(2) Immersing the brass alloy plate into a mixed solution containing 0.5mL/LOP-10 (polyoxyethylene octyl phenol ether-10), 200mL/L sulfuric acid, 10mL/L nitric acid and 5mL/L hydrochloric acid, pickling and derusting for 120s at 20-30 ℃, and then washing with deionized water;
(3) Immersing the degreasing and rust-removing brass alloy plate into a passivation film forming solution on the surface of the brass alloy plate for chemical passivation treatment: firstly, adjusting the pH value of passivation film forming liquid on the surface of the brass alloy plate to 5.25 by using 1mol/L dilute nitric acid, and then, carrying out chromium-free passivation treatment, wherein the passivation temperature is 75 ℃ and the passivation time is 10min;
(4) Washing the passivated brass alloy plate with deionized water, and then drying the brass alloy plate in an oven at 75 ℃ for 5min to obtain a passivation film;
(5) The neutral salt spray test was performed according to ASTM B117 for up to 120 hours.
FIG. 1 is a graph showing the corrosion resistance after the passivation treatment for the copper alloy surface according to the embodiment 1 of the present application; FIG. 2 is a graph showing the corrosion resistance of the copper alloy according to example 1 of the present application after 120 hours of salt spray treatment. Wherein, FIG. 1 is a photograph of a real brass alloy plate after passivation treatment according to the above steps; FIG. 2 is a photograph of a real object of a passivated brass alloy plate after 120 hours of neutral salt spray test; it can be seen that after 120h neutral salt spray test, the surface of the brass alloy plate subjected to passivation treatment does not have any reddish brown rust, which indicates that the corrosion resistance of the brass alloy plate is obviously improved.
Example 2
Film forming liquid for passivation film on surface of red copper alloy plate and application thereof
(1) Preparation of film forming liquid for passivation film on surface of red copper alloy plate
2.5g/L of benzotriazole, 2.5g/L of hydroxybenzotriazole, 50.0mL/L of absolute ethyl alcohol, 0.5g/L of laurylamine, 5.0g/L of 2-methylbenzimidazole and 5.0g/L of glucose are weighed, deionized water is added to 1 liter, and stirring is carried out until dissolution is carried out, so that a film forming solution 2 of a passivation film on the surface of the red copper alloy plate is obtained;
(2) Immersing a red copper alloy plate into a mixed solution containing 0.5mL/LOP-10 (polyoxyethylene octyl phenol ether-10), 200mL/L sulfuric acid, 10mL/L nitric acid and 5mL/L hydrochloric acid, pickling and derusting for 120s at 20-30 ℃, and then washing with deionized water;
(3) Immersing the degreased and derusted red copper alloy plate into a passivation film forming solution on the surface of the red copper alloy plate for chemical passivation treatment: firstly, adjusting the pH value of a film forming solution of a passivation film on the surface of a red copper alloy plate to 4.5 by using 2moL/L dilute sulfuric acid, and then, carrying out chromium-free passivation treatment, wherein the passivation temperature is 60 ℃ and the passivation time is 15min;
(4) Washing the red copper alloy plate after passivation treatment with deionized water, and then drying the red copper alloy plate in an oven at 75 ℃ for 5min to obtain a passivation film;
(5) The neutral salt spray test was performed according to ASTM B117 for 72 hours.
FIG. 3 is a graph showing the corrosion resistance after the passivation treatment for the copper alloy surface according to example 2 of the present application; FIG. 4 is a graph showing the corrosion resistance of the copper alloy surface passivation treatment of example 2 of the present application after salt fog for 72 hours; wherein, figure 3 is a real photo of the red copper alloy plate after passivation treatment according to the steps; FIG. 4 is a photograph of a real object of a passivated red copper alloy plate after 72h neutral salt spray test; it can be seen that the surface of the red copper alloy plate subjected to the passivation treatment of the application does not have any black and green rust after being subjected to a neutral salt spray test for 72 hours, which indicates that the corrosion resistance of the red copper alloy plate subjected to the passivation treatment of the application is obviously improved.
Example 3
Brass alloy plate surface passivation film forming liquid and application thereof
(1) Preparation of passivation film forming liquid for brass alloy plate surface
1.0g/L of hydroxybenzotriazole, 5.0mL/L of absolute ethyl alcohol, 0.1g/L of cyclododecylamine, 1.0g/L of 2-methylbenzimidazole and 2.0g/L of glucose are weighed, deionized water is added to 1 liter, and stirring is carried out until dissolution is carried out, so that a brass alloy plate surface passivation film forming solution 3 is obtained;
(2) Immersing the brass alloy plate into a solution containing 0.5mL/LOP-10 (polyoxyethylene octyl phenol ether-10), 200mL/L sulfuric acid, 10mL/L nitric acid and 5mL/L hydrochloric acid at 20-30 ℃ for pickling and rust removal for 120s, and then washing with deionized water;
(3) Immersing the degreasing and rust-removing brass alloy plate into a passivation film forming solution on the surface of the brass alloy plate for chemical passivation treatment: firstly, adjusting the pH value of passivation film forming liquid on the surface of a brass alloy plate to 6.0 by using 1mol/L dilute nitric acid, and then, carrying out chromium-free passivation treatment, wherein the passivation temperature is 75 ℃ and the passivation time is 10min;
(4) Washing the passivated brass alloy plate with deionized water, and then placing the brass alloy plate into a baking oven at 75 ℃ for drying for 5min to obtain a passivation film;
(5) The neutral salt spray test was performed according to ASTM B117 for 96 hours.
FIG. 5 is a graph showing the corrosion resistance after the passivation treatment for the copper alloy surface according to example 3 of the present application; FIG. 6 is a graph showing the corrosion resistance of the copper alloy surface passivation treatment of example 3 according to the present application after 96 hours of salt spray; wherein, FIG. 5 is a photograph of a real brass alloy plate after passivation treatment according to the above steps; FIG. 6 is a photograph of a real object of a passivated brass alloy plate after 96 hours of neutral salt spray test; it can be seen that after 96h neutral salt spray test, no reddish brown rust appears on the surface of the brass alloy plate after the passivation treatment, which shows that the corrosion resistance of the brass alloy plate is obviously improved.
The nitrogenous heterocyclic compound is polymerized in a solution to form a film on the surface of the copper alloy in the form of a complex. When the concentration of the nitrogen-containing heterocyclic compound is too high, the formation of the complex is affected, and thus the formation of the film is affected.
The nitrogen-containing heterocyclic compound is a mixture of hydroxy benzotriazole and benzotriazole in a mass ratio of 1:1.
And alkylamine forms a layer of single-molecule or multi-molecule film capable of resisting oxygen and carbonic acid etching on the surface of the copper alloy, so that dissolved oxygen and hydrogen ions in water cannot contact with the surface of the copper alloy, and a barrier isolation effect is achieved.
The imidazoles contain nitrogen and sulfur heterocycles, can be firmly adsorbed on the surface of the copper alloy, can promote the generation of complexes such as benzotriazole and the like, and are beneficial to the generation of films.
Although the claimed subject matter has been described in language specific to structural features and/or methodological acts, it is to be understood that the claimed subject matter is not limited to the specific features or acts described in the claims. Rather, the specific structural features and methods described in the claims are merely examples of the application.
Claims (10)
1. A film forming solution for a passivation film on the surface of a copper alloy comprises the following components in parts by weight: 1.0g/L to 5.0g/L of nitrogen-containing heterocyclic compound; alkylamine 0.05g/L-0.5g/L; 5.0mL/L to 50mL/L of organic alcohol; 1.0g/L to 5.0g/L of imidazoles; glucose 2.0g/L-5.0g/L; the balance of water.
2. The film forming solution for the passivation film on the surface of the copper alloy according to claim 1, wherein the ratio is as follows: 1.5g/L to 4.0g/L of nitrogen-containing heterocyclic compound; alkylamine 0.1g/L-0.35g/L; organic alcohol 10.0mL/L-25.0mL/L; 1.5g/L to 3.8g/L of imidazoles; glucose 2.5g/L-3.6g/L; the balance of water.
3. The copper alloy surface passivation film forming liquid according to claim 1 or 2, wherein the nitrogen-containing heterocyclic compound is at least one of benzotriazole or a derivative thereof.
4. The film forming solution for a passivation film on a copper alloy surface according to claim 1 or 2, wherein the nitrogen-containing heterocyclic compound is a mixture of hydroxybenzotriazole and benzotriazole in a mass ratio of 1:1.
5. The film forming solution for a passivation film on a copper alloy surface according to claim 1 or 2, wherein the alkylamine is at least one of laurylamine and cyclododecamine.
6. The film forming solution for a passivation film on a copper alloy surface according to claim 1 or 2, wherein the organic alcohol is at least one of ethanol, ethylene glycol or n-butanol.
7. The copper alloy surface passivation film forming liquid according to claim 1 or 2, wherein the imidazole is at least one of imidazole, 2-methylimidazole or 2-mercaptobenzimidazole.
8. The use of the film forming liquid for passivation film on copper alloy surface according to any one of claims 1 or 2, comprising the steps of:
the temperature of the solution is 60-80 ℃, the passivation time is 10-15 min, and the pH value is adjusted to 5.0-5.7 by non-reducing acid.
9. The application of the passivation film forming liquid for copper alloy surfaces according to claim 8, wherein in the step 2), the pH value of the passivation film forming liquid for copper alloy surfaces is adjusted to be 5.0-5.7 by the non-reducing acid, the passivation temperature is 60-80 ℃, and the passivation time is 10-15 min.
10. The use of the film-forming solution for passivation film on copper alloy surface according to claim 9, wherein the non-reducing acid is dilute nitric acid or dilute sulfuric acid.
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