CN106756967B - A kind of chromium-free passivating agent and method for passivating aluminum or aluminum alloy surface - Google Patents
A kind of chromium-free passivating agent and method for passivating aluminum or aluminum alloy surface Download PDFInfo
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- CN106756967B CN106756967B CN201611094538.9A CN201611094538A CN106756967B CN 106756967 B CN106756967 B CN 106756967B CN 201611094538 A CN201611094538 A CN 201611094538A CN 106756967 B CN106756967 B CN 106756967B
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- aluminum
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 65
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 238000002161 passivation Methods 0.000 claims abstract description 25
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 14
- 239000011147 inorganic material Substances 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 35
- 239000004925 Acrylic resin Substances 0.000 claims description 20
- 229920000178 Acrylic resin Polymers 0.000 claims description 20
- 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 description 19
- 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 description 19
- 239000000467 phytic acid Substances 0.000 claims description 19
- 229940068041 phytic acid Drugs 0.000 claims description 19
- 235000002949 phytic acid Nutrition 0.000 claims description 19
- 238000005238 degreasing Methods 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical group CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- DMOXNIKYXJYCFQ-UHFFFAOYSA-N (2-hydroxy-1-phosphonooxyethyl) dihydrogen phosphate Chemical compound OP(=O)(O)OC(CO)OP(O)(O)=O DMOXNIKYXJYCFQ-UHFFFAOYSA-N 0.000 claims 1
- OTHIIIBULDUCJU-UHFFFAOYSA-N 2-sulfanylcarbonylbutanedioic acid Chemical compound C(=O)(O)C(C(=S)O)CC(=O)O OTHIIIBULDUCJU-UHFFFAOYSA-N 0.000 claims 1
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 13
- 239000007921 spray Substances 0.000 abstract description 13
- 239000004411 aluminium Substances 0.000 abstract description 12
- 238000009835 boiling Methods 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 101100298225 Caenorhabditis elegans pot-2 gene Proteins 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 31
- 239000002253 acid Substances 0.000 description 17
- 238000011282 treatment Methods 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229940044927 ceric oxide Drugs 0.000 description 10
- 230000009849 deactivation Effects 0.000 description 8
- 239000002159 nanocrystal Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- RVUDCHLNIKHKBD-UHFFFAOYSA-N C(C(C(=O)OC(=O)O)S(=O)(=O)O)C(=O)O Chemical compound C(C(C(=O)OC(=O)O)S(=O)(=O)O)C(=O)O RVUDCHLNIKHKBD-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000013527 degreasing agent Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000005237 degreasing agent Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical class [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 3
- -1 3- (methacryloxypropyl) propyl Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- GWKBSZQPLYRAAH-UHFFFAOYSA-N 6-trimethoxysilylhexyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCOC(=O)C(C)=C GWKBSZQPLYRAAH-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WQLQSBNFVQMAKD-UHFFFAOYSA-N methane;silicon Chemical class C.[Si] WQLQSBNFVQMAKD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010998 test method 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
- C23C22/56—Treatment of aluminium or alloys based thereon
-
- 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
- C23C22/07—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 containing phosphates
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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)
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of chrome-free tanning agent, the component including following weight percentage: water 77.3~93.8%, water-soluble resin 5.0~20.0%, coupling agent 0.1~1.0%, nano inorganic material 0.2~0.5%, complexing agent 0.5~1.0%, promotor 0.1~0.5%.Chrome-free tanning agent provided by the invention is applied to the passivation of aluminium and aluminum alloy surface, and obtained passivating film excellent corrosion resistance has excellent binding ability with the paint film and powdery paints of substrate surface.The experimental results showed that, it can be improved using the chrome-free tanning agent of the invention aluminium that treated and aluminium alloy surface anti-corrosion corrosion, passivating film salt spray resistance 72 hours or more, the wet film adhesive force of paint film improves, the boiling of compression resistance pot 2 hours or more, and quality of forming film is not vulnerable to the influence of environmental factor, and it is easy to operate, it is suitble to scene to use.
Description
Technical field
The present invention relates to a kind of field of metal surface treatment technology, in particular to a kind of chrome-free tanning agent and aluminium or aluminium are closed
The method that gold surface is passivated.
Background technique
Aluminium and its alloy have low-density, low cost, high mechanical strength, heating conduction is excellent, electric conductivity is strong, easy processing and
The features such as easily recycling, is widely used in various industries, still, when aluminium and its alloy are influenced by mal-condition for a long time,
Its corrosion resistance can be substantially reduced.The fine and closely woven film of a layer tissue can be formed on its surface by being passivated processing in metal,
The corrosion resistance of metal can be greatly improved.
In aluminium and aluminum alloy surface treatment measures, hexavalent chromate processing technique has been widely used, and utilizes chromate
Strong oxidizing property form the passivating film that oxide and chromate are constituted in aluminium and its alloy surface, which has good with matrix
Binding force can significantly improve the corrosion resistance of aluminium alloy.But in chromate conversion treatments liquid containing to human body and environment extremely
Harmful hexavalent chromium can not only generate pollution in treatment process, but also the Cr VI in conversion film also will lead to processing and produce
Product cause secondary pollution to environment when using and discarding in the future, therefore poison with people's environmental consciousness and to hexavalent chromium
Property understanding raising, hexavalent chromium chemistry conversion processing technology use be increasingly strictly limited.
Based on this, new outlet-chromium-free metal is actively found in aluminium and aluminum alloy surface treatment industry both at home and abroad at present
Surface treating agent.In recent years, it gains public acceptance and the Chrome-free surface treating agent applied in the market has zirconium titanium class chromium-free deactivation
Agent, manganese systems class chrome-free tanning agent and pure silane inorganic agent etc..However, the effect is unsatisfactory for these chrome-free tanning agents, it is formed by
Passivating film is often second-rate, and paint film adhesion is lower.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of environmental-friendly, formation passivating film excellent corrosion resistance Chrome-frees
Passivator, and the factor that forms a film is not affected because of the variation of acidity in environment and temperature, simple to operate, suitable scene makes
With.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of chrome-free tanning agent, the component including following weight percentage: water 77.3~93.8%,
Water-soluble resin 5~20%, coupling agent 0.1~1%, nano inorganic material 0.2~0.5%, complexing agent 0.5~1%, promotor
0.1~0.5%；
Preferably, the water-soluble resin be Hydroxylated acrylic resin, it is organosilicon modified crylic acid resin, epoxy-modified
The mixture of one or more of acrylic resin and aqueous polyurethane.
Preferably, the solid content of the water-soluble resin is 20~30wt%；The Weight-average molecular matter of the water-soluble resin
Amount is 10000~30000.
Preferably, the coupling agent is silane coupling agent.
Preferably, the silane coupling agent is N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, 3- glycidol
Ether oxygen base propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane and 3- (methacryloxypropyl) propyl trimethoxy silicon
The mixture of one or more of alkane.
Preferably, the nano inorganic material is Nano silica sol, nanocrystal silicon, nano ceric oxide and nanometer titanium dioxide
The mixture of one or more of titanium.
Preferably, the partial size of the nano inorganic material is 20~80nm.
Preferably, the complexing agent is one or more of phytic acid, carboxyl sulfosuccinate and 1-hydroxy ethylidene-1,1-diphosphonic acid
Mixture.
Preferably, the promotor is acetic acid and/or nitric acid.
Using chrome-free tanning agent described in above scheme aluminum or aluminum alloy surface is passivated the present invention provides a kind of
Method, comprising the following steps:
Aluminum or aluminum alloy is subjected to ungrease treatment；
Aluminum or aluminum alloy after the degreasing is successively carried out to first of washing, second washing and the washing of third road；
Aluminum or aluminum alloy after third road washing is subjected to chromium-free deactivation；
Aluminum or aluminum alloy after the passivation is subjected to the 4th washing and drying.
The present invention provides a kind of chrome-free tanning agent, the component including following weight percentage: water 77.3~93.8%,
Water-soluble resin 5~20%, coupling agent 0.1~1%, nano inorganic material 0.2~0.5%, complexing agent 0.5~1%, promotor
0.1~0.5%.Chrome-free tanning agent provided by the invention is free of hexavalent chromium, environmental-friendly, pollution-free, can replace tradition
Metal surface is handled using containing chromate and traditional chromium-free metal surface treatment agent, aluminium is especially adapted for use in and aluminium closes
Passivation Treatment before golden coating；Obtained passivating film has a large amount of carboxyl, hydroxyl, amino and epoxy group isoreactivity point, with base
The paint film and powdery paints on material surface have excellent binding ability, excellent corrosion resistance, and its film forming factor is not susceptible to ring
The influence of border factor, it is easy to operate, it is suitble to scene to use.The experimental results showed that after using chrome-free tanning agent processing of the invention
Aluminium and aluminium alloy surface anti-corrosion corrosion can improve, salt spray resistance 72 hours or more, the wet film adhesive force of paint film improved, compression resistance pot
Boiling 2 hours or more.
Specific embodiment
The present invention provides a kind of chrome-free tanning agent, the component including following weight percentage: water 77.3~93.8%,
Water-soluble resin 5~20%, coupling agent 0.1~1%, nano inorganic material 0.2~0.5%, complexing agent 0.5~1%, promotor
0.1~0.5%.
Chrome-free tanning agent provided by the invention include weight percentage be 5~20% water-soluble resin, preferably 10
~18%, more preferably 12~15%.In the present invention, the water-soluble resin is preferably Hydroxylated acrylic resin, organosilicon
The mixture of one or more of acrylic resin modified, epoxy-modified acrylic resin and aqueous polyurethane；The water
The mixture of soluble resin is preferably the mixture of 2~3 kinds of water-soluble resins, more preferably Hydroxylated acrylic resin and organosilicon
The mixture of acrylic resin modified mixture or organosilicon modified crylic acid resin and aqueous polyurethane；The hydroxy
Hydroxylated acrylic resin and organosilicon modified crylic acid resin in the mixture of acid resin and organosilicon modified crylic acid resin
Weight ratio is preferably 1~1.5:1, more preferably 1.2~1.3:1；The organosilicon modified crylic acid resin and aqueous polyurethane
Mixture in the weight ratio of organosilicon modified crylic acid resin and aqueous polyurethane be preferably 1.2~1.8:1, more preferably
1.3~1.5:1.
In the present invention, the solid content of the water-soluble resin is preferably 20~30wt%, more preferably 22~25wt%；
The weight average molecular mass of the water-soluble resin is preferably 10000~30000, and more preferably 15000~25000.
Chrome-free tanning agent provided by the invention include weight percentage be 0.1~1% coupling agent, more preferably 0.3
~0.8%.In the present invention, the coupling agent is preferably silane coupling agent；The silane coupling agent is preferably N- (β-ammonia second
Base)-γ-aminopropyltrimethoxysilane (KH-792), 3- glycidyl ether oxypropyltrimethoxysilane (KH-560),
One in gamma-aminopropyl-triethoxy-silane (KH-550) and 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570)
Kind or several mixtures.In the present invention, the mixture of the silane coupling agent is preferably the mixed of 2~3 kinds of silane coupling agents
Close object, the mixture or KH-550 of more preferably KH-792 and KH-560 and the mixture of KH-560；The KH-792 and KH-
The mass ratio of KH-792 and KH-560 is preferably 1.5~2:1 in 560 mixture, more preferably 1.6~1.8:1；The KH-
The mass ratio of KH-550 and KH-560 is preferably 1.3~1.6:1 in the mixture of 550 and KH-560, and more preferably 1.4~1.5:
1。
The weight percentage of nano inorganic material is 0.2~0.5% in chrome-free tanning agent provided by the invention, more preferably
It is 0.3~0.4%.In the present invention, the nano inorganic material is preferably Nano silica sol, nanocrystal silicon, nanometer titanium dioxide
The mixture of one or more of cerium and nano-titanium dioxide；The nano inorganic material mixture is preferably 2~3 kinds of nanometers
The mixture of inorganic material；The more preferably mixture of nano ceric oxide and nano-titanium dioxide or nanocrystal silicon and nanometer two
The mixture of cerium oxide；Nano ceric oxide and nano-silica in the mixture of the nano ceric oxide and nano-titanium dioxide
The mass ratio for changing titanium is preferably 1~1.5:1, more preferably 1.2~1.3:1；The nanocrystal silicon and nano ceric oxide it is mixed
Closing the mass ratio of nanocrystal silicon and nano ceric oxide in object is preferably 1~1.5:1, more preferably 1.2~1.3:1.
In the present invention, the partial size of the nanocrystal silicon, nano ceric oxide and nano-titanium dioxide is independent preferably
20~80nm, more preferably 30~60nm, most preferably 40~50nm；The partial size of nano silica in the Nano silica sol
Preferably 20~80nm, more preferably 30~60nm, most preferably 40~50nm；The solid content of the Nano silica sol is preferably
25~40wt%, more preferably 30~35wt%.Complexing agent weight percentage is 0.5 in chrome-free tanning agent provided by the invention
~1%, more preferably 0.6~0.8%.In the present invention, the complexing agent is preferably phytic acid, carboxyl sulfosuccinate and hydroxyl
The mixture of one or more of ethylidene diphosphonic acid.In the present invention, the mixture of the complexing agent is preferably 2~3 kinds of networks
The mixture of mixture, the more preferably mixing of the mixture or phytic acid and 1-hydroxy ethylidene-1,1-diphosphonic acid of phytic acid and carboxyl sulfosuccinate
Object；In the mixture of the phytic acid and carboxyl sulfosuccinate the mass ratio of phytic acid and carboxyl sulfosuccinate be preferably 1~
1.8:1, more preferably 1.3~1.5:1；Two phosphorus of phytic acid and hydroxy ethylidene in the mixture of the phytic acid and 1-hydroxy ethylidene-1,1-diphosphonic acid
The mass ratio of acid is preferably 1~1.5:1, more preferably 1.2~1.3:1.
The weight percentage of promotor is preferably 0.1~0.5% in chrome-free tanning agent provided by the invention, more preferably
0.2~0.4%.In the present invention, the promotor is preferably acetic acid and/or nitric acid.
In chrome-free tanning agent provided in the present invention the weight percentage of water be 77.3~93.8%, more preferably 80~
90%.
The present invention does not have special limitation to the preparation method of the chrome-free tanning agent, using known to those skilled in the art
Composition preparation technical solution.In the present invention, the preparation method of the chrome-free tanning agent is preferably by above-mentioned skill
The mixing of raw material described in art scheme, it is preferred the following steps are included:
Promotor is mixed with first part water, is promoted agent solution；
The accelerator solution is successively mixed with modified soluble resin, coupling agent and nano inorganic material, is mixed
Close feed liquid；
Under stirring conditions, remaining water is added into the mixed liquor.
In the present invention, the rate of the stirring is preferably 300~500r/min, more preferably 350~450r/min；Institute
The time for stating stirring is preferably 10~30min, more preferably 15~25min.In the present invention, the volume of first part's water
With the ratio between the total volume of water preferably 0.5~0.7:1, more preferably 0.6:1.
In the present invention, the water-soluble resin is film forming matter, as the skeleton of passivating film, coupling agent and water-soluble tree
Rouge crosslinks reaction and forms finer and close, uniform film layer, while coupling agent and the hydroxyl on inorganic nano material surface carry out
Effect, forms firm bonding action, combines inorganic nano material with film-forming resin, keep passivation film finer and close, mention
The high Corrosion Protection and wet film adhesive force of passivating film；Complexing agent and promotor can control film forming speed, improve passivation
The stability of agent adjusts passivation film color, makes the film forming of passivator not vulnerable to the influence of environmental factor, the operation is more convenient.
And various components are worked in coordination in passivator provided by the invention, and there are a large amount of carboxyls, ammonia on finally formed passivating film
Base hydroxyl and epoxy group isoreactivity group, to improve the binding force of passivating film and substrate and powdery paints etc..
Using chrome-free tanning agent described in above scheme aluminum or aluminum alloy surface is passivated the present invention provides a kind of
Method, comprising the following steps:
Aluminum or aluminum alloy is subjected to ungrease treatment；
Aluminum or aluminum alloy after the degreasing is successively carried out to first of washing, second washing and the washing of third road；
Aluminum or aluminum alloy after third road washing is subjected to chromium-free deactivation；
Aluminum or aluminum alloy after the passivation is subjected to the 4th washing and drying.
Aluminum or aluminum alloy is carried out ungrease treatment by the present invention.Present invention preferably uses acid degreasing agents to carry out ungrease treatment,
The free acid value of the acid degreasing agent is preferably 15~25.In the present invention, the time of the degreasing is preferably 3~10min,
More preferably 5~8min；The temperature of the degreasing is preferably room temperature, without carrying out additional heating and cooling；The present invention is to acid
The type of property degreasing agent does not have particular/special requirement, uses the acid degreasing agent that this field is common.
After the completion of ungrease treatment, the aluminum or aluminum alloy after degreasing is successively carried out first of washing, second water by the present invention
It washes and is washed with third road.In the present invention, the conductivity of first of washing washing water is preferably 200~1000 μ s/cm,
More preferably 300~800 μ s/cm；The pH value of washing water is preferably 3.5~7.0, and more preferably 4.5~6.5；Described first
The time of washing is preferably 30~60s, more preferably 40~50s.In the present invention, the second washing electricity of washing water
Conductance is preferably 200~400 μ s/cm, more preferably 250~350 μ s/cm；The pH of washing water is preferably 6.0~7.0, more preferably
It is 6.3~6.5；The time of the second washing is preferably 30~60s, more preferably 40~50s.In the present invention, described
The conductivity of third road washing washing water is preferably smaller than 50 μ s/cm, more preferably 10~40 μ s/cm；The pH of washing water is preferred
It is 6.5~7.0, more preferably 6.6~6.8；The time of the third road washing is preferably 30~60s, more preferably 40~
50s。
Passivating method provided by the invention is provided with three washings between degreasing and chromium-free deactivation, can be effectively prevented
Degreaser pollutes chromium-free passivation liquid, so as to avoid aluminum alloy surface passivating film it is loose caused by subsequent coating process paint film it is attached
Put forth effort the problem of reducing.
After the completion of the washing, the present invention by the aluminum or aluminum alloy after washing by adopting the above technical scheme the passivator into
Row chromium-free deactivation.The present invention preferably passes through passivator and water mixed preparing passivating solution, quality of the passivator in passivating solution
Concentration is preferably 0.5~5%, and more preferably 1~3%；The pH value of the passivating solution is preferably 2.5~4.0, more preferably 3~
3.5.In a specific embodiment of the present invention, the pH that pH adjusting agent adjusts passivation tank liquor can be used；The pH adjusting agent is preferred
For phosphoric acid.
In the present invention, the time of the passivation is preferably 1~10min, more preferably 2~5min；The temperature of the passivation
Degree is room temperature, without carrying out additional heating and cooling.The present invention does not have particular/special requirement to the dosage of passivating solution, and passivating solution can
Submerge plate.
After the completion of the passivation, the plate after passivation is carried out the 4th washing and drying by the present invention.In the present invention, institute
The conductivity for stating the 4th washing washing water is preferably smaller than 100 μ s/cm, more preferably 10~80 μ s/cm, more preferably 30~
50μs/cm；The pH of the washing water is preferably 6.0~7.0, and more preferably 6.5~6.8.The present invention carries out the 4th after passivation
Road washing, removes remaining passivating solution and impurity on passivating film, stain occurs after avoiding passivating film solidification.
The present invention does not have the concrete operations mode of first of washing, second washing, the washing of third road, the 4th washing
Particular/special requirement uses water-washing method well known to those skilled in the art.
After the completion of 4th washing, aluminum or aluminum alloy is dried in the present invention.In the present invention, the temperature of the drying
Preferably 100~130 DEG C, more preferably 110~120 DEG C；The time of the drying is preferably 10~20min, and more preferably 13
~15min.The present invention solidifies passivating film by drying, and passivating method drying temperature provided by the invention is low, is 100 in temperature
The solidification of passivating film can be realized under the conditions of~130 DEG C, compared with the existing technology for (solidification temperature is generally 180 DEG C or more)
Energy consumption is reduced, it is lower to the ability to cure requirement of production line, reduce production cost.
Below with reference to embodiment to chrome-free tanning agent provided by the invention and the side being passivated to aluminum or aluminum alloy surface
Method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Passivating solution is prepared according to the formula of chrome-free tanning agent, the content of each component in passivator are as follows: water 829kg, organosilicon
Acrylic resin modified 150.0kg (solid content 20wt%, weight average molecular weight 15000), KH-5605.0kg, nano-titanium dioxide
3.0kg, phytic acid 8.0kg, nitric acid 5.0kg；
First by nitric acid and phytic acid by being added in 500.0kg water, it is to be mixed uniformly after sequentially add organic-silicon-modified propylene
Acid resin, KH-560 and nano-titanium dioxide under conditions of being stirred for, are added excess water, stir evenly；
It is spare by above-mentioned passivator by the concentration of 1% and 10% mass ratio with passivation tank liquor；
Degreaser is prepared using sulfuric acid and hydrofluoric acid, controlling the free acid value in degreaser is 15 or so, and standard aluminum is closed
Golden test plate (panel) (10 × 20cm) is immersed in degreaser, degreasing 5min；First of washing is carried out to plate after the completion of degreasing, by plate
It is soaked in water lotion, it is 4.5 or so that the conductivity for controlling wash water, which is 1000 μ s/cm, pH, wash time 30s；It carries out later
Second washing, it is 6.0 or so that the conductivity for controlling wash water, which is 400 μ s/cm, pH, wash time 30s；Third is carried out later
Road washing, it is 6.5 or so that the conductivity for controlling wash water, which is 30 μ s/cm, pH, wash time 30s；
Option A: the standard aluminium alloy test plate (panel) that above-mentioned washing is completed is immersed in the deactivation slot that passivating agent concentration is 1%
2min, after taking out test plate (panel) control water 3min, carrying out the 4th washing, (conductivity of control wash water is 100 μ s/cm, and pH is 6.0 left
The right side, wash time 30s), it is put into 120 DEG C of drying ovens dry 15min, obtains passivating film；According to international standard ISO 3768-
1976 " metal cladding neutral salt spray test (NSS tests) " carry out neutral salt spray test to passivating film, and test result is shown in Table 1；
The aluminium alloy plate that passivation is completed is placed at room temperature for after 16h and carries out spray treatment, after aluminum alloy specimen spraying, room temperature is put
16h is set, pressure cooker boiling test (European Union's Qualicoat quality inspection standard) is carried out to the paint film of spraying, test result is shown in Table
1；
Option b: the standard aluminium alloy test plate (panel) that above-mentioned washing is completed being immersed in the deactivation slot that passivating agent concentration is 5%,
It is passivated, dries and sprays according to the method in option A, carry out neutral salt spray test and pressure according to identical detection method
Pot boiling test, test result are shown in Table 1.
Embodiment 2
Passivating solution is prepared according to the formula of chrome-free tanning agent, the content of each component in passivator are as follows: water 829.0kg, it is organic
Fluorine-silicon modified acrylic resin 100kg (solid content 25wt%, weight average molecular weight 10000), aqueous polyurethane 50kg (solid content
30%, weight average molecular weight 25000), KH-792 5kg, nano-titanium dioxide 3kg, phytic acid 8kg, nitric acid 5kg, acetic acid 3kg；
By nitric acid, phytic acid and acetic acid by above-mentioned additive amount be added 500kg water in, it is to be mixed uniformly after sequentially add KH-
792, under conditions of being stirred for, excess water is added in organosilicon modified crylic acid resin, aqueous polyurethane and nano-titanium dioxide,
It stirs evenly；
It is spare by above-mentioned passivator by the concentration of 1% mass ratio with passivation tank liquor；
Degreasing and washing are carried out to standard aluminium alloy test plate (panel) (10 × 20cm) according to the method in embodiment 1, take two pieces to take off
The standard aluminium alloy test plate (panel) that rouge cleaned is immersed in 2min (being denoted as option A) and 10min (note in the deactivation slot of 1% concentration respectively
For option b), after taking out test plate (panel) control water 3min, it is put into 120 DEG C of drying ovens dry 15min, obtains passivating film；According to embodiment 1
In method passivating film is detected, testing result is shown in Table 1；
It is placed at room temperature for 16h, spray treatment is carried out after aluminum alloy specimen spraying to aluminum alloy plate materials and is placed at room temperature for 16h；It presses
Paint film is detected according to the method in embodiment 1, testing result is shown in Table 1.
Embodiment 3
Passivating solution is prepared according to the formula of chrome-free tanning agent, the content of each component in passivator are as follows: water 830.0kg, hydroxyl
Acrylic resin 150.0kg (solid content 30wt%, weight average molecular weight 30000), KH-550 4.0kg, KH-560 3.0kg, receive
Rice ceria 3.0kg, phytic acid 5.0kg, nitric acid 5.0kg；
Nitric acid and phytic acid are added in 500.0kg water by above-mentioned additive amount, it is to be mixed uniformly after sequentially add KH-550,
Under conditions of being stirred for, excess water is added in KH-560, Hydroxylated acrylic resin and nano ceric oxide, and stirring is abundant；
It is spare by above-mentioned passivator by the concentration of 3% mass ratio with passivation tank liquor；
Degreasing, cleaning are carried out to standard aluminium alloy plate according to the method in embodiment 1, the aluminum alloy plate materials after cleaning are soaked
The not 3min in passivation tank liquor after taking out test plate (panel) control water 3min, is put into 120 DEG C of drying ovens dry 15min, obtains passivating film；
Passivating film is detected according to the method in embodiment 1, testing result is shown in Table 1；
It is placed at room temperature for 16h, spray treatment is carried out after aluminum alloy specimen spraying to aluminum alloy plate materials and is placed at room temperature for 16h；It presses
Paint film is detected according to the method in embodiment 1, testing result is shown in Table 1.
Embodiment 4
Passivating solution is prepared according to the formula of chrome-free tanning agent, the content of each component in passivator are as follows: water 831.0kg, hydroxyl
Acrylic resin 100.0kg (solid content 20wt%, weight average molecular weight 23000), aqueous polyurethane 50.0kg (solid content 25%,
Weight average molecular weight 26000), KH-550 6.0kg, nano ceric oxide 3.0kg, phytic acid 5.0kg, nitric acid 5.0kg；
First nitric acid and phytic acid are added in 500.0kg water by above-mentioned additive amount, it is to be mixed uniformly after sequentially add KH-550,
Under conditions of being stirred for, excess water is added, stirring is sufficiently i.e. in Hydroxylated acrylic resin, aqueous polyurethane and nano ceric oxide
It can；
It is spare by above-mentioned passivator by the concentration of 2% mass ratio with passivation tank liquor；
Degreasing, cleaning are carried out to standard aluminium alloy plate according to the method in embodiment 1, the aluminum alloy plate materials after cleaning are soaked
The not 5min in passivation tank liquor after taking out test plate (panel) control water 3min, is put into 120 DEG C of drying ovens dry 15min, obtains passivating film；
Passivating film is detected according to the method in embodiment 1, testing result is shown in Table 1；
It is placed at room temperature for 16h, spray treatment is carried out after aluminum alloy specimen spraying to aluminum alloy plate materials and is placed at room temperature for 16h；It presses
Paint film is detected according to the method in embodiment 1, testing result is shown in Table 1.
Embodiment 5
Passivating solution is prepared according to the formula of chrome-free tanning agent, the content of each component in passivator are as follows: water 826.0kg, it is organic
Fluorine-silicon modified acrylic resin 75.0kg (solid content 30wt%, weight average molecular weight 10000), epoxy-modified acrylic resin
75.0kg (solid content 25%, weight average molecular weight 13000), KH-560 6.0kg, nanocrystal silicon 5.0kg, phytic acid 5.0kg, carboxyl
Sulfosuccinate 3.0kg, nitric acid 5.0kg；
By nitric acid, phytic acid and carboxyl sulfosuccinate by above-mentioned additive amount be added 500.0kg water in, it is to be mixed uniformly after according to
Secondary addition organosilicon modified crylic acid resin, epoxy-modified acrylic resin, KH-560 and nanocrystal silicon, the item being stirred for
Under part, excess water is added, stirring is abundant；
It is spare by above-mentioned passivator by the concentration of 5% mass ratio with passivation tank liquor；
Degreasing, cleaning are carried out to standard aluminium alloy plate according to the method in embodiment 1, the aluminum alloy plate materials after cleaning are soaked
The not 2min in passivation tank liquor after taking out test plate (panel) control water 3min, is put into 120 DEG C of drying ovens dry 15min, obtains passivating film；
Passivating film is detected according to the method in embodiment 1, testing result is shown in Table 1；
It is placed at room temperature for 16h, spray treatment is carried out after aluminum alloy specimen spraying to aluminum alloy plate materials and is placed at room temperature for 16h；It presses
Paint film is detected according to the method in embodiment 1, testing result is shown in Table 1.
Comparative example 1
It is according to mass percent by zirconium titanium system passivator, manganese systems passivator and pure silicon methane series passivator that market is bought
2% ratio prepares tank liquor, carries out degreasing, cleaning and passivation to standard aluminum alloy plate materials according to the method in embodiment 5, obtains
Passivating film carries out resistance to neutral salt spray test according to identical test method, and test result is shown in Table 1；
Aluminum alloy plate materials are sprayed according to the method in embodiment 5, and paint film is detected, testing result is shown in Table
1。
1 performance characterization result of 1 Examples 1 to 5 of table and comparative example
Note: the pressure kettle detection method standard of European Union's Qualicoat quality regulation is boiling 1 hour, 0 grade；
0 grade of expression paint film is without being bubbled, draw at lattice without falling off, draw lattice after boiling without the scarce limit such as fall off；
0~5% area of lattice is drawn after 1 grade of expression boiling to fall off；
5~15% area of lattice is drawn after 2 grades of expression boilings to fall off；
Corrosion-free defect is indicated for 10 grades in neutral salt spray test；
9 grades of expression corrosion default areas are less than or equal to 0.1%；9-10 grades indicate good but incomplete flawless compared with 9 grades
Sample；
8 grades of expression corrosion default areas are 0.1~0.25%；8-9 grades indicate good compared with 8 grades but 9 grade standards are not achieved
Sample；
4 grades of expression corrosion default areas are 2.5~5%.
As seen from the above embodiment, it after being handled using chrome-free tanning agent provided by the invention aluminum alloy plate materials, obtains
The passivating film good corrosion resistance arrived, and the adhesive force of paint film significantly improves after coating, relative to traditional zirconium titanium system, manganese systems and pure
For silane system chrome-free tanning agent, effect is more excellent；And chrome-free tanning agent provided by the invention is environmental-friendly, pollution-free, behaviour
Facilitate, scene is suitble to use.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
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| CN107829081A (en) * | 2017-11-07 | 2018-03-23 | 北京安邦之星科技有限公司 | A kind of special passivation film agent of aluminum products and preparation method thereof |
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| CN110983319A (en) * | 2019-12-30 | 2020-04-10 | 重庆铁马工业集团有限公司 | Novel energy-saving environment-friendly phosphating substitution process |
| CN111304641A (en) * | 2020-02-21 | 2020-06-19 | 攀钢集团攀枝花钢铁研究院有限公司 | Hot-dip aluminum-zinc plate chromium-free passivation solution and preparation method of hot-dip aluminum-zinc fingerprint-resistant plate |
| CN112144050B (en) * | 2020-09-24 | 2022-12-23 | 蚌埠学院 | Silicon-based chromium-free passivation solution for Bundy tube and preparation method thereof |
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| CN104561970A (en) * | 2014-12-31 | 2015-04-29 | 苏州禾川化学技术服务有限公司 | Corrosion-resistant magnesium aluminum alloy chromium-free passivation solution |
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