CN1169886C - 铝的非铬酸盐防锈剂、防锈方法和防锈铝制品 - Google Patents
铝的非铬酸盐防锈剂、防锈方法和防锈铝制品 Download PDFInfo
- Publication number
- CN1169886C CN1169886C CNB011166894A CN01116689A CN1169886C CN 1169886 C CN1169886 C CN 1169886C CN B011166894 A CNB011166894 A CN B011166894A CN 01116689 A CN01116689 A CN 01116689A CN 1169886 C CN1169886 C CN 1169886C
- Authority
- CN
- China
- Prior art keywords
- aluminium
- rust
- preventive agent
- zirconium
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000004411 aluminium Substances 0.000 title claims description 26
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- -1 aluminum ion Chemical class 0.000 claims description 13
- 159000000013 aluminium salts Chemical class 0.000 claims description 12
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 2
- 230000003449 preventive effect Effects 0.000 abstract 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 230000003628 erosive effect Effects 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- FRHOZLBTKXGMDH-UHFFFAOYSA-N [Zr].[F] Chemical class [Zr].[F] FRHOZLBTKXGMDH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000001263 FEMA 3042 Substances 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229940033123 tannic acid Drugs 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- 239000004846 water-soluble epoxy resin Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HMPRYWSTSPTPFI-UHFFFAOYSA-N [Li].[F] Chemical compound [Li].[F] HMPRYWSTSPTPFI-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 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
- C23C22/34—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 fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明的目的是提供一种铝的非铬酸盐防锈剂,尽管是非铬酸盐类型,但它还具有足够的耐腐蚀性,且例如甚至当其施涂于换热器翅片材料时也不使白锈产生。本发明提供一种铝的非铬酸盐防锈剂,其包括锆化合物、氟离子、水溶性树脂和铝盐,和用所述的非铬酸盐防锈剂进行防锈处理得到的铝制品。
Description
技术领域
本发明涉及铝的非铬酸盐防锈剂,更具体的说,涉及适合用于处理卷材形式铝片的非铬酸盐防锈剂,防锈方法和防锈铝制品。
背景技术
至今,铝或铝合金的防锈都是通过喷雾或浸渍活性铬酸盐或磷酸盐铬酸盐试剂或涂料型铬酸盐处理剂。在这种铬酸盐处理剂领域中,已通过一些发明如减少膜的重量或用毒性低的三价铬来替代有毒的六价铬,开发了那些对环境相对良性的铬酸盐处理试剂。但也不能说废料处理时对环境的污染可能性为零。
另一方面,从非铬酸盐活性类型的处理试剂和涂料类型的处理试剂来看,例如日本公布公报昭-55-38997公开了一种酸性清洗剂,其包括聚丙烯酸树脂和氟化锆,及其他成分。另外,日本公开公报平-4-232281公开了一种酸性水溶液,其包括阴离子丙烯酸-丙烯酰胺共聚物、氟化铵氧锆和硝酸。日本公开公报平-11-106954公开了一种酸性处理组合物,其包括水溶性酚醛树脂、含锆或其他金属的化合物、硅烷偶联剂、和氢氟酸、磷酸和/或醋酸。
但上述专利公报公开的非铬酸盐类型处理试剂的耐腐蚀性与铬酸盐类型处理试剂的耐腐蚀性相比要差,不能满足实际需要。
发明内容
本发明的目的是提供一种铝的非铬酸盐防锈剂,尽管是非铬酸盐类型,但却具有充分的耐腐蚀性,例如甚至施涂在换热器的翅片材料上也不会长白锈。另一目的是提供一种防锈的方法和防锈铝制品。
本发明的铝的非铬酸盐防锈试剂包括锆化合物、氟离子、水溶性树脂和铝盐,所述的锆化合物的浓度以锆离子计为100-100000ppm,所述的氟离子的浓度为125-125000ppm,以非挥发物计所述的水溶性树脂的浓度为100-100000ppm,所述的铝盐的浓度以铝离子计为10-10000ppm。
当将氟锆化合物作为所述的锆化合物使用时,氟离子的浓度为氟化物的氟离子浓度和氟锆化合物的氟离子浓度的总和。
对所述的锆化合物而言,可用氟锆酸和/或氟锆酸铵。
另外,所述的水溶性树脂较佳地具有成膜时能与所述的锆化合物和/或铝结合的官能团。
本发明的非铬酸盐防锈方法包括用所述的防锈剂处理铝底材,形成以锆计重量范围为10-1000mg/m2的膜。
本发明的防锈铝制品可通过用所述的防锈剂进行非铬酸盐防锈处理而得到。
具体实施方式
现在详细描述本发明。
如上所述,本发明的非铬酸盐防锈剂包括锆化合物、氟离子、水溶性树脂和铝盐。
上述锆化合物是主要成分,它能结合于被氟离子浸蚀的铝(包括铝合金,下文中运用到)表面,形成防锈层,并同时结合于水溶性树脂并将其固化,以确保形成强韧树脂膜。这种锆化合物的例子可以是氟锆酸、氟锆酸锂、钠、钾和铵盐、硫酸锆、硫酸氧锆、硝酸锆、硝酸氧锆、氟化锆和碳酸锆等。这些锆化合物可单独使用,或两种或多种组合使用。防锈剂中锆化合物的优选浓度为100-100000ppm锆离子,较佳的是1000-10000ppm。当锆离子的浓度低于100ppm时,与用于换热器翅片的亲水涂膜的粘合性和耐腐蚀性降低。相反,锆化合物高于100000ppm的制剂并不能进一步改善其性能,却增加了生产的成本。
上述氟离子可用如下物质提供:氢氟酸、氟化铵、氟化氢铵、氟化钠、氟化氢钠等。当将含氟的锆化合物(如氟锆酸和氟锆酸钠)作为锆离子供体时,这种化合物也提供部分氟离子。防锈剂氟离子的浓度优选为125-125000ppm,较佳的是1250-12500ppm。上述的氟离子浓度在防锈剂溶液中以游离态存在、且可用带氟离子电极的装置测定。当氟离子的浓度低于125ppm时,铝表面浸蚀的程度不足,从而不能构建合适的防锈膜。超过125000ppm并不能进一步改善其性能,却增加了产品的成本。锆-氟的重量比例(Zr/F)较佳的是0.5到0.9,更佳的是0.6到0.8。高于或低于该范围,不能得到充分的耐腐蚀性。
所述的水溶性树脂较佳地带有官能团,如羧基、羟基、磺基、氨基等,这些基团在成膜时能结合于锆化合物和/或铝底材。这些水溶性树脂的例子可为以下提到的。
(a)带有羧基和/或羟基的不饱和可聚合水溶性聚合物,如聚(甲基)丙烯酸、(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、苯乙烯-(甲基)丙烯酸共聚物、可从部分皂化聚醋酸乙烯树脂得到的聚乙烯醇、聚乙烯基吡咯烷酮、和(甲基)丙烯酰胺衍生物的聚合物(如N-羟甲基化的(甲基)丙烯酰胺)。
(b)带有羧基和/或羟基的天然高分子化合物及其衍生物,如纤维素衍生物:如羧甲基纤维素(CMC)、羟乙基纤维素(HEC)、羟丙基纤维素(HPC)、甲基纤维素(MC)、乙基纤维素(EC)、乙基羟乙基纤维素(EHEC)等,甲基纤维素衍生物和它们的钠、钾和铵盐。
(c)水溶性聚酯树脂,如通过用1,2,4-苯三酸酐半酯化聚酯树脂的羟基,并用胺等中和残留的羧基可得到水增溶(water-solubilized)的树脂,将聚乙二醇与多元酸反应可得到水溶性树脂。
(d)水溶性环氧树脂,例如水溶性环氧树脂,如脂族多元醇的二-或多缩水甘油醚、二羧酸的二缩水甘油酯、含氮含杂环的环氧化合物等,以及借助于乳化剂或改性用环氧树脂,使环氧树脂在水或水-有机溶剂混合物中分散或乳化,使它们成为水溶性或水可分散的和水可乳化的,这样得到的水可分散的环氧树脂。
(e)水溶性聚氨酯树脂,如通过将阴离子或阳离子基团引入分子而增溶的聚氨酯树脂,将亚硫酸氢盐加到氨基甲酸酯预聚物的末端异氰酸根合基团上,以封闭异氰酸根合基团,并通过利用磺酸盐的亲水性使其具有水溶性而得到的树脂,和通过用封端剂封闭氨基甲酸酯预聚物并用力使其乳化或分散而得到的树脂。
(f)水溶性酚醛树脂,如含酚式羟基的化合物如苯酚、二甲苯酚、对-烷基苯酚、对-苯基苯酚、氯酚、双酚A、苯酚磺酸、间苯二酚等,与醛(如甲醛、糠醛等)的缩聚物。它们通常是已知的,如酚醛树脂、甲酚-甲醛树脂、苯酚-糠醛树脂、间苯二酚树脂等。
(g)水溶性氨基树脂,如密胺树脂(如正-丁基化的密胺树脂、异丁基化的密胺树脂等)、尿素树脂和其他树脂(水溶性的)。
可单独使用上述水溶性树脂或将它们两种或多种组合使用。本发明防锈剂中水溶性树脂的浓度较佳的是100到100000ppm,更佳的是1000到10000ppm(以非挥发物质为基准)。当树脂浓度低于100ppm时,耐腐蚀性和耐水性往往会不充分。另外,当浓度高于100000ppm时,不能进一步改善其性能反而增加了成本。
本发明防锈剂中铝盐的浓度较佳的是10到10000ppm,更佳的是100-5000ppm(以铝离子计)。可用的铝盐例子为硝酸铝、硫酸铝、氟化铝、氧化铝、明矾、硅酸铝、铝酸盐(如铝酸钠)和氟铝酸盐(如氟铝酸钠)。当铝离子的浓度低于10ppm时,膜的固化反应可能不充分从而耐腐蚀性也不充分。相反,当其浓度高于10000ppm时,膜的固化反应受阻,在处理溶液中往往会形成碎渣。
在本发明的涂料型防锈剂中,在涂布组合物以后的一段时间里氟离子浸蚀铝底材直到膜干燥,从而锆结合于被浸蚀的表面形成防锈层,且与此同时还作用于树脂以有助树脂层的形成。在此过程中,认为铝盐提供的铝离子似乎增加了锆与树脂的反应性,从而促进防锈膜的形成。
另外,当涂料型防锈剂含有锆化合物作为防锈剂来固化和成膜时,水溶性树脂和锆彼此结合形成膜,从而往往单留下过多氟离子,而使耐腐蚀性受到不利影响。但如果处理试剂中氟离子的浓度为0或极低,铝底材和锆之间的反应将受阻滞,则涂料型防锈剂就不能得到足够的耐腐蚀性。在本发明的防锈剂中,在形成防锈膜过程中铝离子是由铝盐提供的,铝离子捕获了过量的氟离子形成氟铝酸盐。很可能上述机理与增加耐腐蚀性有关。
在本发明的防锈剂中,也可以适量加入各种添加剂。就这些添加剂而言,可提到的铝渣抑制剂如鞣酸、咪唑等,反应加速氧化剂如过氧化氢、钼酸等,树脂固化剂如金属氧化物、酚醛树脂等,和浴槽稳定鳌合剂。
在本发明的非铬酸盐防锈剂方法中,用上述防锈剂在铝片或铝成形制品上形成防锈膜。铝片包括有预涂层的片材和以卷材形式提供的金属薄片。铝成形制品包括饮料铝罐、铝轮和其他铸件。
对于防锈铝片而言,如果需要薄片是事先除油的,然后再施涂本发明的防锈剂。这施涂可用绕线棒刮涂机或辊涂机进行。其他方法包括将薄片浸泡在防锈剂的浴槽中,挤水辊挤干多余的试剂。在处理铝成形制品时,可推荐的方法包括将制品浸泡在浴槽中,然后将其离心或用气幕涂布方法。当使用浸泡方法时,防锈处理浴槽中也充满了由铝底材提供的铝离子。所以通过调节浴槽补充液中铝盐的含量,铝离子的浓度应维持在上述范围中。
防锈剂的涂层量应与膜重量相等,以锆计为10到1000mg/m2锆,较佳的是10到300mg/m2。当膜重量低于10mg/m2时,耐腐蚀性和耐水性都不够。另外,超过1000mg/m2,并不能进一步改善其性能反而增加其成本。最后将铝在70-150℃加热干燥10秒到1分钟。
用上述方法进行防锈处理的本发明的铝制品,带有相当于10-1000mg/m2锆的防锈膜。当防锈铝制品是薄片时,可将其作亲水性处理,且可有利地用于换热器翅片之类的应用。
将本发明的防锈剂配制成含有铝盐,从而当它用于防锈时,在该体系中有铝离子。结果,促进锆和树脂间的反应性,有助于防锈膜的形成。所以,这种组合物提供高度的耐腐蚀性且其防锈性完全达到了由常规铬酸盐处理剂提供的程度。
可用本发明防锈剂替代上述铬酸盐处理剂处理本发明的铝制品,从而其应用范围很广。具体的说,其非常适用于处理作为换热器翅片材料的卷材形式的铝薄片。
以下实施例和比较实施例进一步详细说明了本发明。
实施例1
制备防锈剂
制备非铬酸盐涂料型防锈剂,其在纯水中含有5000ppm氟锆酸(以Zr计),15000ppm聚丙烯酸(以不挥发物质为基准),和1000ppm硝酸铝(以Al离子计)。
防锈
提供用于换热器翅片的铝薄片(Al100)。首先,于70℃用1%质量浓度的去油剂(Surf Cleaner 340,Nippon Paint)喷雾此薄片5秒,漂洗、干燥。然后,用绕线棒涂布机施用上述防锈剂,在120℃烘烤20秒来制备用于评价的测试薄片。调节绕线棒涂布机尺寸(以#10为标准)来控制膜的重量。
评价方法
<盐喷雾测试>
按JIS Z 2371进行5%盐喷雾测试(360小时),放置后研究测试薄片的腐蚀率。表1中的各数据是通过肉眼测定测试薄片上生锈的表面积并以10个等级评定结果而得到的(数字越大,腐蚀率越小)。
<耐湿性测试>
在50℃、RH≥98%的环境中进行耐湿性测试(360小时),放置后评价测试薄片的腐蚀率。表1中的各数据是通过肉眼测定测试薄片上生锈的表面积并以10个等级评定结果得到的(数字越大,腐蚀率越小)。
实施例2-8,比较实施例1-4
除了锆化合物的量和品种、氢氟酸的量、水溶性树脂的品种和量、铝盐的品种和量和/或锆的膜重量变化外,如实施例1制备测试薄片,并进行类似的评价。表2列出了配方和评价结果。
表1
实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
Zr化合物 | 品种 | A | A | A | B | A | A | A | A |
ppm1* | 3000 | 100 | 100000 | 2000 | 3000 | 3000 | 3000 | 3000 | |
F离子浓度(ppm) | 3750 | 125 | 125000 | 2500 | 3750 | 3750 | 3750 | 3750 | |
水溶性树脂 | 品种 | D | D | D | E | D | D | D | D |
ppm | 15000 | 100 | 100000 | 4000 | 15000 | 15000 | 15000 | 15000 | |
Al盐 | 品种 | F | F | F | G | F | F | F | F |
ppm2* | 1000 | 10 | 10000 | 500 | 1000 | 1000 | 1000 | 1000 | |
添加剂 | 品种 | - | - | - | - | 鞣酸 | 过氧化氢 | 酚醛树脂 | 葡糖酸 |
ppm | - | - | - | - | 1000 | 500 | 1000 | 100 | |
Zr膜重量(mg/m2) | 100 | 10 | 1000 | 60 | 100 | 100 | 1000 | 100 | |
盐喷雾测试 | 10 | 8 | 10 | 10 | 10 | 10 | 10 | 10 | |
耐湿性测试 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
*1…为Zr *2…为Al
A…氟化锆酸,B…氟锆酸铵,C…碳酸铵氧锆,
D…聚(丙烯酸),E…聚(乙烯醇),F…硝酸铝,
G…硫酸铝
表2
比较实施例 | 1 | 2 | 3 | 4 | |
Zr化合物 | 品种 | - | A | A | A |
ppm1* | 0 | 3000 | 3000 | 3000 | |
氢氟酸(ppm) | 2500 | 3750 | 3750 | 0 | |
水溶性树脂 | 品种 | D | - | D | D |
ppm | 15000 | 0 | 15000 | 15000 | |
Al盐 | 品种 | F | F | - | F |
ppm2* | 1000 | 1000 | 0 | 1000 | |
添加剂 | 品种 | - | - | - | - |
ppm | - | - | - | - | |
Zr膜重量(mg/m2) | 0 | 100 | 100 | 100 | |
盐喷雾测试 | 1 | 3 | 2 | 2 | |
耐湿性测试 | 1 | 3 | 2 | 2 |
从表1可以看出用实施例的防锈剂处理过的测试薄片,用盐喷雾测试评价的耐腐蚀性能优越,耐湿性测试测得的腐蚀率较低。
Claims (5)
1.一种铝的非铬酸盐防锈剂,其特征在于,
其包括锆化合物、氟离子、水溶性树脂和铝盐,
所述的锆化合物的浓度以锆离子计算为100到100000ppm,
所述的氟离子的浓度为125到125000ppm,
所述的水溶性树脂的浓度以非挥发物质为基准计算为100到100000ppm,
和所述的铝盐的浓度以铝离子计算为10到10000ppm,
其中,所述水溶性树脂带有在成膜时能结合于锆化合物和/或铝底材的羧基和/或羟基官能团。
2.如权利要求1所述的铝的非铬酸盐防锈剂,其特征在于,
用氟锆酸和/或氟锆酸铵作为所述的锆化合物。
3.如权利要求1或2所述的铝的非铬酸盐防锈剂,其特征在于,
所述的水溶性树脂是聚丙烯酸和/或聚乙烯醇。
4.一种铝的非铬酸盐防锈方法,其特征在于,
所述的方法包括用权利要求1-3任一所述的非铬酸盐防锈剂处理铝基材,形成以锆计重量范围为10到1000mg/m2的膜。
5.一种铝制品,其特征在于,
所述的铝制品是用权利要求1-3任一所述的非铬酸盐防锈剂进行防锈处理得到的。
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JP2000119081A JP4099307B2 (ja) | 2000-04-20 | 2000-04-20 | アルミニウム用ノンクロム防錆処理剤、防錆処理方法および防錆処理されたアルミニウム製品 |
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CN1321709A CN1321709A (zh) | 2001-11-14 |
CN1169886C true CN1169886C (zh) | 2004-10-06 |
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US (1) | US6419731B2 (zh) |
JP (1) | JP4099307B2 (zh) |
KR (1) | KR100620296B1 (zh) |
CN (1) | CN1169886C (zh) |
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-
2000
- 2000-04-20 JP JP2000119081A patent/JP4099307B2/ja not_active Expired - Lifetime
-
2001
- 2001-04-12 US US09/833,070 patent/US6419731B2/en not_active Expired - Lifetime
- 2001-04-17 KR KR1020010020507A patent/KR100620296B1/ko active IP Right Grant
- 2001-04-20 CN CNB011166894A patent/CN1169886C/zh not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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US6419731B2 (en) | 2002-07-16 |
US20010050029A1 (en) | 2001-12-13 |
JP2001303267A (ja) | 2001-10-31 |
CN1321709A (zh) | 2001-11-14 |
JP4099307B2 (ja) | 2008-06-11 |
KR100620296B1 (ko) | 2006-09-05 |
KR20010098672A (ko) | 2001-11-08 |
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