CN101044264A - 一种改善金属表面的耐蚀性的方法和具有改善的耐蚀性的金属片 - Google Patents
一种改善金属表面的耐蚀性的方法和具有改善的耐蚀性的金属片 Download PDFInfo
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- CN101044264A CN101044264A CNA2005800357925A CN200580035792A CN101044264A CN 101044264 A CN101044264 A CN 101044264A CN A2005800357925 A CNA2005800357925 A CN A2005800357925A CN 200580035792 A CN200580035792 A CN 200580035792A CN 101044264 A CN101044264 A CN 101044264A
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- China
- Prior art keywords
- zinc
- tinsel
- chromium
- metal
- nickel
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- 238000000034 method Methods 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 238000005260 corrosion Methods 0.000 title claims abstract description 25
- 230000007797 corrosion Effects 0.000 title claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 73
- 239000011248 coating agent Substances 0.000 claims abstract description 65
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 57
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011651 chromium Substances 0.000 claims abstract description 54
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011701 zinc Substances 0.000 claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 36
- 230000002378 acidificating effect Effects 0.000 claims abstract description 31
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 14
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000009713 electroplating Methods 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 24
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 17
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- 239000000314 lubricant Substances 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical group [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 9
- 241000370738 Chlorion Species 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 6
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- -1 zinc fluoroborate Chemical compound 0.000 description 11
- 239000000049 pigment Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
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- 239000011787 zinc oxide Substances 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VPWFPZBFBFHIIL-UHFFFAOYSA-L Lithol Rubine Chemical compound OC=1C(=CC2=CC=CC=C2C1N=NC1=C(C=C(C=C1)C)S(=O)(=O)[O-])C(=O)[O-].[Na+].[Na+] VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000007744 chromate conversion coating Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
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- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
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- NLKOSPLGBAHDND-UHFFFAOYSA-N aluminum chromium(3+) cobalt(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Al+3].[Cr+3].[Co++] NLKOSPLGBAHDND-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
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- 229940078494 nickel acetate Drugs 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- C23C22/50—Treatment of iron or alloys based thereon
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- 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
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- 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
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- 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
- C23C22/53—Treatment of zinc or alloys based thereon
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- 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
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- C23C22/83—Chemical after-treatment
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- 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
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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Abstract
本发明描述了一种具有改善的耐蚀性和粘附性的具有有机涂层的金属片，该金属片包括在其表面上电镀了锌或锌合金的金属片，由包括作为基本仅有的铬离子存在的三价铬的酸性铬水溶液而沉积的铬酸盐膜，以及在铬酸盐膜上的阴极电涂的干燥的有机涂层。本发明还描述了获得这种金属片的方法。
Description
技术领域
本发明涉及一种表现出改善的粘附性和耐蚀性的具有有机涂层的金属片。更具体地，本发明涉及一种改善金属的耐蚀性的方法。
背景技术
相当多的注意力已关注在为金属表面提供改善的防腐蚀性上。一种提供防腐蚀性的方法是通过在金属表面上沉积一种或多种转化涂料以形成涂层，该涂层保护金属不受腐蚀并且还用作基底以改善随后涂上的干燥的有机涂层的粘附性。这些转化涂料通过使用与表面反应以形成所需的涂层的各种化学品溶液对表面进行处理来施用。通常使用的转化涂料组合物为磷酸盐和铬酸盐水溶液。
为金属表面提供改善的防腐蚀性的另一种方法涉及在金属表面上电沉积锌或锌合金涂层。
基于溶剂的干燥的有机涂料组合物通过如喷射、浸渍、辊涂等已施用于金属表面。水溶性的和/或基于可分散的树脂的涂料和漆也可用于涂覆金属表面，并且这些可通过电泳被施用。涂料和漆的电泳应用包括电渗析和电解以及电泳现象。在该方法中，电流通过涂料或漆溶液，同时待涂覆的物品在涂料或漆中成为电极。
虽然上述技术已为金属表面提供防腐蚀，但是仍需要金属和金属表面表现出金属的更高的防腐蚀和干燥涂层的改善的粘附性。
发明内容
本发明描述了一种改善金属的耐蚀性的方法，该方法包括：
(A)使用锌或锌合金电镀金属以形成锌或锌合金表面，
(B)通过锌或锌合金表面与含有作为基本仅有的铬离子存在的三价铬的酸性铬水溶液接触，将铬涂料涂覆到锌或锌合金表面上，以及
(C)使用阴极电涂方法将干燥的有机涂料沉积到铬涂层上。
本发明还描述了具有改善的耐蚀性和粘附性的具有有机涂层的金属片，所述金属片包括在其表面上电镀了锌或锌合金的金属片，由包括作为基本仅有的铬离子存在的三价铬的酸性铬水溶液而沉积的铬酸盐膜，以及在铬酸盐膜上的阴极电涂的干燥的有机涂层。本发明使用的金属片金属可包括铝、铁、钢、镁、镁合金或镀锌铁。
具体实施方式
在一实施方案中，本发明的方法包括：
(A)使用锌或锌合金电镀金属以形成锌或锌合金表面，
(B)通过锌或锌合金表面与含有作为基本仅有的铬离子存在的三价铬的酸性铬水溶液接触，将铬涂料涂覆到锌或锌合金表面上，以及
(C)使用阴极电涂方法将干燥的有机涂料沉积到铬涂层上。
本发明的方法用于改善各种金属的耐蚀性。在一实施方案中，根据本发明可被处理的金属包括铝、铁、钢、镁、镁合金或镀锌铁。根据本发明被处理的金属片可包括未成形的金属片或板、成形的金属板、小金属部件如螺母、螺栓、螺钉以及配件。在一实施方案中，根据本发明可被处理的金属片包括汽车钢板和装配件。
在本发明的方法的第一步骤中，使用锌或锌合金电镀金属。本说明书和权利要求书中的术语“合金”定义为锌和可以是显微均质的或显微非均质的一种或多种金属元素的混合物。在一实施方案中，锌合金可包括锌和一种或多种的铁、镍、钴以及镁。在另一实施方案中，锌镍合金包括锌-镍合金或锌-铁合金。在一实施方案中合金可包括锌-镍-钴，在另一实施方案中合金不含钴。
金属的表面可利用包括电镀锌、热镀锌、电镀锌合金、机械镀覆等的许多本领域公知的方法而使用锌或锌合金电镀。在各种金属上电沉积锌和锌合金的方法在前面已被描述，并且碱性和酸性两种电镀溶液已被描述。例如，用于在基底上沉积光亮锌的电沉积的酸性电镀溶液在美国专利第4,169,772号和美国专利第4,162,947号中被描述。美国专利第5,200,057号描述了使用酸性电镀溶液沉积锌和锌合金的方法和组合物。美国专利第4,832,802号描述了用于电沉积锌-镍合金的酸性锌-镍电镀溶液和方法。美国专利第4,188,271号描述了用于电沉积锌的碱性溶液。这些专利公开的内容通过引用并入本申请。
在一实施方案中，在本发明的方法中使用的酸性锌和锌合金电镀溶液包括常规的含有锌和铵的电镀溶液以及不含铵的酸性电镀溶液。本发明使用的锌电镀溶液包括自由的锌离子，所述溶液可使用硫酸锌、氯化锌、氟硼酸锌、醋酸锌、氨基磺酸锌和/或链烷磺酸锌。在电镀溶液中的锌离子浓度可在约5g/l至约180g/l的范围内，或在约7.5g/l至约100g/l的范围内。当为了沉积锌合金电镀溶液包括其它金属时，所述溶液除锌以外还包括一种或多种另外的金属如镍、铁、钴以及镁。镍离子可以水溶性盐如氯化镍、硫酸镍、氟硼酸镍、醋酸镍、氨基磺酸镍以及链烷磺酸镍的形式存在于电镀水溶液中。当钴离子存在于电镀水溶液中时，钴可以硫酸钴、氯化钴、氟硼酸钴、氨基磺酸钴或醋酸钴的形式存在。同样地，当铁存在时，铁可作为硫酸铁、氯化铁等被引入。当另外的离子如镍、钴、铁、和/或镁存在于电镀溶液中时，这些另外的离子可以约10g/l至约150g/l的浓度存在。
当本发明使用碱性锌电沉积溶液时，锌离子源可以是碱金属锌酸盐，如锌酸钠或锌酸钾。锌离子的其它来源包括氧化锌、硫酸锌、醋酸锌等。电镀溶液还包含通常为碱金属氧氢化物如氢氧化钠或氢氧化钾的碱性物质。
在一实施方案中，当在金属表面上沉积的锌合金是锌镍合金时，该合金可包括从约8重量％至约20重量％的镍。在另一实施方案中，锌镍合金可包括从约10重量％至约18重量％的镍或从约12重量％至约16重量％的镍。当合金为锌-铁合金时，该合金可包括从约0.1重量％至约5重量％的铁。在另一实施方案中，锌离子和镍离子存在的浓度足以沉积具有主要γ结晶相的锌-镍合金。具有主要γ结晶相的锌-镍合金比具有非主要γ结晶相的合金更加耐腐蚀、特别是来自于氯化物或盐的腐蚀。
用于电镀锌合金如锌-镍和锌-铁的程序和溶液也是商业上可获得的。例如，碱性锌-镍电镀溶液和方法可以普通商品名REFLECTALLOYZNA由位于Rockhill，南卡罗来纳29730的Atotech美国公司获得，REFLECTALLOYZNA是一种在宽范围的电流密度产生包括从约10％至约15％的镍的锌-镍合金沉淀物的无氰化物的方法。
用于本发明方法的商业上可获得的锌-铁电镀溶液和方法的例子是ProtedurTM Plus，ProtedurTM Plus是碱性锌-铁电镀溶液和沉积具有功能性的、半光亮的外观的耐蚀性涂层的方法。ProtedurTM Plus也可由Atotech美国公司获得。ProtedurTM碱性锌-铁电镀溶液和方法可用于沉积含有约0.1重量％至约5重量％的铁的锌-铁合金，在一实施方案中，对于最佳的防腐蚀，沉积物的铁含量维持在约0.4重量％至约1重量％的范围内。
上述的电镀了锌或锌合金的金属表面通过锌或锌合金表面与含有作为基本仅有的铬离子存在的三价铬的酸性铬水溶液接触而提供铬(铬酸盐)涂层。采用其中铬基本上完全是以三价状态存在的溶液处理锌表面已公开在例如美国专利第5,415,702号、第4,263,059号、第4,171,231号、第3,932,198号、第3,647,569号、第3,501,352号以及第2,559,878号中。在上述专利中描述的含有作为基本仅有的铬离子存在的三价铬的任意酸性铬水溶液可用于本发明的方法中。上述专利公开的内容通过引用并入本发明。
如所提到的，用于本发明的酸性铬水溶液包括作为基本仅有的铬离子存在的三价铬。在一实施方案中，铬溶液可包括偶然量(incidentalamount)的偶然(inadvertent)六价铬，在另一实施方案中，在溶液中的六价铬的量应当小于将形成含有0.1mg/m2的铬涂层的量。三价铬可直接来源于包括硫酸铬(III)、氯化铬(III)、醋酸铬(III)、硝酸铬(III)等许多来源。在一实施方案中，三价铬来源于氯化铬(III)。在另一实施方案中，用于本发明方法的酸性溶液中的三价铬可通过对含有六价铬的溶液进行还原来制备。如果伴随六价铬引入的阴离子或阳离子对溶液自身或锌或锌镍合金表面无害的话，六价铬的各种水溶性的或水分散性的来源可用于制备三价铬。
在一实施方案中，酸性铬溶液还包括一种或多种的氯离子、硝酸根离子、锌离子以及氟离子。
可存在于酸性铬溶液的氯离子可作为氯化铬或其它氯化物例如氯化钠、氯化钾、氯化铵、氯化锌等被引入。可存在于本发明的一个实施方案中的硝酸根离子可通过使用硝酸和可溶的铵以及碱金属硝酸盐如硝酸铵、硝酸钠、硝酸钾等被引入。在一实施方案中，铬溶液还包括锌离子。锌离子可作为氯化锌、氟化锌、硫酸锌、溴化锌、醋酸锌、甲基磺酸锌、氧化锌等引入电镀溶液中。如果伴随氟离子引入的离子对溶液的性能无害的话，可存在于酸性铬溶液中的氟离子可通过使用任意可溶的氟化物化合物被引入。可以使用金属或铵的氟化物，通常的氟化物物质包括氢氟酸、碱金属氟化物以及碱金属氢氟化物如氟化钠、氟化铵、氟化氢铵等。由于需要高水溶性，一个实施方案中使用高度可溶的氟化物如氟化氢钠或氟化氢铵。
根据本发明的方法在锌和锌合金表面上涂覆铬涂层而使用的铬水溶液是酸性的(即pH值达到6.9)，在一实施方案中，酸性铬水溶液的pH值从约1至约3或4。在另一实施方案中，用于沉积铬涂层的溶液的pH值维持在从约1至约2。铬溶液的酸度可通过加入一种或多种无机酸如硝酸、硫酸、盐酸、氢氟酸等来调节至并且维持在所需的pH值。在另一实施方案中，可使用有机酸如甲酸、醋酸以及丙酸。
在一实施方案中，在涂覆操作中的锌或锌合金表面首先通过化学和/或物理方法清洁以除去任何油脂、污垢或氧化物，尽管这种处理不总是被需要的。用水清洗表面之后，表面使用上述的酸性含铬水溶液处理。该处理可以通过任何常用的技术进行，如喷、刷、浸渍、辊涂、逆向辊涂以及流涂。在一实施方案中，在从约40℃至约70℃的温度下和约10秒至约2分钟的一段时间内将酸性铬溶液涂覆到锌或锌合金表面。
在一实施方案中，使用的铬酸盐转化涂料溶液可由浓缩物制备，该浓缩物包括约41重量份的水、37重量份的含有约13.1重量％至13.5重量％的铬(III)的中间体氯化铬溶液(Cr(OH)xCl3-x)、3重量份的氟化氢铵、18重量份的硝酸钠以及1重量份的氯化锌。该浓缩物在水中稀释至约8-10体积％，并可在pH值为约1.3至约1.8的范围内、在从约122至约144(50-65℃)的温度下和约1至2分钟的一段时间内将其涂到电镀了锌-镍合金的金属上。对于电镀了锌-铁合金和锌-铁-钴的金属表面上的使用，在pH值为约1.8至约2.0的范围内、在从约130至约145(54-63℃)的温度下和约1至2分钟内，使用铬溶液处理该电镀了合金的金属。
各种商业上可获得的三价铬涂料溶液和方法在本发明的方法中是可用的，这些包括可由Atotech美国公司获得的RODIPZnX铬酸盐转化涂料、EcoTri以及CorroTriblue。
如上所述铬酸盐膜已沉积在电镀了锌或锌合金的金属上之后，使用阴极电涂方法将干燥的有机涂料组合物的保护膜涂覆并且沉积在铬涂层上。在电涂方法中，涂覆了铬酸盐的金属物品放置在包含水乳化胶状涂料颗粒的干燥的有机涂料组合物中。在本发明的方法中，负电荷位于成为阴极的涂覆了铬且电镀了锌或锌合金的金属上，正电荷应用于第二电极——通常是涂料的容器。在该电场中，处于悬浮并且具有正电荷的涂料的胶粒被吸引到具有负电荷(阴极)的金属表面。一旦接触带有负电荷的金属表面，胶粒就释放它们的电荷因而破坏乳剂，并且胶粒作为涂料沉积在阴极上(待涂覆的金属部分)
由于涂层形成并且在厚度上增加，干燥有机涂料增加的抵抗性材料特性成为一个因素，并且在某点阴极电流密度落入不再发生电沉积的点。如果需要额外的涂层厚度，则增加电压梯度。因此，在电沉积方法中使用的电位由涂层所需的厚度、电导率、镀液的组成以及分配用于形成涂层的时间来确定。在一实施方案中，从约10伏特至约1000伏特的电压在从每平方英尺约0.1安培至7安培的电流密度时是有用的。在一实施方案中，使用从25伏特至约350伏特的电压获得令人满意的干燥的有机涂层。在一实施方案中，当已使用锌-镍合金电镀金属时，在约120伏特至约150伏特的范围内的电压可被使用。
然后，涂覆的金属片从溶液中取出，清洗并且在炉中烘焙以硬化(cure)沉积的涂层。阴极电沉积的干燥有机涂层的厚度可在较宽范围上变化。在一实施方案中，厚度为从约5微米至约50微米。在另一实施方案中，涂层厚度为从约10微米至约25微米。
在本发明的阴极电涂方法中使用的干燥的有机涂料组合物通常包括基于已使用可溶性酸中和的水可分散或可乳化的合成碱性聚合物树脂的水乳胶、分散体或溶液。在一实施方案中，干燥的有机涂料包括采用可溶性酸中和的热固性树脂，这些热固性树脂包括环氧树脂、氨基树脂、环氧树脂和氨基树脂的混合物等。本发明方法中使用的水性干燥的有机涂料组合物中的树脂的量可在约3重量％至约40重量％的范围内。在另一实施方案中，包括在水性干燥的有机涂料组合物中的树脂的量可在约5重量％至约25重量％的范围内。
本发明使用的干燥的有机涂料组合物还可包含可以是无机颜料或染料的颜料。颜料的选择将取决于在涂层中所需的特殊颜色。加入至本发明的水性组合物中的颜料的量将为组合物总重量的约0％至约25％或更多。
炭黑是经常用在黑色配方中的公知的颜色颜料。可用作本发明中的颜色颜料的炭黑是炉黑、槽法炭黑以及灯黑。颜料粉末还可以是金属粉末、金属氧化物以及其它无机化合物。金属粉末的例子包括镍、镍片、钢片、青铜粉、铝粉等。可用作颜料的金属氧化物是氧化锌、氧化铝、氧化镁、硅、滑石、云母、粘土、氧化铁红、氧化铁黄、氧化铬绿以及二氧化钛白。可用于提供所需颜色的其它无机颜料包括硫化锌、硫化镉、硫代硒化镉、镉汞、碳酸钙、钼酸锌、铬酸锌、铝酸钴、铬钴-氧化铝、群青(ultra marine blue)以及碳酸铅。有机颜料包括对位红(Para Red)、立索尔宝红(Lithol Rubine)、Halio枣红(HalioBordeaux)、硫醇靛蓝(Thio Indigo)、甲苯胺、蒽醌、酞菁蓝、酞菁绿、偶氮等。
除了水、树脂以及可选择的颜料外，用于本发明方法的干燥的有机涂料组合物还可包含改变沉积在金属物品上的水性组合物和/或涂料特性的其它组分。因此，水性组合物可包含一种或多种的表面活性剂、滑润剂、有机磷酸酯、有机溶剂、表面张力改性剂、增粘剂、抑制腐蚀添加剂、流动和润湿改性剂、消泡剂等。
在一实施方案中，用在本发明方法中的干燥的有机涂料组合物可包含基于树脂约0.1重量％至约15重量％的疏水性氟代烯烃聚合物。氟代烯烃聚合物包括氟乙烯、偏二氟乙烯以及四氟乙烯与其它可聚合单体的聚合物及共聚物。聚合物和共聚物可通过悬浮聚合或本体聚合制备。用于干燥的有机涂料组合物的商业上可获得的聚偏二氟乙烯的例子是由Pennwalt公司获得的Kynar 202。聚氟乙烯的例子是由E.I.DuPont，De Nemours and Co.获得的Tedlar。在一实施方案中，氟代烯烃聚合物是聚四氟乙烯(PTFE)。聚四氟乙烯可以普通商品名Teflon由DuPont商业获得。四氟乙烯的共聚物也可被使用，这些包括以少量的基本上氟化的共聚单体而改性的C2F2聚合物和使用氟烯烃的C2F2聚合物等。
可包括在干燥的有机涂料组合物中的另一润滑剂是乙烯-丙烯酸共聚物的锌盐的水性分散体，它可以普通商品名ACquaTM 220由Michelman，Inc.，Cincinnati，Ohio获得。
用于在本发明中使用的阴极电沉积的水性干燥的有机涂料组合物可由几个来源商业获得。例如，PolySeal III和Powercron 645 Black可由PPG获得。这两种涂料认为包括环氧树脂。有用的干燥的有机涂料组合物还可由Atotech美国公司获得。
在一实施方案中，在金属上沉积的干燥的有机涂层已被硬化之后，润滑膜可涂覆在硬化的干燥的有机涂层上。在一实施方案中，在干燥的有机涂料组合物上涂覆的润滑剂是转矩张力改性剂。可在干燥的有机涂层上施用的润滑剂组合物的例子包括聚乙烯蜡、聚四氟乙烯、烃或植物油、氯化的石蜡、磷酸酯、硫化油、硫化脂肪、聚乙二醇、羧酸酯、聚α-烯烃等。上述任意润滑剂的两种或多种的混合物可被使用。取决于使用的特别的润滑剂，润滑剂可施用到在溶液中或在非溶剂如水中分散的纯净的干燥的有机涂层上。润滑剂可使用本领域的公知技术如喷、刷、浸渍、辊涂、逆向辊涂以及流涂等涂覆。涂覆润滑剂组合物之后，润滑剂涂层被干燥以除去任何溶剂和/或水。
根据本发明的方法已被处理的金属物品表现出改善的耐蚀性和耐锈蚀性，如通过将处理后的金属片经受各种测试所证明的，如根据ASTM程序B117的盐雾腐蚀试验、根据试验程序VDA 621-415的循环腐蚀试验(CCT)、根据VDA 621-414的室外耐候试验以及根据Din50021的使用划线的NSS测试。
虽然根据各种实施方式已对本发明进行了说明，但是应当理解为，其中的各种变型对于依据阅读本说明书的本领域的技术人员来说是显而易见的。因此，应当这样理解，在此公开的本发明试图覆盖落入所附权利要求范围的各种变型。
(按照条约第19条的修改)
1、一种改善金属的耐蚀性的方法，该方法包括：
(A)使用锌合金电镀金属以形成具有主要γ结晶相的锌合金表面，
(B)通过锌合金表面与含有作为基本仅有的铬离子存在的三价铬的酸性铬水溶液接触，将铬涂料涂覆到锌合金表面上，以及
(C)使用阴极电涂方法将干燥的有机涂料沉积到铬涂层上。
2、根据权利要求1所述的方法，其中，所述锌合金包括锌和一种或多种的铁、镍、钴以及镁。
3、根据权利要求1所述的方法，其中，所述金属包括铝、铁、钢、镁、镁合金或镀锌铁。
4、根据权利要求1所述的方法，其中，所述金属包括钢。
5、根据权利要求1所述的方法，其中，所述酸性铬水溶液还包括氯离子和硝酸根离子。
6、根据权利要求1所述的方法，其中，所述酸性铬水溶液还包括锌离子。
7、根据权利要求5所述的方法，其中，所述酸性铬水溶液还包括氟离子。
8、根据权利要求1所述的方法，该方法进一步包括(D)硬化干燥的有机涂层和(E)在硬化的干燥的有机涂层之上涂覆润滑剂膜。
9、根据权利要求1所述的方法，其中，所述锌合金表面是锌-镍合金表面。
10、根据权利要求5所述的方法，其中，所述酸性铬水溶液还包括锌离子和氟离子。
11、根据权利要求9所述的方法，其中，所述锌-镍合金包括从约8重量％至约20重量％的镍。
12、根据权利要求1所述的方法，其中，所述锌合金表面是锌-铁表面。
13、一种具有改善的耐蚀性和粘附性的具有有机涂层的金属片，该金属片包括在其表面上电镀了锌合金的金属片，由包括作为基本仅有的铬离子存在的三价铬的酸性铬水溶液而沉积的铬酸盐膜，以及在铬酸盐膜上的阴极电涂的干燥的有机涂层，其中所述锌合金具有主要γ结晶相。
14、根据权利要求13所述的金属片，其中，所述金属包括铝、铁、钢、镁、镁合金或镀锌铁。
15、根据权利要求13所述的金属片，其中，所述金属是钢。
16、根据权利要求13所述的金属片，其中，所述锌合金是锌-镍或锌-铁合金。
17、根据权利要求13所述的金属片，其中，所述铬酸盐膜来自包括作为基本仅有的铬离子存在的三价铬、氯离子以及硝酸根离子的酸性铬水溶液。
18、根据权利要求17所述的金属片，其中，所述酸性铬水溶液还包括锌离子和氟离子。
19、根据权利要求13所述的金属片，其中，所述干燥的有机涂层被涂覆上润滑剂膜。
Claims (26)
1、一种改善金属的耐蚀性的方法，该方法包括：
(A)使用锌或锌合金电镀金属以形成锌或锌合金表面，
(B)通过锌或锌合金表面与含有作为基本仅有的铬离子存在的三价铬的酸性铬水溶液接触，将铬涂料涂覆到锌或锌合金表面上，以及
(C)使用阴极电涂方法将干燥的有机涂料沉积到铬涂层上。
2、根据权利要求1所述的方法，其中，所述锌合金包括锌和一种或多种的铁、镍、钴以及镁。
3、根据权利要求1所述的方法，其中，所述金属使用锌-镍合金电镀以形成锌-镍合金表面。
4、根据权利要求3所述的方法，其中，所述锌-镍合金具有主要γ结晶相。
5、根据权利要求1所述的方法，其中，所述金属包括铝、铁、钢、镁、镁合金或镀锌铁。
6、根据权利要求1所述的方法，其中，所述金属是钢。
7、根据权利要求1所述的方法，其中，所述酸性铬水溶液还包括氯离子和硝酸根离子。
8、根据权利要求1所述的方法，其中，所述酸性铬水溶液还包括锌离子。
9、根据权利要求7所述的方法，其中，所述酸性铬水溶液还包括氟离子。
10、根据权利要求1所述的方法，该方法还包括(D)硬化干燥的有机涂层和(E)在硬化的干燥的有机涂层之上涂覆润滑剂膜。
11、一种改善金属的耐蚀性的方法，该方法包括：
(A)使用包含锌和一种或多种的铁、镍、钴以及镁的锌合金电镀金属以形成锌合金表面，
(B)通过锌合金表面与含有作为基本仅有的铬离子存在的三价铬、氯离子以及硝酸根离子的酸性铬水溶液接触，将铬涂料涂覆到锌合金表面上，以及
(C)使用阴极电涂方法将干燥的有机涂料组合物沉积到铬涂层上。
12、根据权利要求11所述的方法，其中，所述金属包括钢。
13、根据权利要求11所述的方法，其中，所述锌合金表面是锌-镍合金表面。
14、根据权利要求13所述的方法，其中，所述锌-镍合金具有主要γ结晶相。
15、根据权利要求11所述的方法，其中，所述酸性铬水溶液还包括锌离子和氟离子。
16、根据权利要求13所述的方法，其中，所述锌-镍合金包括从约8重量％至约20重量％的镍。
17、根据权利要求11所述的方法，其中，所述锌合金表面是锌-铁表面。
18、根据权利要求11所述的方法，该方法还包括(D)硬化干燥的有机涂层和(E)在硬化的干燥的有机涂层之上涂覆润滑剂膜。
19、一种具有改善的耐蚀性和粘附性的具有有机涂层的金属片，该金属片包括在其表面上电镀了锌或锌合金的金属片，由包括作为基本仅有的铬离子存在的三价铬的酸性铬水溶液而沉积的铬酸盐膜，以及在铬酸盐膜上的阴极电涂的干燥的有机涂层。
20、根据权利要求19所述的金属片，其中，所述金属包括铝、铁、钢、镁、镁合金或镀锌铁。
21、根据权利要求19所述的金属片，其中，所述金属是钢。
22、根据权利要求19所述的金属片，其中，所述金属片包括电镀了锌合金的金属片。
23、根据权利要求19所述的金属片，其中，所述金属片包括电镀了锌-镍或锌-铁合金的金属片。
24、根据权利要求19所述的金属片，其中，所述铬酸盐膜来自包括作为基本仅有的铬离子存在的三价铬、氯离子以及硝酸根离子的酸性铬水溶液。
25、根据权利要求24所述的金属片，其中，所述酸性铬水溶液还包括锌离子和氟离子。
26、根据权利要求19所述的金属片，其中，所述干燥的有机涂层被涂覆上润滑剂膜。
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| US10/985,452 US7101469B2 (en) | 2004-11-10 | 2004-11-10 | Metal pieces and articles having improved corrosion resistance |
| US10/985,452 | 2004-11-10 |
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| US (2) | US7101469B2 (zh) |
| EP (1) | EP1809790B1 (zh) |
| JP (1) | JP2008519907A (zh) |
| CN (1) | CN100585003C (zh) |
| ES (1) | ES2573461T3 (zh) |
| PL (1) | PL1809790T3 (zh) |
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| CN107034501A (zh) * | 2017-06-20 | 2017-08-11 | 珠海市玛斯特五金塑胶制品有限公司 | 一种发动机周边水管表面处理工艺及其电泳治具 |
| CN109750341A (zh) * | 2017-11-06 | 2019-05-14 | 通用汽车环球科技运作有限责任公司 | 涂覆至少一个表面包含铝合金的白车身结构的方法 |
| CN110312823A (zh) * | 2017-02-13 | 2019-10-08 | 德国艾托特克公司 | 用于电解钝化最外侧铬或最外侧铬合金层以增加其抗腐蚀性的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102282296B (zh) * | 2008-11-14 | 2014-10-15 | 恩索恩公司 | 金属层的后处理方法 |
| CN110312823A (zh) * | 2017-02-13 | 2019-10-08 | 德国艾托特克公司 | 用于电解钝化最外侧铬或最外侧铬合金层以增加其抗腐蚀性的方法 |
| CN110312823B (zh) * | 2017-02-13 | 2021-12-10 | 德国艾托特克公司 | 用于电解钝化最外侧铬或最外侧铬合金层以增加其抗腐蚀性的方法 |
| CN107034501A (zh) * | 2017-06-20 | 2017-08-11 | 珠海市玛斯特五金塑胶制品有限公司 | 一种发动机周边水管表面处理工艺及其电泳治具 |
| CN109750341A (zh) * | 2017-11-06 | 2019-05-14 | 通用汽车环球科技运作有限责任公司 | 涂覆至少一个表面包含铝合金的白车身结构的方法 |
| CN109750341B (zh) * | 2017-11-06 | 2021-10-29 | 通用汽车环球科技运作有限责任公司 | 涂覆至少一个表面包含铝合金的白车身结构的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008519907A (ja) | 2008-06-12 |
| PL1809790T3 (pl) | 2016-11-30 |
| US7101469B2 (en) | 2006-09-05 |
| US20060286399A1 (en) | 2006-12-21 |
| CN100585003C (zh) | 2010-01-27 |
| US20060099439A1 (en) | 2006-05-11 |
| PT1809790E (pt) | 2016-06-09 |
| EP1809790A1 (en) | 2007-07-25 |
| EP1809790B1 (en) | 2016-04-27 |
| WO2006052357A1 (en) | 2006-05-18 |
| ES2573461T3 (es) | 2016-06-08 |
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