CN101356301A - 钝化具有锌或锌合金表面的加工件的含水反应溶液和方法 - Google Patents
钝化具有锌或锌合金表面的加工件的含水反应溶液和方法 Download PDFInfo
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- CN101356301A CN101356301A CNA2007800013029A CN200780001302A CN101356301A CN 101356301 A CN101356301 A CN 101356301A CN A2007800013029 A CNA2007800013029 A CN A2007800013029A CN 200780001302 A CN200780001302 A CN 200780001302A CN 101356301 A CN101356301 A CN 101356301A
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- Prior art keywords
- reaction solution
- aqueous reaction
- acid
- zinc
- workpiece
- Prior art date
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- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 68
- 239000011701 zinc Substances 0.000 title claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 29
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229960003512 nicotinic acid Drugs 0.000 claims abstract description 25
- 235000001968 nicotinic acid Nutrition 0.000 claims abstract description 25
- 239000011664 nicotinic acid Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 150000002390 heteroarenes Chemical class 0.000 claims abstract description 12
- 238000002161 passivation Methods 0.000 claims description 33
- -1 lanthanon Inorganic materials 0.000 claims description 21
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 125000000627 niacin group Chemical group 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 229910001430 chromium ion Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 46
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 25
- 238000004532 chromating Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000011651 chromium Substances 0.000 description 12
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 240000007817 Olea europaea Species 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 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 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 210000000959 ear middle Anatomy 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005246 galvanizing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- 229910001436 Cr3+ Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 230000005571 horizontal transmission Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- PRUQOJJEKBMXGH-UHFFFAOYSA-N azane;tetramethyl silicate Chemical compound N.CO[Si](OC)(OC)OC PRUQOJJEKBMXGH-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000002520 cambial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- UUMMHAPECIIHJR-UHFFFAOYSA-N chromium(4+) Chemical compound [Cr+4] UUMMHAPECIIHJR-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- XVHFYNOGAFYRJV-UHFFFAOYSA-L chromium(ii) oxalate Chemical compound [Cr+2].[O-]C(=O)C([O-])=O XVHFYNOGAFYRJV-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004673 fluoride salts Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种含水反应溶液,利用所述含水反应溶液在锌或锌合金表面上产生抗腐蚀性黄色钝化层,其含有三价铬离子、至少一种酸以及至少一种选自烟酸及其盐和衍生物的芳香杂环化合物。
Description
技术领域
本发明涉及钝化具有锌或锌合金表面的加工件的含水反应溶液和方法,以及芳香杂环化合物的用途,所述化合物选自烟酸及其盐和衍生物,用于在锌和锌合金表面上产生有色的钝化层。
背景技术
金属材料,更特别是铁和钢,被镀锌或镀镉以保护其不受腐蚀环境因素影响。锌的防腐蚀性归因于其甚至比基底金属更便宜,使得其首先吸引所有的腐蚀攻击,从而充当了牺牲层。只要其保持完全被锌覆盖,涉及的镀锌组件的基底金属就保持完整,机械功能保持的时间比没有镀锌的部件更长。当然,厚锌层比薄锌层提供更强的防腐蚀性——腐蚀去除较厚的层需要较长的时间。
对锌层的腐蚀攻击可以通过铬酸盐处理而显著延迟,使得对基底金属的腐蚀也比仅镀锌更加延迟。通过层系统锌/铬酸盐处理的防腐蚀性比仅具有相同厚度的锌层提供的防腐蚀性好很多。另外,铬酸盐处理还通过环境因素延迟对组件的光学腐蚀——锌的腐蚀产物,所谓的锌锈,也影响组件的外观。
铬酸盐处理的优点是如此重要以至于几乎任何电镀镀锌表面都另外进行铬酸盐处理。现有技术已知四种以其颜色命名的铬酸盐处理方法,并通过用相应的铬酸盐水溶液处理(浸渍、喷射、滚轧)镀锌表面来应用所述方法。另外,以类似的方式产生的黄色和绿色铬酸盐处理对于铝是已知的。无论如何,这些层具有不同厚度并且基本上由非化学计量组成的无定形锌/氧化铬(或铝/氧化铬)、一定的含水量和掺入的杂质离子制成。下述铬酸盐处理方法是已知的并依据DIN 50960,part 1在方法组中分类:
1)无色和蓝色铬酸盐处理,组A和B:
蓝色铬酸盐处理层为最多80nm厚,自身为淡蓝色并且依据层厚度而具有由光折射而产生的金色、微红、浅蓝色、绿色或黄色的彩虹色彩。非常薄的铬酸盐层几乎没有任何自身的颜色,其被归类为无色铬酸盐处理(组A)。在这两种情况下,铬酸盐处理溶液都可以由六价的和三价的铬酸盐及其混合物、还有支持电解液和无机酸组成。有些变体含有氟化物,有些不含氟化物。铬酸盐处理溶液在室温下使用。依据DIN 50021 SS,在盐雾室中,在最初腐蚀产物出现之前,完整的蓝色铬酸盐处理(组B)的防腐蚀性总计为10-40h。依据DIN 50961,第10章,表3对方法组A和B的最小要求为,对于处于鼓室中的加工件为8h,对于处于架上的加工件为16h。
2)黄色铬酸盐处理,组C:
黄色铬酸盐处理层约0.25-1μm厚,显金黄色和常有的强紫绿彩虹色。铬酸盐处理溶液基本上由水溶性六价铬酸盐、支持电解液和无机酸组成。黄色,除了是由于在形成层的反应过程中通过还原产生的三价铬之外,还由于所包括的很大一部分六价铬(80-220mg/m2)。铬酸盐处理溶液在室温下使用。依据DIN 50021 SS,在盐雾室中,在最初腐蚀产物出现之前,完整的黄色铬酸盐处理的防腐蚀性总计为100-200h。依据DIN 50961,第10章,表3对方法组C的最小要求为,对于处于鼓室中的加工件为72h,对于处于架上的加工件为96h。
3)橄榄色铬酸盐处理,组D:
典型的橄榄色铬酸盐处理层具有最多1.5μm的厚度,并且遍布橄榄绿至橄榄棕。铬酸盐处理溶液基本上由水溶性六价铬酸盐;支持电解液和无机酸,更特别是磷酸盐或磷酸组成,并还可以含有甲酸盐。将大量的铬(VI)(300-400mg/m2)掺入层中。铬酸盐处理溶液在室温下使用。依据DIN 50021SS,在盐雾室中,在最初腐蚀产物出现之前,完整的橄榄色铬酸盐处理的防腐蚀性总计为200-400h。依据DIN 50961,第10章,表3对方法组D的最小要求为,对于处于鼓室中的加工件为72h,对于处于架上的加工件为120h。
4)黑色铬酸盐处理,组F:
黑色铬酸盐处理层基本上是黄色或橄榄色铬酸盐处理,其中掺入胶态银作为色素。铬酸盐处理溶液与黄色或橄榄色铬酸盐处理溶液具有大致相同的组成,并且另外含有银离子。如果铬酸盐处理溶液的组成适合,铁、镍或钴氧化物作为黑色颜料混入锌合金层如Zn/Fe、Zn/Ni或Zn/Co上的铬酸盐层,使得银在这种情况下不是必要的。依据基础是黄色还是橄榄色铬酸盐处理,将80-400mg/m2的大量的铬(VI)掺入铬酸盐层。铬酸盐处理溶液在室温下使用。依据DIN 50021 SS,在盐雾室中,在最初腐蚀产物出现之前,完整的对锌的黑色铬酸盐处理的防腐蚀性总计为50-150h。依据DIN 50961,第10章,表3对方法组F的最小要求为,对于处于鼓室中的加工件为24h,对于处于架上的加工件为48h。对锌合金的黑色铬酸盐处理比所提到的那些具有高得多的值。
5)用于铝的绿色铬酸盐处理,组E:
依据现有技术,依据DIN 50021 SS或ASTM 117-73在盐雾室中,依据DIN 50961(1987年六月)第10章,更特别是10.2.1.2章在最初腐蚀产物出现之前,防腐蚀性>100h的厚铬酸盐层,可以无需密封和任何其它特别的后处理(DIN 50961,第9章),而仅通过用溶解的、明显有毒的铬(VI)化合物处理来制造。因此,满足上述对防腐蚀性的要求的铬酸盐层还含有这些明显有毒的和致癌的铬(VI)化合物,并且所述铬(VI)化合物在层中不是完全固定化的。用铬(VI)化合物的铬酸盐处理在职业安全和健康方面是有问题的。用铬(VI)化合物制得的镀锌铬酸盐处理的应用,如在螺丝钉上广泛应用的黄色铬酸盐处理,对人群构成潜在威胁并且通常增加癌症的风险。
因此,部分或全部避免使用铬(VI)化合物的钝化方法在现有技术中有描述。
美国专利4,384,902,特别是其实施例1、2、4和5描述了达到盐雾试验要求的钝化层。在所有情况下,层含有铈,具有通过Ce(IV)离子强调的微黄色。在电解液中,实施例只含有Ce(III)和作为氧化剂的过氧化氢。说明书讨论了在酸性条件下,过氧化氢没有充当Ce(III)的氧化剂,但是在产生足够量的Ce(IV)的沉积过程中,表面pH大大增加。用所述的电解组合物得到的微黄色实际上是氧化的指示,但是仅仅是Ce(III)氧化为Ce(IV)。四价铈是比六价铬更有效的氧化剂,这就是Ce(IV)将从Cr(III)产生Cr(VI)的原因,而这是要避免的。Cr(VI)具有非常强的黄色,是已知的防腐蚀剂。因此,在美国专利4,384,902中描述的层含有六价铬。
美国专利4,359,348也描述了达到盐雾室试验中上述要求的钝化层。再一次,在所有情况下,层含有铈,其具有由Ce(IV)离子强调的微黄色。因此,此文献未超越美国专利4,384,902。
另外,美国专利申请2003/00234063 A1公开了基于钴的无毒防腐蚀金属表面层。这些金属表面层被描述为适于例如锌基底。其中,所述金属表面层可含有Cr(III)离子和烟酸。
另外,美国专利6,190,780 B1公开了一种具有抗腐蚀涂层的表面处理的金属材料。所述金属材料可以是镀熔融锌钢板。金属表面层可以含有Cr(OH)3和烟酸。
另外,GB-A-2 097 024公开了用含有氧化剂和至少一种金属的酸性水溶液对金属表面处理以改善锌和锌合金表面上的防腐蚀性,其中所述至少一种金属选自铁、钴、镍、钼、锰、铝、镧、镧系元素混合物或铈离子或其混合物,和更特别的是铁和钴离子。另外,GB-A-2 097 024公开了三价铬离子和铁离子与其它金属结合使用的用途,所述其它金属选自上述离子或铈离子,但是主要描述了铬(III)与氧化剂和铈或镧离子的结合。
DE 196 15 664 A1描述了一种产生具有更大的层厚度和增强的防腐蚀性的无铬(VI)钝化层的方法。从而将有机螯合配位体,更特别的是二羧酸、三羧酸和羟基羧酸如草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、邻苯二甲酸、对苯二甲酸、抗坏血酸、苹果酸、酒石酸或柠檬酸添加到反应溶液中。这些螯合配位体与铬(III)形成络合物,所述络合物具有弱的动力学稳定性,并且迅速释放所述铬以高反应速度混入增长的ZnCrO层。将金属离子如二价钴离子以可溶盐的形式加入作为提高反应速度和铬酸盐层厚度增长的额外催化剂。如此产生的钝化层不含有任何铬(IV)并使防腐蚀性达到高于100h,其约相当于传统黄色铬酸盐处理的防腐蚀性。如此产生的铬酸盐层具有绿色、紫绿色彩虹色。在DE 41 35 524 A1中描述了一种可替代的钝化方法,其依赖于铬(III)草酸盐络合物,形成蓝色钝化薄膜。
DE 103 05 449 A1描述了一种物质的混合物和产生有色钝化层的方法,它们都依赖于含有铬(III)离子的反应溶液和喹啉染料的组合。其缺点在于喹啉染料在反应液和钝化层中的稳定性都是差的。其中,这是由于此化合物缺乏紫外稳定性。
在此提到的上述实施例表明铬(III)钝化仍旧仅限于有限的应用。除了通常用蓝色铬酸盐处理的弱防腐蚀性和铬(VI)残留物的风险外,还有用铬(III)钝化着色的可能性受到限制的缺点。通过铬(III)钝化得到的色彩基本上限于铬酸盐的蓝色和绿色层,而基于铬(III)的黄色铬酸盐处理不能赋予均匀的强黄色,而是得到明显的淡彩虹色涂层或倾向于蓝色或绿色的涂层。
已经重复进行尝试以产生仅含小部分铬(VI)或根本不含铬(VI)的黄色钝化层。在传统黄色铬酸盐处理中的强黄色正是通过铬(VI)被赋予。
因此本发明的一个目的是提供一种在基底上产生钝化层的溶液,所述溶液含有铬(III)但不含铬(VI)。
本发明的另一个目的是提供一种在基底上产生钝化层的溶液,所述层是色彩强烈的,持久稳定的黄色。
本发明的另一个目的是提供一种在基底上产生钝化层的溶液,所述层适于防止基底腐蚀。
本发明的另一个目的是提供一种在基底上产生钝化层的方法,所述层几乎不含有任何铬(VI),为色彩强烈的、持久稳定的黄色并适于防止基底腐蚀。
发明内容
通过权利要求1所述的含水反应溶液,用权利要求14所述的钝化包含锌和锌合金表面的加工件表面的方法以及通过使用选自烟酸及其盐和衍生物的芳香杂环化合物来达到这些目的,用于如权利要求20所述在锌和锌合金表面上产生有色钝化层。本发明的优选实施方案在从属权利要求中被陈述。
本发明更特别适于在锌和锌合金表面上产生几乎不含任何铬(VI)的黄色钝化层。依据本发明,黄色钝化处理的效果通过含有铬(III)离子、至少一种酸以及至少一种选自烟酸及其盐和衍生物的芳香杂环化合物的含水反应溶液来得到。通过添加所述芳香杂环化合物得到用于钝化锌和锌合金表面的稳定的化学组合物。烟酸被用作优选的芳香杂环化合物。可以使用所述游离酸的盐,特别是钠盐或钾盐来代替游离酸。这将使酸能够在水溶液中更易于溶解。
具体实施方式
芳香杂环酸的有利浓度强烈取决于黄色钝化想要的色彩强度,并且通常可以为至少4·10-3mol/l(如果使用烟酸,相当于0.5g/l),更特别是至少10-2mol/l(如果使用烟酸,相当于1.25g/l),还更特别是5·10-2mol/l(如果使用烟酸,相当于6.2g/l)并最优选8·10-2mol/l(如果使用烟酸,相当于10g/l)。浓度上限可以是325·10-3mol/l(如果使用烟酸,相当于40g/l),优选240·10-3mol/l(如果使用烟酸,相当于30g/l),并最优选175·10-3mol/l(如果使用烟酸,相当于22g/l)。芳香杂环化合物的优选浓度为至少5g/l,更优选10g/l,还更优选至少15g/l。这些化合物的浓度优选不超过30g/l,更优选20g/l。通常适用的是,黄色越强烈,烟酸含量越高。在烟酸的浓度超过20g/l时,观察到的色彩强度的增加可以忽略。在将前述浓度范围(以g/l计)转换成mol/l的情况下,它们也适用于烟酸的盐和其衍生物。
黄色有特别实际的用途,因为其用于如在汽车工业中区分大规模生产的加工零件中的加工件。有目的的用本发明的组合物染色能够例如可靠和容易地区分出右旋组件和左旋组件。这大大增加了生产安全性,特别是当加工大量非常类似的零件时。
然而,本发明的层是在没有氧化剂的情况下产生的,因此不含任何六价铬。提供有这样的层的加工件具有非常高的抗腐蚀性,这与提供有黄色铬酸盐处理的镀锌表面的抗腐蚀性相当或甚至比其更高。
用于实施该方法的反应溶液的pH可以例如为至少1.5,优选至少1.8。pH上限可以是3.0,优选2.2。期望的pH可以通过添加氢离子,也就是添加至少一种酸,优选柠檬酸或其它无机酸或羧酸而产生,并且然后可以用苛性钠溶液来进行精确调节。
溶解的铬(III)离子的浓度可以为至少0.2g/l,优选至少1g/l。其可以达到最多30g/l,优选最多5g/l。原则上,反应溶液中所含有的铬(III)化合物浓度可以达到饱和极限。氯化铬(CrCl3)、硝酸铬(Cr(NO3)3)、硫酸铬(Cr2(SO4)3)或其它水溶性铬(III)盐可以用作所述铬(III)离子源。
至少一种元素如铝、钴、镍、铁、镓、铟、镧系元素、锆、钪、钛、钒、铬、锰、铜、锌、钇、铌、钼、铪、钽和钨的二价到六价金属离子可以在反应溶液中用作催化剂。可以将这些金属离子以可溶盐的形式,优选硝酸盐、硫酸盐或卤化物的形式加入反应溶液中。在优选实施方案中,所含钴(II)离子的浓度为至少约0.1g/l。其浓度可以优选达到5g/l。含水或非水硝酸钴(Co(NO3)2)、硫酸钴(CoSO4)或氯化钴(CoCl2)是适合的钴(II)源的实例。
另外,化学组合物可以含有至少一种酸稳定的、水溶性硅酸盐用以改善钝化特性和提供钝化层以增加的硬度。优选其浓度为至少0.5g/l。浓度上限优选10g/l。这些浓度值都是基于SiO2。可用的硅酸盐可以是无机的也可以是有机的,只要它们可以溶解在反应液中。有机硅酸盐因为其关于电解槽寿命的稳定性能而是优选的。可用的无机硅酸盐可以是二氧化硅的酸稳定胶体溶液。也可以使用有机硅酸盐。此类硅酸盐可以是四甲基硅酸铵、苯基三甲基硅酸铵、苯基三甲基二硅酸铵和苯基三甲基三硅酸铵以及苄基三甲基硅酸铵和苄基三甲基二硅酸铵。具有化学通式ROR’:xSiO2:yH2O的有机硅酸盐是适用的,其中R为季铵基,其用选自烷基、烯基、烷醇、芳基、芳烷基和其混合物的四个有机残基取代,其中R’是R或者是氢,以及x=1-3和y=0-15。此类有机硅酸盐可以用当前的化学方法合成。合成方法例如在Merrill和Spencer的″Some Quaternary Ammonium Silicates″,Journal ofPhysical and Colloid Chemistry,55,187(1951)以及美国专利3,993,548中有描述。
反应溶液可以含有卤化物,更特别的是氯化物和氟化物;硫酸根离子;硝酸根离子;磷酸、磷酸酯或磷酸根离子;硅酸根离子;硅酸;氨基酸;胺和表面活性剂作为其它组分或支持离子。适合的表面活性剂为例如脂肪族氟碳磺酸盐,如美国3M公司的产品例如FC 98。另外,铬(III)离子的络合剂如丙二酸和草酸,可以含在其中。
使用本发明的反应溶液优选向具有由锌或锌合金制成的表面的加工件提供钝化层。具有由碱性的、氰化的或酸性的、非氰化的电解锌沉积产生的锌镀层的加工件和依靠熔融镀锌的或其本身由锌或锌合金制成的加工件两者都可用本发明的反应溶液钝化。加工件表面上的锌合金可以例如是Zn/Fe、Zn/Ni和Zn/Co合金。另外,这样的加工件可以用所述反应溶液以本发明教导的方式处理,其除了锌或锌合金表面之外,还具有不是由锌或锌合金制成的暴露面,例如含有铁的表面如钢表面。这些额外的表面可以与锌或锌合金表面一起被钝化。原则上,也有用本发明的反应溶液钝化铝表面、铝合金表面以及由镉制成的表面的可能性。
钝化方法包括将具有锌或锌合金表面的加工件与反应溶液接触。反应优选在至少约10℃的温度下进行。最大电镀槽温度可以例如为80℃。特别优选的电镀槽温度为30℃-50℃。
加工件可以优选通过浸渍与反应溶液接触,也就是将加工件浸入盛在槽中的反应溶液中。为此,加工件可以留在架上并与之一起浸入反应溶液中,或者位于鼓室中或托盘上并与所述鼓室或托盘一起浸入反应溶液中。在可替换的程序中,将加工件通过喷射浸渍与反应溶液接触。在加工的另一种方式中,将加工件通过喷射与反应溶液接触。加工件也可以用反应溶液例如通过流出反应溶液流的喷嘴喷溅。另一种处理加工件的方式为通过涂抹、滚轧或任何其它施涂技术将反应溶液施涂到加工件表面上。所述处理可以在传统生产线上进行,其中加工件分批处理,或在水平传送线上处理,加工件通过水平传送线连续通过并从而被处理。
如果加工件通过浸渍在反应溶液中进行处理,加工时间可以为20-200s;在优选实施方案中,其为约30s-约90s。根据将加工件与反应液接触所用的技术,可能需要较长或较短的加工时间。
为了实施本发明的钝化,加工件在与反应溶液接触前需要清洗。然而,如果加工件在电镀锌之后并随后将镀锌溶液冲洗掉之后立即与反应溶液接触的话,加工件的清洗可以避免。在完成本发明的钝化方法时,加工件优选例如用热空气干燥。另外,在干燥之前也可以冲洗加工件以从表面去除过量的反应溶液。
下列实施例用于进一步解释本发明:
实施例
实施例1:
在水中制备具有如下组成的反应溶液:
2g/l硝酸铬形式的Cr(III)
1.5g/l氟化氢铵
1ml/I硝酸(浓)
10g/l钠盐的形式的烟酸
将反应溶液的pH用硝酸或苛性钠调节至pH为2.0。将溶液加热至45℃。置于架上的镀锌零件浸渍在反应溶液中60秒,而后冲洗和干燥。得到的钝化层具有均匀的黄绿彩虹色。在最初的白锈信号出现前,其抗腐蚀性依据DIN 50021 SS被测定为约72h。
实施例2
重复实施例1所述的试验,另外将0.5g/l的硝酸钴(II)加到溶液中。在白锈出现之前,此层的抗腐蚀性依据DIN 50021 SS被测定为96h。
实施例3
重复实施例1的试验,其中水中的组成改变如下:
3g/l硝酸铬形式的铬(III)
2g/l氟化钠
1ml/l硝酸(浓)
1g/l丙二酸
5g/l钠盐形式的烟酸
得到的钝化层具有均匀的黄绿彩虹色。在白锈最初出现前,其抗腐蚀性依据DIN 50021 SS被测定为约96h。
需要理解的是,在此所述的实施例和实施方案仅用于说明的目的,依据其的各种改变和变化以及在此申请中所述的特征的结合都是本领域技术人员所能想到的,并包括在所述发明的精神和范围以及所附权利要求的范围内。在此引用的所有出版物、专利和专利申请均并入作为参考。
Claims (20)
1.用于钝化具有锌或锌合金表面的加工件的含水反应溶液,其含有三价铬离子以及至少一种酸,其特征在于,所述反应溶液含有至少一种选自烟酸及其盐和衍生物的芳香杂环化合物。
2.权利要求1所述的含水反应溶液,其特征在于,所述烟酸的盐为钠盐。
3.任一前述权利要求所述的含水反应溶液,其特征在于,所述至少一种芳香杂环化合物的浓度为约4·10-3mol/l-约325·10-3mol/l。
4.任一前述权利要求所述的含水反应溶液,其特征在于,在所述反应溶液中烟酸的浓度为约0.5-约30g/l。
5.任一前述权利要求所述的含水反应溶液,其特征在于,在所述反应溶液中烟酸的浓度为约10-约20g/l。
6.任一前述权利要求所述的含水反应溶液,其特征在于,所述三价铬离子的浓度为约0.2-约30g/l。
7.任一前述权利要求所述的含水反应溶液,其特征在于,所述三价铬离子的浓度为约1-约5g/l。
8.任一前述权利要求所述的含水反应溶液,其特征在于,所述反应溶液另外含有至少一种选自Al、Co、Ni、Fe、Ga、In、镧系元素、Zr、Sc、Ti、V、Cr、Mn、Cu、Zn、Y、Nb、Mo、Hf、Ta和W的元素的二价到六价金属离子。
9.任一前述权利要求所述的含水反应溶液,其特征在于,所述反应溶液另外含有浓度为约0.1-约5g/l的钴(II)离子。
10.任一前述权利要求所述的含水反应溶液,其特征在于,所述至少一种酸选自烟酸、盐酸和硫酸。
11.任一前述权利要求所述的含水反应溶液,其特征在于,所述反应溶液另外含有至少一种酸稳定的水溶性硅酸盐化合物。
12.权利要求9中所述的含水反应溶液,其特征在于,所述反应溶液含有至少一种卤素离子源。
13.任一前述权利要求所述的含水反应溶液,其特征在于,所述反应溶液含有至少一种氟离子源。
14.一种钝化具有锌或锌合金表面的加工件的方法,其包括将加工件与含有三价铬离子以及至少一种酸的含水反应溶液接触,其特征在于,所述反应溶液含有至少一种选自烟酸及其盐和衍生物的芳香杂环化合物。
15.权利要求14所述的方法,其特征在于,所述芳香杂环化合物的浓度为约4·10-3mol/l-约325·10-3mol/l。
16.权利要求14-15之一所述的方法,其特征在于,将加工件在约10℃-约80℃的反应温度下与所述含水反应溶液接触。
17.权利要求14-16之一所述的方法,其特征在于,将加工件在约30℃-约50℃的反应温度下与所述含水反应溶液接触。
18.权利要求14-17之一所述的方法,其特征在于,将加工件通过浸渍与所述含水反应溶液接触约20-约200秒。
19.权利要求14-18之一所述的方法,其特征在于,将加工件通过浸渍与所述含水反应溶液接触约30-约90秒。
20.一种选自烟酸及其盐和衍生物的芳香杂环化合物用于在锌或锌合金表面上产生有色钝化层的用途。
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JP2005327741A (ja) * | 2005-07-13 | 2005-11-24 | Ngk Spark Plug Co Ltd | スパークプラグ用ガスケット及びそれを備えたスパークプラグ |
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2006
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- 2006-01-31 PL PL06001930T patent/PL1816234T3/pl unknown
- 2006-01-31 EP EP06001930A patent/EP1816234B1/de active Active
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2007
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- 2007-01-23 CA CA2624215A patent/CA2624215C/en active Active
- 2007-01-23 JP JP2008551736A patent/JP5130226B2/ja active Active
- 2007-01-23 WO PCT/EP2007/000805 patent/WO2007088030A1/en active Application Filing
- 2007-01-23 CN CN2007800013029A patent/CN101356301B/zh active Active
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101665935B (zh) * | 2009-09-27 | 2012-04-11 | 大连三达奥克化学股份有限公司 | 钢铁工件电泳涂装前常温皮膜钝化剂及其制备方法 |
CN103866307A (zh) * | 2014-03-13 | 2014-06-18 | 沈阳市环东电镀厂 | 环保型一剂双色镀锌三价铬钝化剂及其制备和使用方法 |
TWI787775B (zh) * | 2020-04-03 | 2022-12-21 | 德商德國艾托特克公司 | 於鋅鐵合金上形成黑色鈍化層之方法及黑色鈍化組合物 |
Also Published As
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CA2624215A1 (en) | 2007-08-09 |
EP1979507A1 (en) | 2008-10-15 |
JP2009525398A (ja) | 2009-07-09 |
PL1816234T3 (pl) | 2009-10-30 |
CA2624215C (en) | 2013-07-02 |
WO2007088030A1 (en) | 2007-08-09 |
JP5130226B2 (ja) | 2013-01-30 |
ATE431442T1 (de) | 2009-05-15 |
US20090032146A1 (en) | 2009-02-05 |
EP1816234B1 (de) | 2009-05-13 |
DE502006003710D1 (de) | 2009-06-25 |
EP1816234A1 (de) | 2007-08-08 |
US8262811B2 (en) | 2012-09-11 |
CN101356301B (zh) | 2011-12-28 |
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