TWI500813B - 在金屬表面形成腐蝕保護層之方法 - Google Patents
在金屬表面形成腐蝕保護層之方法 Download PDFInfo
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- TWI500813B TWI500813B TW099111843A TW99111843A TWI500813B TW I500813 B TWI500813 B TW I500813B TW 099111843 A TW099111843 A TW 099111843A TW 99111843 A TW99111843 A TW 99111843A TW I500813 B TWI500813 B TW I500813B
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- Prior art keywords
- acid
- treatment
- solution
- chromium
- metal
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- 238000000034 method Methods 0.000 title claims description 39
- 229910052751 metal Inorganic materials 0.000 title claims description 25
- 239000002184 metal Substances 0.000 title claims description 25
- 238000005260 corrosion Methods 0.000 title claims description 21
- 230000007797 corrosion Effects 0.000 title claims description 21
- 230000008569 process Effects 0.000 title description 4
- 238000002161 passivation Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- -1 chromium (III) ions Chemical class 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 9
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001436 Cr3+ Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 150000001869 cobalt compounds Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 60
- 239000010410 layer Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 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 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
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- 239000002585 base Substances 0.000 description 4
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- 229910017604 nitric acid Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 150000001450 anions Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
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- 235000002906 tartaric acid Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
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- 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 2
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- 235000012208 gluconic acid Nutrition 0.000 description 2
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 description 2
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- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- 229940097043 glucuronic acid Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940099690 malic acid Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 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
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000723 toxicological property Toxicity 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- C23C22/36—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 containing also phosphates
- C23C22/362—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 containing also phosphates containing also zinc cations
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
本發明係關於一種製造在鋅、鋁或鎂亦及該等金屬之合金表面上基本上不含鉻(VI)之腐蝕保護層之方法。
一種以轉換層使陰極腐蝕保護系統之保護作用增加及作為清漆及油漆底漆之用途已為吾人知曉許久。除了磷化處理法之外，已確立一種使表面進行鉻酸鹽處理之方法，尤其針對含鋅基材、含鋁基材及含鎂基材而言。
此情況下，待處理之表面曝露於其主成分為鉻(VI)化合物之處理溶液。由此製得之轉換層因此亦包括鉻(VI)離子。鉻酸鹽處理層大體上顯示良好腐蝕保護及良好裝飾之性質。使用含鉻(VI)溶液或含鉻(VI)塗層之優點為鉻(VI)化合物之毒理學性質。因此，例如，含鉻(VI)轉換層之用途會極大地受限於EC指令2000/53/EC(EC舊車指令(old vehicle directVIe))。
已提議，作為鉻酸鹽處理溶液之替代品，對照鉻酸鹽處理而言，含鉻(III)之酸處理溶液通稱為「鈍化物」或「鈍化溶液」。例如，如DE 196 15 664 A1中所提議般，該等處理溶液基本上係藉由礦物酸溶液中之鉻(III)鹽、二羧酸或羥基羧酸、及鈷鹽組成。在約40至60℃之高溫下採用該等稱為「厚膜鈍化」之方法，以得到足以使鋅表面受保護免遭腐蝕之鈍化層厚度。需在高於室溫之溫度下進行該方法係由於鉻(III)離子相對於鉻(VI)離子之反應性特徵大大不足所致。作為溫度增加之替代之反應時間之明顯增加一般由於經濟原因而不可行。
作為替代方法，可藉著利用如US 5,415,702中所述額外包括磷之含氧酸之酸性含鉻(III)溶液處理，而在鋅-鎳合金層上製得不含Cr(VI)之黑色轉換層。在該方法中，形成具有良好裝飾性質之均勻黑色轉換層。
WO 03/05429描述同樣採用額外包括磷酸根離子之含鉻(III)酸性處理溶液製得之類似之轉換層。此同樣具有良好裝飾性質而沒有進一步進行後處理步驟(諸如密封)之表面無法達成令人滿意之腐蝕保護性質。
EP 1 484 432 A1描述用於鋅合金表面之包括鉻(III)離子及硝酸根亦及羧酸(諸如酒石酸、馬來酸、草酸、琥珀酸、檸檬酸、丙二酸或己二酸)之含鉻(III)黑色鈍化溶液。為改良腐蝕保護，利用該等溶液處理之表面必須經過隨後之密封。該等處理溶液係在高於正常室溫之溫度下採用。
US 2004/0156999同樣描述一種用於使鋅合金表面進行黑色鈍化之方法。該等處理溶液包括鉻(III)離子及含磷陰離子亦及硝酸根及有機羧酸。所給有機羧酸之實例為檸檬酸、酒石酸、馬來酸、甘油酸、乳酸、乙醇酸、丙二酸、琥珀酸、草酸及戊二酸。
基本上，在製造保護層中進行以下製程步驟：使金屬表面活化，在酸性鈍化浴中製得轉換層，藉由一次或更多次清洗操作使侵蝕性鈍化浴液自該表面移除，進行乾燥繼而施用另一種密封劑或在後浸塗溶液中進行後浸塗繼而進行乾燥。
該過程具有如下缺點：清洗廢水被相當大量重金屬污染且形成可能之錯合劑之，並必須加以處置或以複雜且昂貴之方式進行處理。
由於該等缺點，近來，吾人已努力發展「免清洗」法。此情況下，基本上施加包括使鈍化增加之金屬組分(例如鉻、鈦或鋯)、亦及藉由有機聚合物組成之膜成形組分之轉換層。該等方法主要用於鋁表面之處理。亦通常描述與膜成形聚合物組合之「免清洗」磷化處理。
因此，例如文獻US 6,117,251描述可使金屬表面進行磷酸鋅處理之包括氧化鋅、磷酸、聚乙烯醇及另一種金屬鹽之水性溶液。
就鋅、鋁及鎂表面而言，該等方法之使用僅僅係極其有限，因為儘管其可形成嵌入有機基質中之膜，但是令人滿意之腐蝕保護所需要之封閉氧化鉻層或表面金屬混合氧化物層並未形成。
本發明之一個目標係提供一種用於使鋅、鋁或鎂亦及該等金屬合金之金屬表面進行不含鉻(VI)鈍化之方法，藉由該方法，該等表面可得到極其良好之腐蝕保護性質，而同時不會獲得經污染之清洗水。
該目標可藉由一種在鋅、鋁或鎂表面亦及該等金屬合金表面形成腐蝕保護層之方法實現，該方法包括如下步驟：
i) 使前述金屬或所提及之金屬合金表面與包括如下之溶液接觸：鉻(III)離子，選自前述之表面金屬鋅、鋁或鎂或表面金屬合金之金屬離子，及至少一種選自由羧酸、聚羧酸、羥基羧酸、胺基羧酸、醇、胺基醚組成之群之錯合劑，其中該處理溶液具有1.0至4.0之pH。
ii) 然後，使所提及之等金屬之表面與包括如下之溶液直接接觸，鉻(III)離子，選自前述之表面金屬鋅、鋁或鎂或表面金屬合金之金屬離子，及至少一種選自由羧酸、聚羧酸、羥基羧酸、胺基羧酸、醇、胺及醚組成之群之錯合劑，其中該處理溶液具有3.0至12.0之pH。
在所提及之金屬及金屬合金表面形成腐蝕保護層之方法之特徵在於：在該方法之第一步驟中，金屬表面經過鈍化且在第二步驟中，於具有近似該組成之溶液中進行後處理。後處理使該鈍化層固定於該金屬表面上及因此得到耐用性腐蝕保護。由於兩步驟中皆採用具有基本上該組成之溶液，先前技術方法中必不可少地會在處理步驟之間進行清洗操作以避免夾帶繼而實現良好之腐蝕保護，可省略。在習知方法中需要之清洗操作會產生污染有重金屬離子及其他化學品且必須進行相當大費用之處置及純化之廢水，繼而導致環境污染。
本發明之方法使鈍化及後處理兩者首次在表面之腐蝕保護未受不利之影響下，採用具有基本上相同組分之溶液成為可能。
兩步驟中溶液不同pH值之鈀向設定使本身相同之處理溶液之功能得到控制。
使步驟1中所採用之基本上藉由鉻(III)鹽及針對金屬鋅、鎂或鋁及其合金而言之錯合劑組成之處理溶液設定至1.0至4.0之pH,1.2至3.0為較佳,1.5至2.5為最佳。因此，根據溶液之最初pH，可採用酸或鹼。硫酸及硝酸尤其適用於作為酸。較佳採用鹼金屬氫氧化物(具體之NaOH及KOH)作為鹼。
鉻(III)離子可以無機鉻(III)鹽(諸如鹼式硫酸鉻(III)、氫氧化鉻(III)、磷酸二氫鉻(III)、氯化鉻(III)、硝酸鉻(III)、硫酸鉀鉻(III))或有機酸之鉻(III)鹽(例如甲磺酸鉻(III)、檸檬酸鉻(III))之形式加至處理步驟1及2之處理溶液，或可藉由合適之鉻(VI)化合物在存在合適之還原劑下進行還原得到。例如，合適之鉻(VI)化合物為氧化鉻(VI)、鉻酸鹽(諸如鉻酸鉀或鉻酸鈉)、重鉻酸鹽(諸如重鉻酸鉀或重鉻酸鈉)。例如，原位產生鉻(III)離子之合適之還原劑為亞硫酸鹽(諸如亞硫酸鈉)、二氧化硫、亞磷酸鹽(諸如次磷酸鈉)、磷酸、過氧化氫、甲醇、葡萄糖酸。鉻(III)離子亦可以無機鉻(III)鹽、鉻(VI)鹽及合適還原劑之混合物之形式進行添加。
兩種處理溶液咸包括含量為0.5至10 g/l之鉻(III)，2至6 g/l為較佳及2.5至3.5 g/l為最佳。
步驟1之處理溶液一般具有10至40℃之溫度，20至30℃為較佳。
於該處理溶液中之處理時間較佳為10至600 s，更佳為20至120 s，最佳為30至90 s。
在該方法之一個較佳之實施例中，鈍化處理在鈍化溶液中係藉由連接基材作為陰極得到促進。此情況下，該基材上之陰極電流密度較佳為0.05至10 A/dm2
，更佳為0.1至5 A/dm2
，最佳為0.1至3 A/dm2
。
吾等假設，在第一步驟中，在所設定之強酸性pH值下，含鉻(III)物種在處理溶液中明顯優先發生鈍化反應。結果，在該步驟中，不滲透鈍化層極其可靠地在遍及鋅、鎂或鋁及其合金金屬表面之整個區域上形成。然而，該層還未具特定之耐用性，具體言之，幾乎無抗機械應力性。
第一步驟中形成之鈍化層因此得到固定及因此在第二步驟中實現耐用性。
步驟2中之處理溶液同樣係基本上藉由鉻(III)鹽及針對金屬鋅、鎂或鋁亦及其合金而言之錯合劑組成。將該溶液設定至2.0至12.0之pH，較佳為3.0至7.0，最佳為3.5至5.0。因此，根據溶液之最初pH，可採用酸或鹼。硫酸及硝酸尤其適用於作為酸。較佳採用鹼金屬氫氧化物(具體之NaOH及KOH)作為鹼。
步驟2之處理溶液一般具有10至70℃之溫度，40至60℃為較佳。
於該處理溶液中之處理時間較佳為5至600 s，更佳為8至120 s，最佳為10至90 s。
在第二步驟中，處理溶液之鈍化用組分實際上不扮演任何角色，以致該方法可藉由第二步驟中最初藉由唯一之錯合劑組成之溶液及由於夾帶而唯一在生產製程過程中應用步驟1及步驟2處理溶液之組成進行修改。
吾等假設，在第二步驟中，在所設定之較弱酸性、中性或鹼性pH值下，錯合劑在處理溶液中明顯優先發生固定反應。結果，已先前施用在遍及金屬表面整個區域上之鈍化層在該步驟中得到可靠固定。僅僅由於該步驟，在該表面上形成可長期耐受機械及其他應力之耐用性腐蝕保護層。
鋅、鎂或鋁或其合金可電化學沈積於基材上或已藉由其他方法(諸如熱鍍鋅)進行施用，或可組成待處理構件之材料。該等方法為熟習此項相關技藝之人士知曉。
一般，用於含鋅表面之不含鉻(VI)之鈍化溶液大體上包括鉻(III)離子之來源及一種或多種錯合劑。該等溶液為熟習此項相關技藝之人士知曉。處理溶液之pH一般小於2。
在本發明方法之兩步驟中，錯合劑係選自由如下組成之群：羧酸、聚羧酸、羥基羧酸、胺基羧酸、醇、醚及胺。
合適之錯合劑為甲酸、乙酸、丙酸、丁酸、異丁酸、戊酸、己烷羧酸、環戊烷羧酸、乙醯基水楊酸、苯甲酸、硝基苯甲酸、3,5-二硝基苯甲酸、四氫呋喃-2-甲酸、山梨酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、馬來酸、苯二甲酸、對苯二甲酸、伸乙二氮基四乙酸、乙二胺四乙酸、二伸乙基二胺五乙酸、氮基三乙酸、酒石酸、檸檬酸、異檸檬酸、蘋果酸、抗壞血酸、乳酸、葡萄糖酸、葡糖醛酸、沒食子酸、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、1-戊醇、乙二醇、丙二醇、乙二醇丁醚及乙二醇醚。
兩種處理溶液各者中所有錯合劑之含量各為0.75至200 g/l，較佳為5至100 g/l，最佳為10至50 g/l。
當待處理之表面係由鋅或鋅合金組成時，兩種處理溶液包括含量各為0.75至200 mmol/l之水溶性鋅化合物，較佳為3至100 mmol/l，最佳為10至40 mmol/l。
當待處理之表面係由鎂或鎂合金組成時，兩種處理溶液包括含量各為2至210 mmol/l之水溶性鎂化合物，較佳為8至75 mmol/l，最佳為12至40 mmol/l。
當待處理之表面係由鋁或鋁合金組成時，兩種處理溶液包括含量各為1.8至185 mmol/l之水溶性鋁化合物，較佳為7.5至85 mmol/l，最佳為11至40 mmol/l。
處理步驟1及2中之兩浴視需要包括選自由NaF、KF、NH4
F、NaHF2
、KHF2
及NH4
HF2
組成之群之氟離子之來源。氟離子係以各為0.001至10 g/l之含量添加，較佳為0.01至5 g/l及最佳為0.05至2 g/l。
處理步驟1及2中之兩浴視需要包括選自由NaCl、KCl及NH4
Cl組成之群之氯離子之來源。氯離子係以各為0.01至20 g/l之含量添加，較佳為0.1至10 g/l及最佳為0.5至5 g/l。
處理步驟1及2之兩浴中另一種視需要之組分為磷酸鹽化合物，且至少一種磷酸鹽化合物係選自由如下組成之群：正磷酸、聚磷酸、偏磷酸、此等酸之鹽、具有含至多12個碳原子之有機基之此等酸之酯及該等化合物之混合物。磷酸鹽化合物係以各為0.5至100 g/l之含量添加，較佳為3至50 g/l及最佳為5至20 g/l。
為增加腐蝕保護，選自由Sc、Y、Ti、Zr、Mo、W、Mn、Fe、Co、Ni、Zn、B、Al、Si組成之群之至少一種金屬或類金屬可在處理步驟1及2中視需要添加至兩種處理溶液。該等元素可以其鹽之形式或以錯合陰離子或該等陰離子之相應酸(例如六氟硼酸、六氟矽酸、六氟酞酸或六氟鋯酸、四氟硼酸或六氟磷酸)或其鹽之形式添加。
本發明之方法可用於極多鈍化系統中。當可溶性鈷鹽係以各為0.2至3 g/l(較佳為0.5至1 g/l)之含量添加至處理步驟1及2中之各個浴時，可實現黑色鈍化之優秀腐蝕保護價值。
針對後處理而言，已取自處理溶液2之基材係在沒有進行先前之清洗下進行乾燥。例如，乾燥可在乾燥鼓中完成。黏附在乾燥鼓中處理溶液2之殘餘物可藉由熱鹼溶液之方式移除。
製得具有以下組成之水性反應溶液：用於步驟1之反應溶液：以74重量%強度之硝酸鉻(III)溶液之形式添加之3.61 g/l之Cr(III)離子、10.9 g/l之磷酸根離子、2.5 g/l之鋅離子、12.1 g/l之葡萄糖酸、10 g/l之酒石酸、0.088 g/l之氟離子及1.22 g/l之氯離子。
藉由硝酸使該溶液之pH設定至1.8。
用於步驟2之反應溶液：以74重量%強度之硝酸鉻(III)溶液之形式添加之3.61 g/l之Cr(III)離子、10.9 g/l之磷酸根離子、2.5 g/l之鋅離子、12.1 g/l之葡萄糖酸、10 g/l之酒石酸、0.088 g/l之氟離子及1.22 g/l之氯離子。
藉由氫氧化鈉使該溶液之pH設定至4。
在酸性鋅電解質(商標名：獲自Atotech Deutschland GmbH之Unizink NCZ 420)中使鋼元件塗覆有10 μm厚之鋅層。然後，於20℃下，使該鋼元件浸入硝酸/水混合物(約0.2%之HNO3
)中10 s以得到表面。隨後，利用去礦物質水清洗該部件且於25℃下，立即浸入如上述製得之反應溶液1中40 s。在無進一步之清洗步驟下，接著，於50℃下，使該部件立即浸入如上述製得之反應溶液2中15 s。在令處理溶液滴完之後，在無最終之清洗步驟下，使該部件於120℃下進行乾燥15分鐘。
在根據DIN 50021 SS之鹽霧試驗中，表面保持不變400 h，顯示5%之僅僅在700 h後之白銹腐蝕及僅僅在多於1000 h後之紅銹腐蝕。藉由本發明之方法實現之腐蝕保護係至少與藉由先前技術所習知之方法實現之腐蝕保護一樣佳，不同的係，在本發明之方法中，污染有重金屬之廢水量明顯減少。
Claims (12)
- 鋁或鎂及該等金屬之合金表面上形成腐蝕保護層之方法，其包括以下步驟：i)使前述金屬或金屬合金之表面與包括如下組份之溶液接觸：鉻(III)離子，選自前述之表面金屬鋅、鋁或鎂或表面金屬合金之金屬離子，及至少一種選自由羧酸、聚羧酸、羥基羧酸、胺基羧酸、醇、胺及醚組成之群之錯合劑，其中該處理溶液具有1.0至4.0之pH；ii)然後，在無清洗操作下使該等金屬之表面與包括如下組份之溶液直接接觸，鉻(III)離子，選自前述之表面金屬鋅、鋁或鎂或表面金屬合金之金屬離子，及至少一種選自由羧酸、聚羧酸、羥基羧酸、胺基羧酸、醇、胺及醚組成之群之錯合劑，其中該處理溶液具有3.0至12.0之pH；及iii)在與兩種處理溶液接觸之後，於無最終清洗步驟下直接乾燥待處理之基材。
- 如請求項1之方法，其中該兩種處理溶液各包括0.5至200g/l之錯合劑。
- 如請求項1或2之方法，其中該兩種處理溶液皆包括至少 一種水溶性鈷化合物。
- 如請求項1或2之方法，其中該兩種處理溶液各包括至少一種選自由正磷酸、聚磷酸、偏磷酸、該等酸之鹽、具有含至多12個碳原子之有機基之該等酸之酯及該等化合物之混合物組成群之磷酸鹽化合物。
- 如請求項1或2之方法，其中該兩種處理溶液皆包括含量分別為0.001至10g/l之氟離子。
- 如請求項1或2之方法，其中該兩種處理溶液皆包括含量分別為0.1至10g/l之氯離子。
- 如請求項1或2之方法，其中步驟1中之該處理溶液具有10至50℃之溫度。
- 如請求項1或2之方法，其中步驟2中之該處理溶液具有10至80℃之溫度。
- 如請求項1或2之方法，其中兩步驟中在該處理溶液中之處理時間為10至600s。
- 如請求項1或2之方法，其中可溶性鉻(III)離子係以0.5至10g/l之含量添加至該兩種處理溶液之各者中。
- 如請求項1或2之方法，其中步驟1中之鈍化處理係藉著在鈍化溶液中連接該基材作為陰極而促進。
- 如請求項11之方法，其中該基材上之陰極電流密度為0.05至10A/dm2 。
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