EP0459549B1 - Obtention de couches de conversion sur des surfaces en zinc ou en alliage de zinc - Google Patents
Obtention de couches de conversion sur des surfaces en zinc ou en alliage de zinc Download PDFInfo
- Publication number
- EP0459549B1 EP0459549B1 EP91201020A EP91201020A EP0459549B1 EP 0459549 B1 EP0459549 B1 EP 0459549B1 EP 91201020 A EP91201020 A EP 91201020A EP 91201020 A EP91201020 A EP 91201020A EP 0459549 B1 EP0459549 B1 EP 0459549B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rinsing
- solution
- post
- effected
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011701 zinc Substances 0.000 title claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 15
- 229910052725 zinc Inorganic materials 0.000 title claims description 14
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 11
- 238000007739 conversion coating Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000243 solution Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 23
- 239000012487 rinsing solution Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- -1 anions benzoate Chemical class 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000010422 painting Methods 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000007888 film coating Substances 0.000 claims description 4
- 238000009501 film coating Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- OFXXQEVJFJUPBD-UHFFFAOYSA-N 2,2,3,3,4,4-hexahydroxyheptanoic acid Chemical compound CCCC(O)(O)C(O)(O)C(O)(O)C(O)=O OFXXQEVJFJUPBD-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000005985 organic acids 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
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 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 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the invention relates to a method for producing conversion coatings on surfaces of zinc or zinc alloys, in which in a first step the surfaces are brought into contact with a solution which contains at least two different polyvalent metal ions and complexing agents in such an amount that the polyvalent metal ions are kept in solution, and has a pH ⁇ 11, and in which rinsing is carried out in a subsequent step with a rinsing solution, and its use as a pretreatment for subsequent painting, film coating or adhesive coating.
- Such a method for producing a conversion layer is known in particular as a pretreatment before painting and film coating from DE-C-1 521 854.
- aqueous alkaline solutions which act as so-called non-alkali metal ions of one or more of the metals silver, magnesium, cadmium, aluminum, tin, titanium, antimony, molybdenum, chromium, cerium, tungsten, manganese, cobalt , Iron and nickel included.
- Particularly suitable solutions are those which contain ions of iron or cobalt with another of the metals mentioned as non-alkali metal ions.
- the solutions contain sufficient organic complexing agents to keep the non-alkali metal ions in solution.
- the conversion coatings produced by means of these ions increase the corrosion resistance and improve the adhesion of subsequently applied organic coatings.
- Corrosion resistance and adhesion are further improved if the surfaces are rinsed with an acidic, hexavalent chromium and possibly additionally trivalent chromium solution after the conversion layer has been produced. (DE-C-1 521 854)
- metal surfaces in particular made of steel, aluminum or zinc, and alloys thereof, which may have a conversion coating
- an aqueous solution which contains reactive organosilane and additional titanium and / or zirconium compound EP-A-153 973
- Concrete coatings are zinc or iron phosphate layers or chromate layers, in the illustration of the prior art u. a. also called metal oxide coatings.
- metal surfaces made of iron or steel are to be treated with solutions containing aluminum ions, up to 200 ppm fluoride ions and preferably additionally up to 1000 ppm in order to avoid rust spots during drying and until they are finally protected by painting or another type of surface treatment
- Ions contain at least one of the metals titanium, zirconium and hafnium.
- the object of the invention is to provide a method for producing conversion coatings on surfaces made of zinc or zinc alloys, which avoids the disadvantages of the method mentioned and in particular does not or only to a very small extent burden the environment and is at least the same in terms of corrosion protection and paint adhesion behaves well.
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that rinsing is carried out with a rinsing solution which contains aluminum, zirconium and fluoride with a molar ratio of Al: Zr: F of (0.15 to 2.0): 1: (5 to 16) and whose pH is set to 2 to 5.
- Rinse solutions containing aluminum fluorozirconate with a molar ratio of Al: Zr: F of (0.15 to 0.67): 1: (5 to 7) and a total concentration of Al + Zr + F of 0.1 to 2 g are admittedly included / l have, described in EP-A1-410 497. However, they are used for the passivative rinsing of phosphate layers applied to metal surfaces.
- the method according to the invention is suitable for all surfaces which contain zinc or zinc alloys, such as, for example, materials made of solid zinc or solid zinc alloys, but also for those whose surface is electrolytically galvanized or alloy-galvanized by deposition from the gas phase or in the hot-dip process has been.
- zinc or zinc alloys such as, for example, materials made of solid zinc or solid zinc alloys, but also for those whose surface is electrolytically galvanized or alloy-galvanized by deposition from the gas phase or in the hot-dip process has been.
- Aluminum, silicon, lead, iron, nickel, cobalt and manganese are particularly suitable alloying partners for zinc.
- both one-sided and two-sided galvanizing or alloy galvanizing can be used.
- the surfaces should be bare and as free of grease as possible. If necessary, they are cleaned alkaline, neutral or acidic before the conversion treatment and then expediently rinsed with water.
- the surface may not need to be cleaned and degreased beforehand. Instead, in these cases, by adding surfactants to the treatment in the first stage, cleaning and degreasing are carried out using the same treatment solution that is used to produce the conversion coating.
- the main advantage of this embodiment is that the entire pretreatment of the surface can be carried out in fewer steps, since the separate cleaning and the associated water rinsing are eliminated.
- the application of the alkaline solution used in the first stage can e.g. in spraying, dipping or flooding.
- alkaline solutions have been found to be those containing iron (III) ions and additionally cobalt and / or nickel and / or chromium (III) and / or aluminum ions, the total content of which was between 0.3 and 3 g / l, preferably between 0.4 and 1.2 g / l.
- the polyvalent metal ions can be used as salts of inorganic acids, for example nitric acid, or as salts of organic acids, for example formic acid, in particular also Acetic acid can be used. Salts of organic acids, which can simultaneously serve as complexing agents, are also suitable.
- Amphoteric metals, such as aluminum, can also be dissolved in the form of the hydroxyl complex without an additional anion or complexing agent.
- organic chelating agents of various types can be used as complexing agents: for example dicarboxylic acids (malonic acid, fumaric acid etc.); Amino acids (eg glycine); Hydroxycarboxylic acids (e.g. citric acid, gluconic acid, lactic acid); 1,3-diketones (e.g. acetylacetone); aliphatic polyalcohols (e.g. sorbitol, 1,2-ethanediol); aromatic carboxylic acids (eg salicylic acid, phthalic acid); Aminocarboxylic acid (e.g. ethylenediaminetetraacetic acid).
- Other complexing agents such as methanephosphonic acid diethanolamide, can also be used.
- the solution must contain at least such an amount of complexing agent that the multivalent metal ions present can be bound in a completely complex manner.
- the complexing agent content must also be increased. Since increasing amounts of certain complexing agents, which are acidic in nature, can reduce the alkalinity of the solution, complexing agents are preferably used in Form of neutral salts, especially the alkali metal salts used. It has been found that excess amounts of complexing agents are of no benefit.
- salts of gluconic acid but especially hexahydroxyheptanoic acid
- the content of complexing agent in the solution should be between 0.05 and 10 g / l, in most applications between 1.5 and 5.5 g / l (based on the sodium salt of hexahydroxyheptanoic acid).
- the aqueous solution must have a pH ⁇ 11.
- the best results are achieved in the pH range from 12.2 to 13.3.
- the adjustment of the pH value can e.g. by triethanolamine, alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, alkali metal polyphosphates, alkali metal pyrophosphates, alkali metal borates, alkali metal silicates or mixtures thereof.
- the most advantageous are alkali metal hydroxides, especially sodium hydroxide.
- the temperature of the solution of the first stage can in principle be between 20 ° C and 90 ° C.
- the preferred temperature range is 45 to 65 ° C.
- the treatment time is usually 2 to 60 seconds, preferably 5 to 30 seconds. It depends, among other things, on the application technology. For example, the duration of treatment in spraying is shorter than in diving under otherwise the same circumstances.
- solutions with a lower metal ion concentration require higher temperatures and longer treatment times than those with a higher metal ion concentration.
- excess treatment solution should be removed as far as possible from the zinc or zinc alloy surface. This can e.g. by draining, squeezing, blowing off or rinsing with water or with an aqueous solution which has been acidified, for example with an inorganic or organic acid (hydrofluoric acid, boric acid, nitric acid, formic acid, acetic acid etc.).
- an inorganic or organic acid hydrofluoric acid, boric acid, nitric acid, formic acid, acetic acid etc.
- the application of the rinse solution can e.g. by dipping, flooding, spraying or rolling.
- a preferred embodiment of the invention consists in rinsing with a solution which contains aluminum, zirconium and fluoride in a total concentration Al + Zr + F between 0.1 and 8 g / l, preferably between 0.2 and 5 g / l.
- the molar ratios Al: Zr: F should advantageously be set to (0.15 to 0.67): 1: (5 to 7).
- the rinsing solutions used in the process according to the invention contain, inter alia, acidic aluminum fluorozirconates and, in the case of an excess of aluminum, other salts of aluminum (for example fluorides Tetrafluoroborates, nitrates). They can be produced, for example, by first dissolving metallic zirconium or zirconium carbonate in aqueous hydrofluoric acid, forming complex fluorozirconic acid. Then metallic aluminum or aluminum hydroxide or an aluminum salt, for example nitrate, fluoride, tetrafluoroborate, formate, acetate, preferably in dissolved form, is added and, if necessary, dissolved. A possible slight clouding of the solution does not impair the effectiveness. Although the described manufacturing route is preferred, the solutions can also be prepared in other ways.
- the pH of the solution is preferably adjusted with cations of volatile bases. These include in particular ammonium, ethanolammonium and di- and tri-ethanolammonium.
- volatile bases include in particular ammonium, ethanolammonium and di- and tri-ethanolammonium.
- rinsing is carried out with an aqueous solution which additionally contains at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of preferably 0.05 to 0.5 g / l.
- the anions can be introduced via the corresponding acids or their salts.
- the duration of the application of the rinse solution is generally between about 1 and 120 seconds, according to a further expedient embodiment of the invention between 1 and 30 seconds.
- the application temperature can be between 20 ° C and about 80 ° C. Temperatures between 20 and 50 ° C are preferred.
- Demineralized or low-salt water is preferably used to prepare the rinse bath. Water with a high salt content is less suitable for bath preparation.
- the surface can e.g. air-dried or oven-dried, if necessary rinsed with deionized water beforehand.
- An advantageous embodiment of the invention provides that the surface is accelerated after the passivative rinsing, e.g. dry with hot air or infrared radiation.
- the method according to the invention primarily serves as preparation of the zinc or zinc alloy surfaces before painting, film coating or the application of adhesives. It increases the adhesion of the organic films to the metallic substrate, improves their resistance to blistering when exposed to corrosion and inhibits the corrosion penetration from damage points in the film.
- the sheets were then rinsed with water and rinsed passively. For this purpose, the sheets were immersed in the rinse solution for 5 seconds and then excess solution was removed by squeezing. After a drying time of 0.5 min in a forced air oven at 75 ° C, the pretreated sheets were coated with an epoxy primer and an acrylate top coat. The layer thickness of the total varnish was approx. 25 ⁇ m.
- the percentage of the chipped paint surface of the total curved surface is given as the tested size in%.
- the rinsing solutions used were diluted 1.6 g / l (rinsing solution A) or 20 g / l (rinsing solution B) of an aqueous concentrate with 0.855% by weight Al and 8.62% by weight Zr and 10 , 7 wt .-% F using deionized water.
- the pH in both solutions had been adjusted to approximately 3.6 with ammonia.
- composition of the rinse solutions was:
- a comparison of the table values shows that the method according to the invention in any case provided at least as good or better values as the comparison method also tested with a rinsing solution based on Cr (VI) / Cr (III).
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Claims (12)
- Procédé de production de couches de conversion sur des surfaces en zinc ou en alliages de zinc, dans lequel, dans une première étape, les surfaces sont mises en contact avec une solution contenant au moins deux ions métalliques polyvalents différents, ainsi que des agents de complexation en quantités telles que les ions métalliques polyvalents sont maintenus en solution, solution dont le pH est supérieur ou égal à 11, et dans lequel, ensuite, on rince les surfaces avec une solution de rinçage, caractérisé en ce que l'on rince avec une solution de rinçage contenant de l'aluminium, du zirconium et du fluorure selon un rapport molaire Al:Zr:F de (0,15 à 2,0):1: (5 à 16), et dont le pH est ajusté à une valeur comprise entre 2 et 5.
- Procédé selon la revendication 1, caractérisé en ce que l'on rince avec une solution de rinçage dont la concentration totale en Al+Zr+F est comprise entre 0,1 et 8,0 g/l.
- Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on rince avec une solution de rinçage dont la concentration totale en Al+Zr+F est comprise entre 0,2 et 5,0 g/l.
- Procédé selon la revendication 1, 2 ou 3, caractérisé en ce que l'on rince avec une solution de rinçage dans laquelle les rapports molaires Al:Zr:F sont ajustés pour valoir (de 0,15 à 0,67):1:(de 5 à 7).
- Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce que l'on rince avec une solution de rinçage dont le pH est ajusté à l'aide de cations de bases volatiles.
- Procédé selon la revendication 5, caractérisé en ce que l'on rince avec une solution de rinçage dont le pH est ajusté à l'aide de composés d'ammonium, d'éthanolammonium, de di- ou de tri-éthanolammonium.
- Procédé selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que l'on rince avec une solution de rinçage qui contient, en plus, au moins l'un des anions benzoate, caprylate, éthylhexoate, salicylate, en une concentration totale comprise entre 0,05 et 0,5 g/l.
- Procédé selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce que l'on rince avec une solution de rinçage pour une durée comprise entre 1 et 30 secondes.
- Procédé selon l'une ou plusieurs des revendications 1 à 8, caractérisé en ce que l'on rince avec une solution de rinçage dont la température est comprise entre 20 et 80 °C.
- Procédé selon l'une ou plusieurs des revendications 1 à 9, caractérisé en ce que l'on rince avec une solution de rinçage dont la température est comprise entre 20 et 50 °C.
- Procédé selon l'une ou plusieurs des revendications 1 à 10, caractérisé en ce que l'on sèche la surface après le rinçage.
- Utilisation du procédé selon l'une ou plusieurs des revendications 1 à 11, comme préparation à un traitement ultérieur de revêtement par une peinture, de revêtement par un film ou de revêtement par un adhésif.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4017186A DE4017186A1 (de) | 1990-05-29 | 1990-05-29 | Erzeugung von konversionsueberzuegen auf zink- oder zinklegierungsoberflaechen |
DE4017186 | 1990-05-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0459549A1 EP0459549A1 (fr) | 1991-12-04 |
EP0459549B1 true EP0459549B1 (fr) | 1994-08-17 |
Family
ID=6407363
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91201020A Expired - Lifetime EP0459549B1 (fr) | 1990-05-29 | 1991-04-29 | Obtention de couches de conversion sur des surfaces en zinc ou en alliage de zinc |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0459549B1 (fr) |
JP (1) | JP3083872B2 (fr) |
AU (1) | AU633728B2 (fr) |
BR (1) | BR9102173A (fr) |
CA (1) | CA2041892C (fr) |
DE (2) | DE4017186A1 (fr) |
ES (1) | ES2057734T3 (fr) |
ZA (1) | ZA914085B (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19733972A1 (de) | 1997-08-06 | 1999-02-11 | Henkel Kgaa | Alkalische Bandpassivierung |
DE102010001686A1 (de) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Zusammensetzung für die alkalische Passivierung von Zinkoberflächen |
ITMI20102198A1 (it) * | 2010-11-26 | 2012-05-27 | Np Coil Dexter Ind Srl | Processo di pretrattamento su coil in acciaio zincato preverniciato esente da metalli pesanti |
JP6051171B2 (ja) | 2011-02-08 | 2016-12-27 | 日本パーカライジング株式会社 | ジルコニウム酸化物で前処理された亜鉛表面の腐食性能を改善するためのプロセス及び組成物 |
EP2503025B1 (fr) | 2011-03-22 | 2013-07-03 | Henkel AG & Co. KGaA | Traitement en plusieurs étapes de protection contre la corrosion des pièces métalliques ayant au moins partiellement une surface en zinc ou en alliages de zinc |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0410497A1 (fr) * | 1989-07-28 | 1991-01-30 | METALLGESELLSCHAFT Aktiengesellschaft | Procédé pour le rinçage passif de couches de phosphates |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3501352A (en) * | 1965-08-02 | 1970-03-17 | Hooker Chemical Corp | Composition and method for treating zinc surfaces |
US3695942A (en) * | 1970-12-02 | 1972-10-03 | Amchem Prod | Zirconium rinse for phosphate coated metal surfaces |
US3852123A (en) * | 1972-11-20 | 1974-12-03 | Pennwalt Corp | Sealing rinses for phosphate coatings on metal |
JPS6022067B2 (ja) * | 1982-09-30 | 1985-05-30 | 日本パ−カライジング株式会社 | 金属表面の皮膜形成方法 |
US4496404A (en) * | 1984-05-18 | 1985-01-29 | Parker Chemical Company | Composition and process for treatment of ferrous substrates |
US4650526A (en) * | 1986-03-18 | 1987-03-17 | Man-Gill Chemical Company | Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes |
-
1990
- 1990-05-29 DE DE4017186A patent/DE4017186A1/de not_active Withdrawn
-
1991
- 1991-04-29 EP EP91201020A patent/EP0459549B1/fr not_active Expired - Lifetime
- 1991-04-29 DE DE59102544T patent/DE59102544D1/de not_active Expired - Fee Related
- 1991-04-29 ES ES91201020T patent/ES2057734T3/es not_active Expired - Lifetime
- 1991-04-29 AU AU76178/91A patent/AU633728B2/en not_active Ceased
- 1991-05-06 CA CA002041892A patent/CA2041892C/fr not_active Expired - Fee Related
- 1991-05-28 BR BR919102173A patent/BR9102173A/pt unknown
- 1991-05-28 JP JP03152482A patent/JP3083872B2/ja not_active Expired - Fee Related
- 1991-05-29 ZA ZA914085A patent/ZA914085B/xx unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0410497A1 (fr) * | 1989-07-28 | 1991-01-30 | METALLGESELLSCHAFT Aktiengesellschaft | Procédé pour le rinçage passif de couches de phosphates |
Also Published As
Publication number | Publication date |
---|---|
AU633728B2 (en) | 1993-02-04 |
CA2041892C (fr) | 2000-10-03 |
JPH04231479A (ja) | 1992-08-20 |
EP0459549A1 (fr) | 1991-12-04 |
JP3083872B2 (ja) | 2000-09-04 |
AU7617891A (en) | 1991-12-05 |
ES2057734T3 (es) | 1994-10-16 |
BR9102173A (pt) | 1991-12-24 |
ZA914085B (en) | 1993-01-27 |
CA2041892A1 (fr) | 1991-11-30 |
DE59102544D1 (de) | 1994-09-22 |
DE4017186A1 (de) | 1991-12-05 |
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