EP1171648A1 - Composition et procede de traitement de surfaces metalliques - Google Patents
Composition et procede de traitement de surfaces metalliquesInfo
- Publication number
- EP1171648A1 EP1171648A1 EP99963840A EP99963840A EP1171648A1 EP 1171648 A1 EP1171648 A1 EP 1171648A1 EP 99963840 A EP99963840 A EP 99963840A EP 99963840 A EP99963840 A EP 99963840A EP 1171648 A1 EP1171648 A1 EP 1171648A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- bath
- treatment
- aqueous liquid
- alloys
- 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.)
- Withdrawn
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 title claims description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 47
- 230000007797 corrosion Effects 0.000 claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011777 magnesium Substances 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 16
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims abstract description 14
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000003973 paint Substances 0.000 abstract description 23
- 150000002739 metals Chemical class 0.000 abstract description 6
- 238000011282 treatment Methods 0.000 description 50
- 238000004381 surface treatment Methods 0.000 description 43
- 238000007739 conversion coating Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 15
- 239000010959 steel Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 229910000861 Mg alloy Inorganic materials 0.000 description 13
- 229910000838 Al alloy Inorganic materials 0.000 description 12
- 239000010936 titanium Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- 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 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- KHEMNHQQEMAABL-UHFFFAOYSA-J dihydroxy(dioxo)chromium Chemical compound O[Cr](O)(=O)=O.O[Cr](O)(=O)=O KHEMNHQQEMAABL-UHFFFAOYSA-J 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- -1 oxysulfates Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011825 aerospace material Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- 229910018464 Al—Mg—Si Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910018571 Al—Zn—Mg Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 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
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 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
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
Definitions
- This invention relates to a novel aqueous liquid composition, which is usually hereinafter called a "bath” for brevity, without any implication thereby that it must be used by immersion only, and to a process for treating a metal surface.
- the composition and process can provide the surfaces of various metals, especially aluminum, aluminum alloys, magnesium, magnesium alloys, and galvanized steel sheet, with an excellent corrosion resistance and excellent paint adherence.
- the baths used to treat aluminum and aluminum alloy surfaces can be broadly classified into chromate-type baths and non-chromate-type baths. Chromic acid chro- mate conversion baths and phosphoric acid chromate conversion baths are typical examples of the chromate-type treatment baths.
- Chromic acid chromate conversion baths first reached practical application in about 1950 and even now are widely used for the surface treatment of automotive heat exchangers, aluminum wheels, building materials, and aerospace materials.
- the main components in chromic acid chromate conversion baths are chromic acid and a fluoride reaction accelerator. This type of bath produces a conversion coating containing moderate amounts of hexavalent chromium on the metal surface.
- Phosphoric acid chromate conversion baths originated with the invention disclosed in United States Patent No. 2,438,877.
- the main components in phosphoric acid chromate conversion baths are chromic acid, phosphoric acid, and hydrofluoric acid.
- a conversion coating whose main component is hydrated chromium phosphate is formed by this type of bath on the metal surface. Since the resulting conversion coating does not contain hexavalent chromium, this type of bath is in wide use at the present time as an underpaint treatment for the body stock and lid stock of beverage cans.
- the treatment bath disclosed in Japanese Laid Open (Kokai or Unexamined) Patent Application Number Sho 52-131937 (131 ,937/1977) is an invention typical of the chromium-free non-chromate-type surface treatment baths.
- This non-chromate-type surface treatment bath offers the advantage of not containing hexavalent chromium and for this reason is widely used at present for treating aluminum drawn-and-ironed, hereinafter usually abbreviated as "Dl", can surfaces.
- Dl aluminum drawn-and-ironed
- the treatment method disclosed in Japanese Laid Open (Kokai or Unexamined) Patent Application Number Sho 57-41376 (41 ,376/1982) comprises treating the surface of aluminum, magnesium, or an alloy thereof with an aqueous solution containing at least one selection from titanium salts and zirconium salts, at least one selection from imida- zole derivatives, and an oxidizer selected from nitric acid, hydrogen peroxide, and potassium permanganate. While the corrosion resistance of the coatings produced by this treatment bath would have been considered acceptable 15 years ago, this level of corrosion resistance is not unequivocally satisfactory at the present time.
- Japanese Laid Open (Kokai or Unexamined) Patent Application Number Sho 56- 136978 (136,978/1981) teaches a conversion bath that characteristically comprises an aqueous solution containing a vanadium compound and at least one compound selected from the group consisting of titanium salts, zirconium salts, and zinc salts.
- the conversion coating formed by this treatment bath cannot be expected to have a corrosion resistance better than or even as good as that of a chromate film in the case of challenge by long-term anticorrosion testing.
- This treatment process comprises a phosphate treatment followed by a silicate treatment and then execution of a silicone treatment after the silicate treatment.
- the phosphate treatment coating by itself provides a low level of corrosion resistance and paint adherence when used as an underpaint treatment for magnesium and magnesium alloy surfaces.
- This treatment method also requires a multistage treatment process, uses high treatment temperatures, and requires long treatment times.
- the known phosphate-based surface treatment methods for magnesium and its alloys include methods that employ treatment baths based on zinc phosphate, iron phosphate, calcium phosphate, or zirconium phosphate. However, these methods are not believed to have consistently provided a corrosion resistance that is satisfactory at a practical level.
- a manganese phosphate treatment is disclosed in category 7 of JIS H-8651. This treatment bath is not acceptable from a practical standpoint because it contains chromium, requires high treatment temperatures of 80 °C to 90 °C, and requires long treatment times of 30 to 60 minutes.
- Non-chromate-type technology is found in Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 9-228062 (228,062/1997), which teaches a surface treatment process that uses an aqueous solution that contains at least one organometal compound selected from metal alkoxides, metal acetylaceton- ates, and metal carboxylates and at least one film-formation stabilizer or film-formation auxiliary selected from acids, bases, their salts, and organic compounds containing the hydroxyl group, carboxyl group, or amino group.
- This aqueous solution is applied to magnesium stock at from 0 to 50 °C.
- the conversion coating formed by this treatment bath cannot be expected to have a corrosion resistance better than or even as good as that of a chromate film in the case of challenge by long-term anticorrosion testing.
- Chromate treatments and zinc phosphate treatments are the treatment processes generally applied to galvanized materials.
- the chromate treatments provide an excellent coating performance, but the corresponding treatment baths contain toxic chromium and hence raise issues with regard to the working environment and effluent discharge.
- the zinc phosphate treatments in some cases are unable to provide an acceptable corrosion resistance.
- Patent Application Number Hei 1 -104783 discloses a process for producing surface-treated steel sheet.
- steel sheet plated with zinc, aluminum, or a zinc-aluminum alloy is coated with an alcohol solution containing at least one selection from the alkoxides and acetylacetonates of Si, Ti, Zr, Al, W, Ce, Sn, and Y.
- An oxide of the metal present in the solution is then formed on the surface of the steel sheet by heating to 200 to 500 °C after application of the bath.
- This preparative method suffers from issues with the working environment and energy costs, because it must use a flammable alcohol and requires fairly high temperatures for coating formation.
- a major object of the present invention is to provide a non-polluting composition and process for treating surfaces of at least one of aluminum and its alloys, magnesium and its alloys, and steel coated with zinc and its alloys that can impart thereto an excellent corrosion resistance and excellent paint adherence.
- highly corrosion-resistant, highly paint-adherent conversion coatings can be formed on metal surfaces by the use of a special surface treatment composition that contains in suitable proportions at least one metal acetylacetonate selected from the group consisting of AI(C 5 H 7 O 2 ) 3 , V(C 5 H 7 O 2 ) 3 , VO(C 5 H 7 O 2 ) 2 , Zn(C 5 H 7 O 2 ) 2 , and Zr(C 5 H 7 O 2 ) 4 , and at least one compound selected from water-soluble inorganic titanium compounds and water-soluble inorganic zirconium compounds.
- a special surface treatment composition that contains in suitable proportions at least one metal acetylacetonate selected from the group consisting of AI(C 5 H 7 O 2 ) 3 , V(C 5 H 7 O 2 ) 3 , VO(C 5 H 7 O 2 ) 2 , Zn(C 5 H 7 O 2 ) 2 , and Zr(C 5 H 7 O 2 ) 4
- a composition according to the present invention for treating metal surfaces comprises, preferably consists essentially of, or more preferably consists of, water and the following components:
- (B) a component of at least one compound selected from water-soluble inorganic titanium compounds and water-soluble inorganic zirconium compounds, components (A) and (B) being present at a weight ratio of (A) to (B) that is from 1 : 5,000 to 5,000 : 1.
- a bath according to the present invention for treating metal surfaces preferably, independently for each preference: has a pH from 2.0 to 7.0; contains from 0.01 to 50 grams of component (A) as described above per liter of bath, this unit of concentration being freely applied hereinafter to any constituent of the bath and being usually abbreviated as "g/l"; and contains from 0.01 to 50 g/l of component (B) as described above.
- a process according to the present invention for treating metal surfaces preferably forms on said metal surface an organic-inorganic composite conversion coating at a coating weight of 5 to 2,000 milligrams of coating per square meter of the surface coated, this unit of coating weight being hereinafter usually abbreviated as "mg/m 2 ", by bringing the above-described bath for treating metal surfaces into contact with aluminum or an alloy thereof, magnesium or an alloy thereof, or zinc or an alloy thereof.
- An important feature of the present invention is the formation of an organic- inorganic composite coating. It is believed that the corrosion resistance of the resulting conversion coating in particular is improved through the formation of this organic- inorganic composite coating.
- the water-soluble inorganic titanium compound and/or water-soluble inorganic zirconium compound which is an essential component in the surface treatment composi- tion of the present invention, can be one or more selections, for example, from the sul- fates, oxysulfates, nitrates, phosphates, chlorides, ammonium salts, and fluorides of titanium and zirconium.
- this component is a water-soluble inorganic compound, its specific type is not critical. However, at least for economy, at least one of fluorotitanic and fluorozirconic acids and the salts of both of these acids are preferred.
- the water-soluble inorganic titanium and/or zirconium compound(s) are believed to precipitate on the surface of the metal workpiece as, for example, the oxide, phosphate, or fluoride of Ti or Zr and thus to form a framework or skeletal element of the organic-inorganic composite coating that is produced with the simultaneously precipitating metal acetylacetonate.
- the presence of the Ti and/or Zr also improves the barrier performance (interception capability) of the coating with respect to corrosive environments and as a result makes possible the formation of a coating that has a corrosion resistance and paint adherence superior to the use of only the metal acetylacetonate.
- the metal acetylacetonate : water-soluble inorganic compound concentration ratio preferably is at least, with increasing preference in the order given, 1.00:100, 1.00:50, 1.00:10, 1.00:7.0, 1.00:5.0, 1.00:3.0, 1.00:2.0, or 1.00:1.40 and independently preferably is not more than, with increasing preference in the order given, 400:1.00, 100:1.00, 10:1.00, 7.0:1.00, 5.0:1.00, or 2.5:1.00.
- the organic-inorganic composite coating formed when this weight ratio is below 1 :5000 will have a poor corrosion resistance, while production of the organic-inorganic composite coating itself becomes difficult at above 5000:1.
- a bath according to the present invention for treating metal surfaces essentially employs water and the hereinabove described surface treatment composition.
- This bath contains the metal acetylacetonate preferably at from 0.01 to 50 g/l and more preferably at from 0.1 , or still more preferably, 1.0, to 20 g/l. While a conversion coating will be formed at a metal acetylacetonate content below 0.01 g/l, such a coating will usually have a poor corrosion resistance and paint adherence. Good quality conversion coatings are still formed at above 50 g/l, but since no additional increment in performance is obtained above 50 g/l, such concentrations are uneconomical due to the additional cost of the bath.
- the content of water-soluble inorganic titanium compound(s) and/or water- soluble inorganic zirconium compound(s) is preferably from 0.01 to 50 g/l and more preferably from 0.05, or still more preferably 0.5, to 10 g/l. While a conversion coating will be formed at a content below 0.01 g/l, such a coating will usually have a poor corrosion resistance. Good quality conversion coatings are still formed at above 50 g/l, but since no additional improvement in performance is obtained above 50 g/l, such s concentrations are uneconomical due to the additional cost of the bath.
- the pH of a surface treatment bath according to the present invention must be within the range from 2.0 to 7.0 and preferably is within the range from 3.0 to 6.0.
- a pH below 2.0 hinders precipitation of the metal acetylacetonate on the metal surface and can cause irregularities or unevenness in appearance due to excessive etching of the o metal surface.
- Formation of a highly corrosion-resistant conversion coating is strongly impaired at a pH above 7.0, and a pH above 7.0 can also cause problems with bath stability due to a pronounced tendency for the metal ions present in the bath to form a precipitate at such pH values.
- the pH of the surface treatment bath of the present invention can be adjusted into the desired range through the use of an acid such s as nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, or fluorosilicic acid, or a base such as sodium hydroxide, sodium carbonate, potassium hydroxide, or ammonium hydroxide.
- an acid such as nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, or fluorosilicic acid
- a base such as sodium hydroxide, sodium carbonate, potassium hydroxide, or ammonium hydroxide.
- the stability of the treatment bath can be strongly impaired during execution of the surface treatment of the present invention by elution into the bath of metal ions, e.g., o aluminum, magnesium, or zinc ions, from the metal workpiece.
- metal ions e.g., o aluminum, magnesium, or zinc ions
- an organic acid or alkali metal salt thereof may be added to the bath as a sequestering agent in order to chelate the metal ions.
- Organic acids used for this purpose can be exemplified by gluconic acid, heptogluconic acid, oxalic acid, tartaric acid, organophosphonic acids, and ethylenediaminetetraacetic acid. 5
- An oxidizing agent can also be used in order to accelerate formation of the conversion coating of the present invention.
- This oxidizing agent can be exemplified by hydrogen peroxide, tungstic acid and its salts, molybdic acid and its salts, permanganic acid and its salts, and water-soluble organoperoxides such as tert-butyl hydroperoxide ((CH 3 ) 3 C-O-OH).
- the mass per unit area, usually called "coating weight”, of the organic-inorganic composite conversion coating formed by the hereinabove described process is preferably from 5 to 2,000 mg/m 2 and more preferably is from 50, or still more preferably 140, to 500 mg/m 2 .
- the corrosion resistance and paint adherence may be inadequate at a coating weight below 5 mg/m 2 . While an excellent corrosion resistance is obtained
- Coating weights above 2,000 mg/m 2 are also undesirable because they can cause a conspicuous unevenness in coating appearance and tend to impair the paint adherence.
- metal components Al, V, Zn, Zr, Ti
- their chemical characteristics in the coating itself for example, their bonding status, oxidation state, extent of polymerization or increase in molecular weight, and the like, are not critical.
- Highly corrosion-resistant, highly paint-adherent conversion coatings can be formed by bringing the surface treatment bath of the invention into contact with aluminum or an alloy thereof, magnesium or an alloy thereof, or zinc or an alloy thereof. This process for treating the surface of various types of metals will be explained in greater detail in the following.
- the surface treatment bath of the invention is used in a preferred embodiment as part of the following process operations: (1 ) Surface cleaning/degreasing (this can be acidic, neutral, alkaline, or solvent cleaning/degreasing)
- the surface treatment bath of the present invention is preferably brought into contact with the metal surface for 1 to 600 seconds at 10, or more preferably 35, to 80 °C.
- the reactivity between the treatment bath and metal surface usually will be inadequate at contact temperatures below 10 °C, and inadequate reactivity will prevent the formation of good quality conversion coatings.
- a conversion coating is still formed at contact temperatures above 80 °C, but the correspondingly increased energy costs create undesirable economics for such temperatures.
- the extent of reaction will usually be inadequate at a treatment time below 1 second, preventing the formation of a highly corrosion-resistant conversion coating. At the other end of this range, no additional improvements are seen in the corrosion resistance and paint adherence of the conversion coating at times in excess of 600 seconds.
- a surface treatment composition bath according to the invention can be advantageously applied to pure aluminum and aluminum alloys that contain at least 50 % by weight of aluminum.
- the applicable aluminum alloys encompass both multicomponent alloys, e.g., Al-Cu, Al-Mn, Al-Si, Al-Mg, Al-Mg-Si, and Al-Zn-Mg, and metals on which Al plating or Al alloy plating has been executed, for example, Al-plated steel sheet.
- the surface treatment composition and bath according to the invention can also be advantageously applied to pure magnesium and magnesium alloys that contain at least 50 % by weight of magnesium.
- Applicable magnesium alloys encompass multi- component alloys such as Mg-AI-Zn, Mg-Zn, and Mg-AI-Zn-Mn, and the magnesium or alloys can be plated on other metals.
- Zinc and zinc alloys to which the invention can be advantageously applied include in particular metals on which Zn plating has been executed, including hot-dip zinc-plated steel sheet, galvannealed hot-dip zinc-plated steel sheet, Al/Zn alloy-plated steel sheet
- the surface of the workpiece may be in any condition as long as a metal as described above is present at least at a portion of the surface.
- the surface can be cold rolled or plated as such, or can have been subjected to a treatment such as shot blasting, roughening with acid or alkali, or activation.
- sample substrate materials were used in these examples: AL-Mn alloy sheets according to Japanese Industrial Standard ("JIS") 3004, with dimensions of 150 millimeters (hereinafter usually abbreviated as "mm") x 70 mm x 0.2 mm thick; Die-cast sheets with dimensions of 150 mm x 100 mm x 1 mm thick of AZ91 D magnesium alloy as specified by JIS H2222; and Galvannealed hot-dip zinc-plated steel sheets with dimensions of 150 mm x 70 mm x 0.8 mm thick.
- JIS Japanese Industrial Standard
- mm 150 millimeters
- Die-cast sheets with dimensions of 150 mm x 100 mm x 1 mm thick of AZ91 D magnesium alloy as specified by JIS H2222
- Galvannealed hot-dip zinc-plated steel sheets with dimensions of 150 mm x 70 mm x 0.8 mm thick.
- the surface-treated samples were prepared by treatment according to the following operations in the sequence (1 ) - (2) - (3) - (4) - (5) - (6).
- Ambient temperature means temperature as normally maintained in buildings for human comfort, i.e., about 18 - 23 °C.
- the metal acetylacetonates used are listed below in Table 1
- the water-soluble titanium compounds used are listed below in Table 2
- the water-soluble zirconium compounds used are listed below in Table 3
- the reagents used to adjust the pH of the surface treatment baths are listed below in Table 4, in each instance together with the identifying symbols used for them in later tables.
- Comparative Example 1 used a metal acetylacetonate as the only component of the treatment bath in order to provide a comparative example testing the formation of a coating of the metal acetylacetonate alone.
- Comparative Example 2 used a water-soluble titanium compound as the only component of the treatment bath in order to provide a comparative example testing the formation of a coating of the inorganic titanium compound alone.
- Comparative Example 3 employed a treatment bath comprising both the water-soluble inorganic titanium compound and the water-soluble inorganic zirconium compound in order to provide a comparative example testing the formation of an inorganic composite coating constituted of titanium and zirconium but lacking the metal acetylacetonate.
- Comparative Example 4 was directed to the formation of coatings with very low coating weights.
- Comparative Example 5 a 2 % solution in water of a commercial zirconium phosphate surface treatment agent (ALODINE® 4040 from Nihon Parkerizing Co., Ltd.) was used to carry out surface treatment. This solution was applied to the above-de- scribed Al alloy sheet by spraying for 60 seconds at 50 °C, after which the corrosion resistance and paint adherence were evaluated.
- AODINE® 4040 from Nihon Parkerizing Co., Ltd.
- Comparative Example 6 an aqueous solution of a commercial phosphoric acid chromate surface treatment agent (mixed aqueous solution of 4 % of ALCHROM® K702SL and 0.3 % of ALCHROM® K702AC, both from Nihon Parkerizing Co., Ltd.) was used to carry out surface treatment. This solution was applied to the above-described Al alloy sheet by spraying for 20 seconds at 50 °C, after which the corrosion resistance and paint adherence were evaluated. Table 5 - Part A
- Comparative Example 7 a 7 % solution in water of a commercial chromic acid chromate surface treatment agent (ALCHROM® 713M from Nihon Parkerizing Co., Ltd.) was used to carry out surface treatment. This solution was applied to the above-described Al alloy sheet, Mg alloy sheet, and Zn-plated steel sheet by dipping for 60 sec- onds at 40 °C, after which the corrosion resistance and paint adherence were evaluated.
- a treatment bath based on MIL-M-3171 C TYPE III, with a main component of sodium bichromate
- Coating Weight The coating weight of the entire organic-inorganic composite coating was measured using either a fluorescence x-ray analyzer or stripping by dipping for 5 minutes at 90 °C in 5 weight % aqueous chromic acid solution.
- Corrosion Resistance The corrosion resistance was evaluated using the salt spray test described in JIS Z-2371. The extent of corrosion development on the surface- treated sheet was evaluated visually after the salt spray test and reported on the following scale:
- Paint Adherence Paint adherence testing was carried out on the Al alloy sheet, Mg alloy sheet, and Zn-plated steel sheet samples after surface treatment under the conditions of Examples 1 to 5 and Comparative Examples 1 to 9.
- the surface of the sample was coated to a dry film thickness of 10 micrometres (hereinafter usually abbreviated as " ⁇ m") with an epoxy resin paint from Kansai Paint Co., Ltd. and the sample was then baked for 10 minutes at 200 °C.
- a grid of 100 squares (width 2 mm) was subsequently introduced in the center of the painted sheet using a cutter, after which the sample was dipped for 60 minutes in boiling deionized water. After this boiling water challenge, the painted sheet was air-dried and then subjected to a peeling test with cellophane tape. The paint adherence was evaluated on the basis of the number of grid squares that were not peeled off.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
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Abstract
Une composition de traitement de surfaces métalliques contenant, en un rapport pondéral de 1:5000 à 5000:1, au moins un acétylacétonate métallique choisi dans le groupe contenant Al(C5H7O2)3, V(C5H7O2)3, VO(C5H7O2)2, Zn(C5H7O2)2, et Zr(C5H7O2)4, ainsi qu'au moins un composé choisi entre des composés de titane organiques hydrosolubles et des composés de zirconium organiques hydrosolubles, fournit une composition de type non chromate conférant une excellente résistance à la corrosion et une excellente adhérence des peintures à des surfaces de métaux, en particulier l'aluminium et ses alliages, le magnésium et ses alliages, le zinc et ses alliages.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30766598 | 1998-10-28 | ||
| JP30766598 | 1998-10-28 | ||
| JP29196799A JP3992173B2 (ja) | 1998-10-28 | 1999-10-14 | 金属表面処理用組成物及び表面処理液ならびに表面処理方法 |
| JP29196799 | 1999-10-14 | ||
| PCT/US1999/023982 WO2000024948A1 (fr) | 1998-10-28 | 1999-10-27 | Composition et procede de traitement de surfaces metalliques |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1171648A1 true EP1171648A1 (fr) | 2002-01-16 |
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ID=26558781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99963840A Withdrawn EP1171648A1 (fr) | 1998-10-28 | 1999-10-27 | Composition et procede de traitement de surfaces metalliques |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1171648A1 (fr) |
| JP (1) | JP3992173B2 (fr) |
| KR (1) | KR20000029286A (fr) |
| AU (1) | AU2020200A (fr) |
| BR (1) | BR9914970A (fr) |
| CA (1) | CA2349376A1 (fr) |
| WO (1) | WO2000024948A1 (fr) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2408675A1 (fr) * | 2000-05-11 | 2001-11-15 | Henkel Corporation | Agent de traitement de surface metallique |
| DE60127793T2 (de) * | 2000-11-07 | 2007-12-27 | Nisshin Steel Co., Ltd. | Chemisch bearbeitetes Stahlblech mit ausgezeichneter Korrosionsbeständigkeit |
| US7147934B2 (en) | 2000-11-07 | 2006-12-12 | Nisshin Steel Co., Ltd. | Chemically processed steel sheet excellent in corrosion resistance |
| TWI268965B (en) | 2001-06-15 | 2006-12-21 | Nihon Parkerizing | Treating solution for surface treatment of metal and surface treatment method |
| TW567242B (en) | 2002-03-05 | 2003-12-21 | Nihon Parkerizing | Treating liquid for surface treatment of aluminum or magnesium based metal and method of surface treatment |
| JP4242827B2 (ja) | 2004-12-08 | 2009-03-25 | 日本パーカライジング株式会社 | 金属の表面処理用組成物、表面処理用処理液、表面処理方法、及び表面処理金属材料 |
| KR100921116B1 (ko) | 2005-03-16 | 2009-10-12 | 니혼 파커라이징 가부시키가이샤 | 표면처리 금속재료 |
| US7695771B2 (en) * | 2005-04-14 | 2010-04-13 | Chemetall Gmbh | Process for forming a well visible non-chromate conversion coating for magnesium and magnesium alloys |
| JP2007162098A (ja) * | 2005-12-15 | 2007-06-28 | Nippon Parkerizing Co Ltd | 水系金属表面処理剤、表面処理方法及び表面処理金属材料 |
| JP4983078B2 (ja) * | 2006-04-13 | 2012-07-25 | Jfeスチール株式会社 | 亜鉛系めっき鋼材用の表面処理剤および表面処理亜鉛系めっき鋼板 |
| AU2007241748B2 (en) * | 2006-04-20 | 2010-12-16 | Nippon Steel Corporation | Zinc-plated steel material coated with composite film excellent in corrosion resistance, unsusceptibility to blackening, coating adhesion, and alkali resistance |
| JP4975378B2 (ja) | 2006-06-07 | 2012-07-11 | 日本パーカライジング株式会社 | 金属の表面処理液、表面処理方法、表面処理材料 |
| JP2007314888A (ja) * | 2007-07-17 | 2007-12-06 | Toyota Motor Corp | 多層塗膜構造 |
| JP2010013677A (ja) | 2008-07-01 | 2010-01-21 | Nippon Parkerizing Co Ltd | 金属構造物用化成処理液および表面処理方法 |
| BR112012031325B1 (pt) * | 2010-06-09 | 2020-11-24 | Chemetall Gmbh | agente de tratamento de superfície de metal livre de cromo inorgânico |
| JP6184051B2 (ja) | 2011-09-21 | 2017-08-23 | 日本ペイント・サーフケミカルズ株式会社 | アルミニウム製熱交換器の表面処理方法 |
| JP6146954B2 (ja) * | 2012-03-09 | 2017-06-14 | 日本ペイント・サーフケミカルズ株式会社 | 化成処理剤及び化成処理皮膜 |
| DE112013003429T5 (de) * | 2012-03-09 | 2015-04-09 | Nippon Paint Co., Ltd. | Oberflächenbehandlungsverfahren für Aluminiumwärmetauscher |
| KR101622681B1 (ko) | 2013-02-28 | 2016-05-31 | 닛테쓰 스미킨 고한 가부시키가이샤 | 알루미늄 함유 아연계 도금 강판 및 그 제조 방법 |
| KR101715283B1 (ko) | 2013-04-03 | 2017-03-10 | 니뽄 페인트 서프 케미컬즈 컴퍼니 리미티드 | 화성처리제 및 금속표면처리방법 |
| JP6055086B2 (ja) | 2013-04-03 | 2016-12-27 | 日本ペイント・サーフケミカルズ株式会社 | アルミニウム製熱交換器の表面処理方法 |
| JP6837332B2 (ja) | 2016-12-28 | 2021-03-03 | 日本パーカライジング株式会社 | 化成処理剤、化成皮膜の製造方法、化成皮膜付き金属材料、及び塗装金属材料 |
| KR102110222B1 (ko) * | 2018-07-26 | 2020-05-13 | 주식회사 노루코일코팅 | 마그네슘 함유 도금 강판용 전처리 조성물 및 이를 이용한 pcm 강판의 제조 방법 |
| KR20220050197A (ko) * | 2019-10-02 | 2022-04-22 | 노벨리스 인크. | 경량 포장 솔루션을 위한 고재활용 함량을 갖는 알루미늄 평판 압연 제품 및 그 제조방법 |
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| US4148670A (en) * | 1976-04-05 | 1979-04-10 | Amchem Products, Inc. | Coating solution for metal surface |
| US5718817A (en) * | 1993-07-28 | 1998-02-17 | Elf Atochem North America, Inc. | Catalyst for low temperature cure of blocked isocyanates |
| US5667845A (en) * | 1993-08-05 | 1997-09-16 | Henkel Corporation | Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces |
| US5397390A (en) * | 1993-08-13 | 1995-03-14 | Ardrox, Inc. | Composition and method for treatment of phosphated metal surfaces |
| US5415749A (en) * | 1994-03-04 | 1995-05-16 | E. I. Du Pont De Nemours And Company | Process for electrodeposition of resist formulations which contain metal salts of β-diketones |
| US5783539A (en) * | 1995-05-19 | 1998-07-21 | Lever Brothers Company | Process for incorporating aluminum salts into an automatic dishwashing composition |
| US5711996A (en) * | 1995-09-28 | 1998-01-27 | Man-Gill Chemical Company | Aqueous coating compositions and coated metal surfaces |
| JP3598163B2 (ja) * | 1996-02-20 | 2004-12-08 | ソニー株式会社 | 金属の表面処理方法 |
| AU5561696A (en) * | 1996-04-18 | 1997-11-07 | International Business Machines Corporation | Organic-metallic composite coating for copper surface protection |
| US6020034A (en) * | 1997-11-14 | 2000-02-01 | E. I. Du Pont De Nemours And Company | Process for producing corrosion- and creep resistant coatings |
-
1999
- 1999-10-14 JP JP29196799A patent/JP3992173B2/ja not_active Expired - Fee Related
- 1999-10-25 KR KR1019990046319A patent/KR20000029286A/ko not_active Abandoned
- 1999-10-27 CA CA002349376A patent/CA2349376A1/fr not_active Abandoned
- 1999-10-27 EP EP99963840A patent/EP1171648A1/fr not_active Withdrawn
- 1999-10-27 WO PCT/US1999/023982 patent/WO2000024948A1/fr not_active Ceased
- 1999-10-27 AU AU20202/00A patent/AU2020200A/en not_active Abandoned
- 1999-10-27 BR BR9914970-2A patent/BR9914970A/pt not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0024948A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3992173B2 (ja) | 2007-10-17 |
| JP2000199077A (ja) | 2000-07-18 |
| AU2020200A (en) | 2000-05-15 |
| BR9914970A (pt) | 2001-10-30 |
| KR20000029286A (ko) | 2000-05-25 |
| WO2000024948A1 (fr) | 2000-05-04 |
| CA2349376A1 (fr) | 2000-05-04 |
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