WO1994014999A1 - Substantially nickel-free phosphate conversion coating composition and process - Google Patents
Substantially nickel-free phosphate conversion coating composition and process Download PDFInfo
- Publication number
- WO1994014999A1 WO1994014999A1 PCT/US1993/012044 US9312044W WO9414999A1 WO 1994014999 A1 WO1994014999 A1 WO 1994014999A1 US 9312044 W US9312044 W US 9312044W WO 9414999 A1 WO9414999 A1 WO 9414999A1
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- WO
- WIPO (PCT)
- Prior art keywords
- ions
- range
- phosphate coating
- forming
- dissolved
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 41
- 230000008569 process Effects 0.000 title claims description 37
- 238000007746 phosphate conversion coating Methods 0.000 title abstract description 6
- 239000008199 coating composition Substances 0.000 title abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 60
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- -1 Zn+2 ions Chemical class 0.000 claims description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 44
- 238000000576 coating method Methods 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 41
- 229910019142 PO4 Inorganic materials 0.000 claims description 36
- 239000010452 phosphate Substances 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000011253 protective coating Substances 0.000 claims description 7
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 6
- 230000003213 activating effect Effects 0.000 claims 6
- 239000007787 solid Substances 0.000 claims 6
- 239000010936 titanium Substances 0.000 claims 6
- 229910052719 titanium Inorganic materials 0.000 claims 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 239000011701 zinc Substances 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000007739 conversion coating Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical group C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 229910000831 Steel 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
- 239000012190 activator Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- NUHCTOLBWMJMLX-UHFFFAOYSA-N bromothymol blue Chemical compound BrC1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=C(Br)C(O)=C(C(C)C)C=2)C)=C1C NUHCTOLBWMJMLX-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/186—Orthophosphates containing manganese cations containing also copper cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/368—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing magnesium cations
Definitions
- This invention relates to a composition and process for forming a phosphate conversion coating on active metal surfaces in order to increase the corrosion resist- ance of the surfaces, either as treated or after subsequent conventional overcoating of the conversion coating layer formed by an organic based protective coating such as a paint or lacquer.
- a composition according to this invention is well adapted to treat ⁇ ing any of a variety of base metals, including at least steel and galvanized steel and aluminum and aluminum based alloys.
- Nickel has been implicated as a carcinogen in some studies, so that avoidance of its use in metal finishing is desirable for health reasons. Nickel is also considered a serious pollutant, and at the levels of 0.5 - 1.5 grams per liter (hereinafter often ab- breviated "g/L") at which it is conventionally used, nickel contributes significantly to the cost of the zinc phosphate conversion coating compositions. It is an object of this invention to minimize or eliminate the use of nickel, without worsening the quality of conversion coating obtained with conventional compositions containing zinc, nickel, and manganese.
- a working composition according to this invention is an aqueous liquid compo- 5 sition that comprises, preferably consists essentially of, still more preferably consists of, water and:
- (C) from 1 to 200, or with increasing preference in the order given, from 20 to 100, 24 to 74, or 24 to 60 milligrams per liter ("mg/L") of dissolved Cu +2 ions;
- Points of free acid and total acid are defined for use herein as the number of milliliters (hereinafter “ml") of 0.1 N ⁇ aOH solution required to titrate a 10 ml sample of the composition, to a phenolphthalein end point (pH 9.0) for total acid and a bromthymol blue end point (pH 3.8) for free acid, except that if the composition has a pH greater than 3.8 initially, the points of free acid are defined as the negative of the number of ml of 0.1 N strong acid solution required to titrate a 10 ml sample of the composition to a pH of 3.8.
- a process according to this invention comprises at a minimum a step of con ⁇ tacting a metal surface to be treated with a composition according to the invention for a sufficient time to form on the metal surface a detectable conversion coating.
- Con- ventional metal surface cleaning and/or activation steps before contact between the metal to be treated and compositions according to the invention may be used if de ⁇ sired, and are generally preferred, as part of a process according to this invention.
- a process according to the invention also may, and usually preferably does, include con ⁇ ventional steps subsequent to the contact between the metal surface to be treated and the compositions according to the invention.
- the phosphate ions required for the compositions according to this invention are preferably PO 4 "3 ions or other ions derivable from less complete ionization of ortho- phosphoric acid (H 3 PO 4 ). Any free unionized phosphoric acid that may be present is considered part of the content of phosphate ions, to the extent of its stoichiometric cor ⁇ respondence to PO 4 '3 ions. Other free phosphoric acids such as metaphosphoric acid and condensed phosphoric acids such as pyrophosphoric acid and all anions derivable from them may also be used to supply the necessary phosphate ions.
- the phosphate ions are derived from orthophosphoric acid and/or its neutral or acid salts of the metal cations also specified above as part of the compositions according to this invention.
- the zinc cations required as part of the compositions are preferably derived from neutral or acid zinc salts of orthophosphoric acid, which may be formed in situ by dissolving zinc or zinc oxide or hydroxide in a solution containing the acid.
- cupric cations required as part of the compositions according to this inven ⁇ tion may be derived from salts such as cupric sulfate and/or nitrate, or may be ob ⁇ tained by dissolving cupric oxide in part of the phosphoric acid used.
- the accelerator component required in compositions according to the invention preferably includes at least one of the following: (i) from 0.01 to 0.2 g/1 of nitrite ions, (ii) from 0.5 to 5 g/1 of H 2 O 2 , (iii) from 0.05 to 2 g/1 of m-nitrobenzenesulfonate ions, (iv) from 0.05 to 2 g/1 of m-nitrobenzoate ions, (v) from 0.05 to 2 g/1 of p-nitro- phenol, and (vi) from 0.1 to 10, more preferably from 0.5 to 6, or still more preferably from 0.5 to 2.0, g L, measured as it stoichiometric equivalent as hydroxylamine, of a component capable of furnishing hydroxylamine in water solution.
- the accelerator is hydroxylamine sulfate (hereinafter often abbreviated "HAS") or a similar safe and readily available source of dissolved hydroxylamine.
- HAS hydroxylamine sulfate
- the second most preferable accelerator is nitrite ions.
- the acidity of the compositions according to the invention is preferably derived from phosphoric, sulfuric, and/or nitric acids.
- the free fluoride may be derived from complex fluoride ions such as fluoborate (BF 4 2 ), fluohafnate (HfF 6 "2 ), fluosilicate (SiF 6 '2 ), fluotitanate (TiF 6 "2 ), fluozirconate (ZrF 6 “2 ), and mixtures thereof; more preferably, from fluoborate and fluo- silicate and mixtures thereof.
- complex fluoride ions such as fluoborate (BF 4 2 ), fluohafnate (HfF 6 "2 ), fluosilicate (SiF 6 '2 ), fluotitanate (TiF 6 "2 ), fluozirconate (ZrF 6 “2 ), and mixtures thereof; more preferably, from fluoborate and fluo- silicate and mixtures thereof.
- simple fluorides such as alkali metal fluorides are also entirely satisfactory sources of free fluoride.
- compositions according to the invention contain no more than 0.5, 0.2, 0.10, 0.07, 0.03, 0.01, 0.005, or 0.001 g/L of each of Ni +2 , any cation with a valence of three or higher, chloride ions including complex chloride ions, and chlorate ions.
- chloride ions are present in sufficient quantity to be readily determined analytically, it is preferred that the ratio of the concentration in g/L of complex fluoride ions to the concentration in g/L of chloride ions have a value of at least 8:1, or more preferably a value of at least 14:1.
- contact between the metal surface to be treated and a composition according to the invention may be accomplished by spraying, dipping, or any other convenient method or combination of methods.
- the temperature during contact between the metal treated and the composition according to the invention preferably is, with increasing preference in the order given, in the range from 21 to 85, 25 to 55, or 31 to 44, ° C.
- the total time of contact between the composition according to the invention and the metal surface to be conversion coated preferably is, with increasing preference in the order given, in the range from 5 sec to 15 minutes (hereinafter often abbreviated "min"), 15 seconds (hereinafter often abbreviated "sec”) to 10 min, 30 sec to 5 min, or 90 to 120 sec.
- the add-on mass of the phosphate coating formed preferably is, with increasing preference in the order given, in the range from 1.1 to 5.4, 1.6 to 4.3, or 2.2 to 3.8, grams per square meter (hereinafter "g/m 2 ) of surface treated.
- the weight percent of copper in the coat ⁇ ing formed preferably is, with increasing preference in the order given, from 0.50 to 10, 1.0 to 8.0, 2.0 to 6.0, 3.0 to 4.1.
- compositions except for one comparison example, illustrate the use of
- HAS accelerator HAS accelerator. Specific compositions are shown in Table 1 below. These composi- tions, except for comparison example 13 which was prepared from a commercially compounded concentrate, were prepared according to the following general procedure: An amount of water equal to about three-quarters of the volume eventually desired for the composition was initially used, and an amount of zinc dihydrogen phosphate suffi ⁇ cient to provide the desired zinc ion concentration in the final desired volume was dis ⁇ solved in this water. An amount of 75 % aqueous solution of orthophosphoric acid that was sufficient, together with the previously added zinc dihydrogen phosphate, to provide the desired final concentration of phosphate ions in the desired final volume was then added.
- Test panels of cold rolled steel, galvanized steel, and/or conventional aluminum alloys used in automobile and appliance manufacture were used and subjected to the following general sequence of process steps: (1) Conventional alkaline cleaner for 120 sec at 43° C; (2) Water rinse at 38° C for 60 sec; (3) Conventional colloidal titanium phosphate activator for 30 sec at 38° C; (4) Contact with one of Composi ⁇ tions 1 - 12 from Table 1 below for 120 sec at 35° C or at 43° C; (5) Cold water rinse at 20 - 25 ° C for 60 sec; (6) Post treatment for 30 sec with a conventional commer ⁇ cial post treatment composition containing hexavalent and trivalent chromium; and (7) Rinse with deionized water for 30 sec at 20 - 25 ° C.
- compositions were prepared in the same general manner as for Group I, except that sodium nitrite instead of HAS was used as the accelerator and cupric ni ⁇ trate with an average of 2.5 molecules of water of hydration per cupric ion was used as the copper source.
- Compositions are as follows:
- Example 14 was used for spray phosphating at 33° C in a process sequence other ⁇ wise like those of Group I above.
- Example 14 was used for immersion phosphating at 57° C in a process sequence otherwise like those of Group I above.
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
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Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES94904428T ES2136726T3 (es) | 1992-12-22 | 1993-12-15 | Composicion y procedimiento de revestimiento de conversion de fosfato practicamente exento de niquel. |
| JP6515227A JPH08504890A (ja) | 1992-12-22 | 1993-12-15 | 実質的にニッケルを含まないリン酸塩化被膜を形成するための組成物および方法 |
| PL93309404A PL309404A1 (en) | 1992-12-22 | 1993-12-15 | Stable nickel-free phosphate coating composition and method of obtaining same |
| DE69326021T DE69326021T2 (de) | 1992-12-22 | 1993-12-15 | Im wesentlichen nickelfreier phosphatkonversionsüberzug-zusammensetzung und verfahren |
| AU58481/94A AU5848194A (en) | 1992-12-22 | 1993-12-15 | Substantially nickel-free phosphate conversion coating composition and process |
| BR9307702-5A BR9307702A (pt) | 1992-12-22 | 1993-12-15 | Composição lìquida aquosa, e, processo para a produção de um revestimento de fosfato e um revestimento protetor sobre a superfìcie de um substrato metálico |
| EP94904428A EP0675972B1 (en) | 1992-12-22 | 1993-12-15 | Substantially nickel-free phosphate conversion coating composition and process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US99546592A | 1992-12-22 | 1992-12-22 | |
| US07/995,465 | 1992-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994014999A1 true WO1994014999A1 (en) | 1994-07-07 |
Family
ID=25541841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1993/012044 WO1994014999A1 (en) | 1992-12-22 | 1993-12-15 | Substantially nickel-free phosphate conversion coating composition and process |
Country Status (14)
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0711849A1 (de) * | 1994-11-11 | 1996-05-15 | Metallgesellschaft Aktiengesellschaft | Verfahren zum Aufbringen von Phosphatüberzügen |
| WO1997014821A1 (de) * | 1995-10-18 | 1997-04-24 | Henkel Kommanditgesellschaft Auf Aktien | Schichtgewichtssteuerung bei hydroxylamin-beschleunigten phosphatiersystemen |
| WO1997016581A3 (de) * | 1995-10-27 | 1997-06-19 | Henkel Kgaa | Nitratarme, manganfreie zinkphosphatierung |
| WO1997030190A1 (de) * | 1996-02-19 | 1997-08-21 | Henkel Kommanditgesellschaft Auf Aktien | Zinkphosphatierung mit geringen gehalten an kupfer und mangan |
| AU697424B2 (en) * | 1995-03-29 | 1998-10-08 | Henkel Kommanditgesellschaft Auf Aktien | A phosphating process with a metal-containing after-rinse |
| WO1999014397A1 (de) * | 1997-09-17 | 1999-03-25 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur phosphatierung von stahlband |
| EP1828436A4 (en) * | 2004-12-28 | 2011-01-26 | Henkel Ag & Co Kgaa | LASERZUNDER VERRINGERND AND THEREFORE IN IMPROVED PUNCHING RESULTING IRON PHOSPHATING PROCESS |
| WO2024149790A1 (en) * | 2023-01-11 | 2024-07-18 | Chemetall Gmbh | Composition for phosphatizing of ferrous surfaces and method making use thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10320313B4 (de) * | 2003-05-06 | 2005-08-11 | Chemetall Gmbh | Verfahren zum Beschichten von metallischen Körpern mit einer Phosphatierungslösung, Phosphatierungslösung und die Verwendung des beschichteten Gegenstandes |
| DE102006052919A1 (de) * | 2006-11-08 | 2008-05-15 | Henkel Kgaa | Zr-/Ti-haltige Phosphatierlösung zur Passivierung von Metallverbundoberflächen |
| CN103924226B (zh) * | 2014-04-25 | 2016-06-15 | 山东大学 | 一种分级结构磷酸锌化学转化膜的制备方法 |
| CN104032293B (zh) * | 2014-06-11 | 2016-02-17 | 安徽江南机械有限责任公司 | 一种不含镍单组分高耐蚀性环保黑色磷化液 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0459541A1 (de) * | 1990-04-27 | 1991-12-04 | METALLGESELLSCHAFT Aktiengesellschaft | Verfahren zur Phosphatierung von Metalloberflächen |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB526816A (en) * | 1939-03-14 | 1940-09-26 | Samuel Thomas Roberts | Improvements in the conversion of zinc, zinc alloy, galvanised, cadmium and cadmium alloy surfaces for ensuring paint and enamel adhesion |
| US2813812A (en) * | 1952-06-24 | 1957-11-19 | Parker Rust Proof Co | Method for coating iron or zinc with phosphate composition and aqueous solution therefor |
| DE1287413B (de) * | 1965-11-06 | 1969-01-16 | Metallgesellschaft Ag | Verfahren zur Vorbereitung von Stahl fuer die elektrophoretische Beschichtung mit Lacken |
| US3597283A (en) * | 1969-10-08 | 1971-08-03 | Lubrizol Corp | Phosphating solutions for use on ferrous metal and zinc surfaces |
| IT975560B (it) * | 1972-10-20 | 1974-08-10 | Sec Accomandita Semplice Fosfa | Procedimento di fosfatazione di su perfici metalliche destinate a ver niciatura particolarmente per elet troforesi e soluzione relativa a tale procedimento |
| JPS5811514B2 (ja) * | 1979-05-02 | 1983-03-03 | 日本ペイント株式会社 | 金属表面の保護方法 |
| US4717431A (en) * | 1987-02-25 | 1988-01-05 | Amchem Products, Inc. | Nickel-free metal phosphating composition and method for use |
| CN1022496C (zh) * | 1991-06-29 | 1993-10-20 | 兰州中进高新技术公司 | 室温磷化液及其配制方法 |
| DE4210513A1 (de) * | 1992-03-31 | 1993-10-07 | Henkel Kgaa | Nickel-freie Phosphatierverfahren |
| CN1026341C (zh) * | 1992-04-21 | 1994-10-26 | 陈金田 | 常温快速磷化液 |
| DE4214992A1 (de) * | 1992-05-06 | 1993-11-11 | Henkel Kgaa | Kupfer enthaltendes, nickelfreies Phosphatierverfahren |
-
1993
- 1993-12-15 WO PCT/US1993/012044 patent/WO1994014999A1/en active IP Right Grant
- 1993-12-15 EP EP94904428A patent/EP0675972B1/en not_active Expired - Lifetime
- 1993-12-15 AT AT94904428T patent/ATE183247T1/de not_active IP Right Cessation
- 1993-12-15 ES ES94904428T patent/ES2136726T3/es not_active Expired - Lifetime
- 1993-12-15 BR BR9307702-5A patent/BR9307702A/pt not_active IP Right Cessation
- 1993-12-15 AU AU58481/94A patent/AU5848194A/en not_active Abandoned
- 1993-12-15 JP JP6515227A patent/JPH08504890A/ja active Pending
- 1993-12-15 PL PL93309404A patent/PL309404A1/xx unknown
- 1993-12-15 SG SG1996005336A patent/SG55084A1/en unknown
- 1993-12-15 DE DE69326021T patent/DE69326021T2/de not_active Expired - Fee Related
- 1993-12-15 CA CA002150545A patent/CA2150545A1/en not_active Abandoned
- 1993-12-15 CZ CZ19951649A patent/CZ287997B6/cs not_active IP Right Cessation
- 1993-12-22 ZA ZA939636A patent/ZA939636B/xx unknown
- 1993-12-22 CN CN93119949A patent/CN1092245C/zh not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0459541A1 (de) * | 1990-04-27 | 1991-12-04 | METALLGESELLSCHAFT Aktiengesellschaft | Verfahren zur Phosphatierung von Metalloberflächen |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0711849A1 (de) * | 1994-11-11 | 1996-05-15 | Metallgesellschaft Aktiengesellschaft | Verfahren zum Aufbringen von Phosphatüberzügen |
| AU697424B2 (en) * | 1995-03-29 | 1998-10-08 | Henkel Kommanditgesellschaft Auf Aktien | A phosphating process with a metal-containing after-rinse |
| WO1997014821A1 (de) * | 1995-10-18 | 1997-04-24 | Henkel Kommanditgesellschaft Auf Aktien | Schichtgewichtssteuerung bei hydroxylamin-beschleunigten phosphatiersystemen |
| WO1997016581A3 (de) * | 1995-10-27 | 1997-06-19 | Henkel Kgaa | Nitratarme, manganfreie zinkphosphatierung |
| WO1997030190A1 (de) * | 1996-02-19 | 1997-08-21 | Henkel Kommanditgesellschaft Auf Aktien | Zinkphosphatierung mit geringen gehalten an kupfer und mangan |
| AU708141B2 (en) * | 1996-02-19 | 1999-07-29 | Henkel Kommanditgesellschaft Auf Aktien | Zinc phosphatizing using low concentrations of copper and manganese |
| WO1999014397A1 (de) * | 1997-09-17 | 1999-03-25 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur phosphatierung von stahlband |
| EP1828436A4 (en) * | 2004-12-28 | 2011-01-26 | Henkel Ag & Co Kgaa | LASERZUNDER VERRINGERND AND THEREFORE IN IMPROVED PUNCHING RESULTING IRON PHOSPHATING PROCESS |
| WO2024149790A1 (en) * | 2023-01-11 | 2024-07-18 | Chemetall Gmbh | Composition for phosphatizing of ferrous surfaces and method making use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0675972A4 (enrdf_load_stackoverflow) | 1995-11-02 |
| AU5848194A (en) | 1994-07-19 |
| DE69326021T2 (de) | 1999-12-23 |
| BR9307702A (pt) | 1999-08-31 |
| CZ164995A3 (en) | 1996-01-17 |
| SG55084A1 (en) | 1998-12-21 |
| EP0675972A1 (en) | 1995-10-11 |
| EP0675972B1 (en) | 1999-08-11 |
| PL309404A1 (en) | 1995-10-02 |
| DE69326021D1 (de) | 1999-09-16 |
| ES2136726T3 (es) | 1999-12-01 |
| CZ287997B6 (cs) | 2001-03-14 |
| ZA939636B (en) | 1994-08-15 |
| JPH08504890A (ja) | 1996-05-28 |
| CN1090606A (zh) | 1994-08-10 |
| CN1092245C (zh) | 2002-10-09 |
| ATE183247T1 (de) | 1999-08-15 |
| CA2150545A1 (en) | 1994-07-07 |
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