EP0717787B1 - Nickel-free phosphatization process - Google Patents
Nickel-free phosphatization process Download PDFInfo
- Publication number
- EP0717787B1 EP0717787B1 EP94925483A EP94925483A EP0717787B1 EP 0717787 B1 EP0717787 B1 EP 0717787B1 EP 94925483 A EP94925483 A EP 94925483A EP 94925483 A EP94925483 A EP 94925483A EP 0717787 B1 EP0717787 B1 EP 0717787B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- hydroxylamine
- free
- phosphating solution
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 19
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 18
- ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 13
- 239000010959 steel Substances 0.000 claims abstract description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008397 galvanized steel Substances 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000680 Aluminized steel Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 35
- 229910052725 zinc Inorganic materials 0.000 claims description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 25
- 229910002651 NO3 Inorganic materials 0.000 claims description 23
- -1 hydroxylamine compound Chemical class 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 19
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 235000021317 phosphate Nutrition 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 238000004070 electrodeposition Methods 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 20
- 150000001768 cations Chemical class 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000010422 painting Methods 0.000 description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007613 environmental effect Effects 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
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 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 4
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000009189 diving Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000002443 hydroxylamines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- OHAVYOCBYILSBZ-UHFFFAOYSA-M dihydroxyboron;hydroxy(dioxo)tungsten Chemical compound O[B]O.O[W](=O)=O OHAVYOCBYILSBZ-UHFFFAOYSA-M 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- VRXOQUOGDYKXFA-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical class ON.ON.OS(O)(=O)=O VRXOQUOGDYKXFA-UHFFFAOYSA-N 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—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
- C23C22/182—Orthophosphates containing manganese cations 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
- C23C22/364—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 manganese cations
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- 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
Definitions
- the invention relates to methods for phosphating metal surfaces with aqueous, acid phosphating solutions, the zinc, manganese and phosphate ions and hydroxylamine in free or bound form and / or m-nitrobenzenesulfonic acid or contain their water-soluble salts, and their Application as pretreatment of the metal surfaces for a subsequent Painting, especially an electro dip painting.
- the procedure is applicable for the treatment of surfaces made of steel, galvanized or galvanized alloy Steel, aluminum, aluminized or alloy aluminized Steel, in particular for the treatment of galvanized on one or both sides, preferably electrolytically galvanized steel.
- the phosphating of metals pursues the goal on the metal surface to produce firmly grown metal phosphate layers that are in themselves improve the corrosion resistance and in connection with paints and other organic coatings to significantly increase the Paint adhesion and resistance to infiltration when exposed to corrosion contribute.
- Such phosphating processes have long been known.
- For pretreatment before painting is particularly suitable for low-zinc phosphating processes, where the phosphating solutions are comparatively low levels of zinc ions of e.g. B. 0.5 to 2 g / l.
- An essential parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually is in the range> 8 and can take values up to 30.
- the high content of nickel ions in the phosphating solutions of the trication processes and of nickel and nickel compounds in the phosphate layers formed however, has disadvantages in that nickel and nickel compounds from the point of view of environmental protection and workplace hygiene as be critically classified.
- low-zinc phosphating processes have been becoming increasingly common described without sharing from nickel to high-quality phosphate layers similar to that lead nickel-containing processes.
- nitrite and Nitrates are increasingly raised concerns about possible formation of nitrous gases.
- DE-A-39 20 296 describes a phosphating process which dispenses with nickel and uses magnesium ions in addition to zinc and manganese ions.
- the phosphating baths described here contain from 0.2 to 10 g / l nitrate ions other oxidizing agents acting as accelerators, selected from nitrite, chlorate or an organic oxidizing agent.
- EP-A-60 716 discloses low zinc phosphating baths which are considered essential Cations contain zinc and manganese and that as an optional ingredient May contain nickel.
- the necessary accelerator is preferred selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
- EP-A-228 151 also describes phosphating baths which are essential Cations contain zinc and manganese.
- the phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzenesulfonate, m-nitrobenzoate or p-nitrophenol.
- the nitrate content to 5 to about 15 g / l and an optional nickel content specified between 0.4 and 4 g / l.
- the exemplary embodiments contain this all nickel and nitrate.
- the main focus of this application is due to the fact that chlorate-free phosphating processes are provided will.
- EP-A-544 650 teaches something similar.
- the phosphating process disclosed in WO-A-86/04931 works without nitrates.
- the accelerator system is based on a combination of 0.5 - 1 g / l Bromate and 0.2-0.5 g / l m-nitrobenzenesulfonate.
- the phosphating solutions preferably contain in addition to zinc, at least 2 of these optional metals.
- EP-A-36689 teaches the use of preferably 0.03-0.2% by weight of nitrobenzenesulfonate in Combination with preferably 0.1-0.5% by weight chlorate in phosphating baths, whose manganese content is 5-33% by weight of the zinc content.
- DE-A-40 13 483 discloses phosphating processes with which similarly good ones Corrosion protection properties as achieved with the trication process can. These processes do without nickel and use instead Copper in low concentrations, 0.001 to 0.03 g / l.
- Oxygen and / or other equivalent functions serve in the trivalent stage Oxidizing agent. As such are nitrite, chlorate, bromate, peroxy compounds and organic nitro compounds, such as nitrobenzenesulfonate, specified.
- German patent application with the file number P 42 10 513.7 modifies this process in that as a modifying agent for the Morphology of the phosphate crystals formed hydroxylamine, its salts or complexes are added in an amount of 0.5 to 5 g / l hydroxylamine.
- EP-A-321 059 teaches zinc phosphating baths which contain 0.1 to 2.0 g / l zinc and an accelerator also 0.01 to 20 g / l tungsten in the form of a soluble tungsten compound, preferably alkali metal or ammonium tungstate or silicotungstate, alkaline earth metal silicotungstate or boro- or silicotungstic acid.
- the accelerator is selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
- nickel in quantities of 0.1 - 4 g / l and nitrate in quantities 0.1 - 15 g / l.
- DE-C-27 39 006 describes a phosphating process for surfaces Zinc or zinc alloys that are free of nitrate and ammonium ions.
- an essential content of zinc in amounts between 0.1 and 5 g / l are 1 to 10 parts by weight of nickel and / or cobalt per part by weight of zinc required.
- Hydrogen peroxide is used as an accelerator. From the From the point of view of workplace hygiene and environmental protection, cobalt is not one Alternative to nickel.
- the object of the invention is to provide phosphating baths positions that are free from environmental and workplace hygiene Reasonably questionable nickel or the similarly questionable cobalt, no Contain nitrite and at the same time a greatly reduced nitrate content have and are preferably free of nitrate. Furthermore, the Phosphating baths should be free of copper, the dosage of which according to DE-A-40 13 483 effective concentration range of 1 - 30 ppm is problematic.
- phosphating baths are free of nickel, copper, nitrite and oxo anions Halogens mean that these elements or ions not deliberately added to the phosphating baths. However, it is in the Practice does not rule out that such components are beyond what is to be treated Material, the preparation water or the ambient air in traces in the Phosphating baths are entered. In particular, it cannot be ruled out that in the phosphating of coated with zinc-nickel alloys Steel nickel ions are introduced into the phosphating solution. However, the expectation is placed on the phosphating baths according to the invention that that under technical conditions the nickel concentration in the Baths is below 0.01 g / l, in particular below 0.0001 g / l.
- baths Preferably no nitrate is added to the baths.
- the baths contain the nitrate content of the locally available drinking water (according to Drinking water regulation in Germany maximum 50 mg / l) or by evaporation have higher nitrate levels due to The invention
- baths should have a maximum nitrate content of 0.5 g / l and preferably contain less than 0.1 g / l nitrate.
- Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of Hydroxylammonium salts are used. If you add free hydroxylamine Phosphating bath or a phosphating bath concentrate too, it is due of the acidic character of these solutions largely as a hydroxylammonium cation available.
- Sulfates and the phosphates are particularly suitable. In the case of the phosphates the acidic salts are preferred because of their better solubility.
- Hydroxylamine or its compounds in the phosphating bath in such Amounts added that the calculated concentration of free hydroxylamine is between 0.1 and 5 g / l, in particular between 0.4 and 2 g / l. It has proven to be beneficial to choose the hydroxylamine concentration so that the ratio of the sum of the concentrations of zinc and manganese for the concentration of the hydroxylamine, in each case in g / l, 1.0 to 6.0, preferably Is 2.0 to 4.0.
- the inventive Phosphating baths containing hydroxylamine or hydroxylamine compounds the presence of soluble compounds of hexavalent tungsten Advantages in terms of corrosion resistance and paint adhesion, although with the Phosphating method according to the invention, in contrast to the teaching of EP-A-321 059, without the accelerators nitrite or hydrogen peroxide can be.
- Phosphating solutions are used that additionally 20 to 800 mg / l, preferably 50 to 600 mg / l tungsten in the form of water-soluble tungstates, Silicotungstates and / or borotungstates contain.
- the mentioned anions in the form of their acids and / or their ammonium, Alkali metal and / or alkaline earth metal salts are used.
- m-Nitrobenzenesulfonate can be used as a free acid or in the form of water-soluble Salts are used.
- Such salts become "water-soluble” referred to, which dissolve in the phosphating baths so far that the required concentrations of 0.2 to 2 g / l m-nitrobenzenesulfonate can be achieved.
- the alkali metal salts are particularly suitable for this the sodium salts.
- the phosphating baths preferably contain 0.4 to 1 g / l m-nitrobenzenesulfonate.
- a ratio of 1:10 to 10: 1 between the more reductive Hydroxylamine and the more oxidative m-nitrobenzenesulfonate can lead to special advantages with regard to layer formation, in particular regarding the shape of the crystals formed.
- the phosphating baths contain either hydroxylamine or m-nitrobenzenesulfonic acid.
- the weight ratio of phosphate ions to zinc ions in the phosphating baths can fluctuate within wide limits, provided it is in the range between 3.7 and 30 lies. A weight ratio between 10 and 20 is particularly preferred.
- Those skilled in the art are further parameters for controlling phosphating baths the free acid and total acid contents are known. The one in this Font used determination method of this parameter is in the example part specified. Free acid values between 0.3 and 1.5 points for partial phosphating, with band phosphating up to 2.5 points and the total acidity between about 15 and about 25 points are in the usual technical range Range and are suitable in the context of this invention.
- the manganese content of the phosphating bath should be between 0.3 and 4 g / l, since the lower the manganese content, the positive influence on the corrosion behavior the phosphate layers no longer exist and at higher ones Manganese content no further positive effect occurs. Keep between 0.3 and 2 g / l and in particular between 0.5 and 1.5 g / l are preferred.
- the zinc content is set in phosphating baths, which only act as accelerators Contain hydroxylamine, according to EP-A-315 059 preferably to values between 0.45 and 1.1 g / l, for phosphating baths, which only accelerate m-nitrobenzenesulfonate contain, preferably to values between 0.6 and 1.4 g / l a.
- the current zinc content of the worker Bath increases up to 2 g / l. It is important to ensure that the manganese content is at least 50% of the zinc content, otherwise it is insufficient Corrosion protection properties result.
- the Zinc and manganese ions are introduced into the phosphating baths basically irrelevant. In order to meet the conditions according to the invention, however, are the nitrites, nitrates, and salts with oxo anions of halogens these cations cannot be used. It is particularly useful as Zinc and / or manganese source to use the oxides and / or carbonates. In addition to the divalent cations mentioned, they contain phosphating baths usually sodium, potassium and / or ammonium ions to adjust the parameters free acid and total acid are used. Ammonium ions can also be formed by degradation of the hydroxylamine.
- iron goes in the form of iron (II) ions in solution. Since the phosphating baths according to the invention do not contain substances that are strong compared to iron (II) have an oxidizing effect, the divalent iron mainly goes off in succession Air oxidation into the trivalent state, so that it is called ferric phosphate can fail. Therefore, in the phosphating baths according to the invention Build up iron (II) levels that are well above the levels which contain baths containing oxidizing agents. With that in mind Iron (II) concentrations up to 50 ppm normal, with short-term in the production process Values up to 500 ppm can also occur. For the invention Phosphating processes are such iron (II) concentrations not harmful.
- the phosphating baths can be used in hard water also the hardness cations Mg (II) and Ca (II) in a total concentration up to 7 mmol / l.
- the method according to the invention is suitable for phosphating surfaces made of steel, galvanized or alloy galvanized steel, aluminum, aluminized or alloy aluminized steel.
- Baths containing hydroxylamine are especially designed for the treatment of galvanized on one or both sides, preferably electrolytically galvanized steel.
- the materials mentioned can - as is increasingly common in automotive engineering will also exist side by side.
- the procedure is for the application suitable in immersion, spray or spray / immersion processes. It can be used in particular in the automotive industry, where treatment times between 1 and 8 minutes are common. Use in tape phosphating in the steel mill, with treatment times between 5 and 12 seconds, is also possible.
- Suitable bath temperatures are also common in the prior art between 30 and 70 ° C, the temperature range between 40 and 60 ° C is preferred.
- the phosphating process according to the invention is used to produce a sliding layer for forming and in particular for treating the metal surfaces mentioned before painting, for example before a cathodic one Electro-dip coating thought as it is common in automotive engineering.
- the phosphating process is part of the technically usual pretreatment chain to see. In this chain, phosphating is common the steps cleaning / degreasing, rinsing and activating upstream, the activation usually with titanium phosphate-containing Activating agents are carried out.
- the phosphating according to the invention can if necessary after an intermediate rinse, a passivating after-treatment consequences. Chromic acid-containing ones are used for such a passivating aftertreatment Treatment baths widely used.
- the mass per unit area (“layer weight”) was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942, Table 6. Corrosion tests were carried out according to the VDA alternating climate test 621-415 with KTL primer (KTL-light gray from BASF, FT 85- 7042); partly also with a complete paint structure (top coat: alpine white, VW).
- KTL primer KTL-light gray from BASF, FT 85- 7042
- top coat alpine white, VW.
- Layer weights were determined by dissolving in 5% chromic acid solution. Corrosion tests were carried out according to the VDA alternating climate test 621-415 both with KTL primer (ED 12 MB from PPG) and with a complete paint system (KTL as above, filler: 1-component high-solid PU filler gray, top coat: DB 744 metallic basecoat and clearcoat). The paint infiltration (mm) was evaluated after every 10 week test cycles. In addition, a shot put test was carried out according to the Mercedes-Benz standard analogous to DIN 53 230 (6 bar corresponding to 250 km / h), evaluation at substrate temperature -20 ° C. The damage area was assessed in mm 2 (Mercedes-Benz standard: max.
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Abstract
Description
Die Erfindung betrifft Verfahren zur Phosphatierung von Metalloberflächen mit wäßrigen, sauren Phosphatierlösungen, die Zink-, Mangan- und Phosphationen sowie Hydroxylamin in freier oder gebundener Form und/oder m-Nitrobenzolsulfonsäure oder deren wasserlösliche Salze enthalten, sowie deren Anwendung als Vorbehandlung der Metalloberflächen für eine anschließende Lackierung, insbesondere eine Elektrotauchlackierung. Das Verfahren ist anwendbar zur Behandlung von Oberflächen aus Stahl, verzinktem oder legierungsverzinktem Stahl, Aluminium, aluminiertem oder legierungsaluminiertem Stahl, insbesondere zur Behandlung von ein- oder beidseitig verzinktem, vorzugsweise elektrolytisch verzinktem Stahl.The invention relates to methods for phosphating metal surfaces with aqueous, acid phosphating solutions, the zinc, manganese and phosphate ions and hydroxylamine in free or bound form and / or m-nitrobenzenesulfonic acid or contain their water-soluble salts, and their Application as pretreatment of the metal surfaces for a subsequent Painting, especially an electro dip painting. The procedure is applicable for the treatment of surfaces made of steel, galvanized or galvanized alloy Steel, aluminum, aluminized or alloy aluminized Steel, in particular for the treatment of galvanized on one or both sides, preferably electrolytically galvanized steel.
Die Phosphatierung von Metallen verfolgt das Ziel, auf der Metalloberfläche festverwachsene Metallphosphatschichten zu erzeugen, die für sich bereits die Korrosionsbeständigkeit verbessern und in Verbindung mit Lacken und anderen organischen Beschichtungen zu einer wesentlichen Erhöhung der Lackhaftung und der Resistenz gegen Unterwanderung bei Korrosionsbeanspruchung beitragen. Solche Phosphatierverfahren sind seit langem bekannt. Für die Vorbehandlung vor der Lackierung eignen sich insbesondere die Niedrig-Zink-Phosphatierverfahren, bei denen die Phosphatierlösungen vergleichsweise geringe Gehalte an Zinkionen von z. B. 0,5 bis 2 g/l aufweisen. Ein wesentlicher Parameter in diesen Niedrig-Zink-Phosphatierbädern ist das Gewichtsverhältnis Phosphationen zu Zinkionen, das üblicherweise im Bereich > 8 liegt und Werte bis zu 30 annehmen kann.The phosphating of metals pursues the goal on the metal surface to produce firmly grown metal phosphate layers that are in themselves improve the corrosion resistance and in connection with paints and other organic coatings to significantly increase the Paint adhesion and resistance to infiltration when exposed to corrosion contribute. Such phosphating processes have long been known. For pretreatment before painting is particularly suitable for low-zinc phosphating processes, where the phosphating solutions are comparatively low levels of zinc ions of e.g. B. 0.5 to 2 g / l. An essential parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually is in the range> 8 and can take values up to 30.
Es hat sich gezeigt, daß durch die Mitverwendung anderer mehrwertiger Kationen in den Zink-Phosphatierbädern Phosphatschichten mit deutlich verbesserten Korrosionsschutz- und Lackhaftungseigenschaften ausgebildet werden können. Beispielsweise finden Niedrig-Zink-Verfahren mit Zusatz von z. B. 0,5 bis 1,5 g/l Manganionen und z. B. 0,3 bis 2,0 g/l Nickelionen als sogenannte Trikation-Verfahren zur Vorbereitung von Metalloberflächen für die Lackierung, beispielsweise für die kathodische Elektrotauchlackierung von Autokarosserien, weite Anwendung.It has been shown that by using other polyvalent cations in the zinc phosphating baths phosphate layers with significantly improved Corrosion protection and paint adhesion properties are formed can. For example, find low-zinc processes with the addition of z. B. 0.5 to 1.5 g / l of manganese ions and z. B. 0.3 to 2.0 g / l of nickel ions as so-called trication process for the preparation of metal surfaces for painting, for example for cathodic electro-painting of car bodies, wide application.
Der hohe Gehalt an Nickelionen in den Phosphatierlösungen der Trikation-Verfahren und von Nickel und Nickelverbindungen in den gebildeten Phosphatschichten bringt jedoch insofern Nachteile, als Nickel und Nickelverbindungen aus der Sicht des Umweltschutzes und der Arbeitsplatzhygiene als kritisch eingestuft werden. In letzter Zeit werden daher zunehmend Niedrig-Zink-Phosphatierverfahren beschrieben, die ohne eine Mitverwendung von Nickel zu qualitativ ähnlich hochwertigen Phosphatschichten wie die nickelhaltigen Verfahren führen. Auch gegen die Beschleuniger Nitrit und Nitrat werden wegen möglicher Bildung Nitroser Gase zunehmend Bedenken geäußert. Darüber hinaus hat sich gezeigt, daß die Phosphatierung von verzinktem Stahl mit nickelfreien Phosphatierbädern zu unzureichendem Korrosionsschutz und unzureichender Lackhaftung führt, wenn die Phosphatierbäder größere Mengen (> 0,5 g/l) Nitrat enthalten.The high content of nickel ions in the phosphating solutions of the trication processes and of nickel and nickel compounds in the phosphate layers formed however, has disadvantages in that nickel and nickel compounds from the point of view of environmental protection and workplace hygiene as be critically classified. Recently, low-zinc phosphating processes have been becoming increasingly common described without sharing from nickel to high-quality phosphate layers similar to that lead nickel-containing processes. Also against the accelerators nitrite and Nitrates are increasingly raised concerns about possible formation of nitrous gases. In addition, it has been shown that the phosphating of galvanized Steel with nickel-free phosphating baths for insufficient corrosion protection and insufficient paint adhesion results when the phosphating baths contain larger quantities (> 0.5 g / l) nitrate.
Beispielsweise beschreibt die DE-A-39 20 296 ein Phosphatierverfahren, das auf Nickel verzichtet und neben Zink und Manganionen Magnesiumionen verwendet. Die hier beschriebenen Phosphatierbäder enthalten außer 0,2 bis 10 g/l Nitrationen weitere als Beschleuniger wirkende Oxidationsmittel, ausgewählt aus Nitrit, Chlorat oder einem organischen Oxidationsmittel.For example, DE-A-39 20 296 describes a phosphating process which dispenses with nickel and uses magnesium ions in addition to zinc and manganese ions. The phosphating baths described here contain from 0.2 to 10 g / l nitrate ions other oxidizing agents acting as accelerators, selected from nitrite, chlorate or an organic oxidizing agent.
EP-A-60 716 offenbart Niedrig-Zink-Phosphatierbäder, die als essentielle Kationen Zink und Mangan enthalten und die als fakultativen Bestandteil Nickel beinhalten können. Der notwendige Beschleuniger wird vorzugsweise ausgewählt aus Nitrit, m-Nitrobenzolsulfonat oder Wasserstoffperoxid. In einem abhängigen Patentanspruch wird die Verwendung von 1 bis 10 g/l Nitrat angegeben; alle Erfindungsbeispiele enthalten 4 g/l Nitrat.EP-A-60 716 discloses low zinc phosphating baths which are considered essential Cations contain zinc and manganese and that as an optional ingredient May contain nickel. The necessary accelerator is preferred selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide. In a dependent claim, the use of 1 to 10 g / l nitrate specified; all examples of the invention contain 4 g / l of nitrate.
Auch in der EP-A-228 151 werden Phosphatierbäder beschrieben, die als essentielle Kationen Zink und Mangan enthalten. Der Phosphatierbeschleuniger wird ausgewählt aus Nitrit, Nitrat, Wasserstoffperoxid, m-Nitrobenzolsulfonat, m-Nitrobenzoat oder p-Nitrophenol. In abhängigen Ansprüchen wird der Nitratgehalt auf 5 bis etwa 15 g/l sowie ein fakultativer Nickelgehalt zwischen 0,4 und 4 g/l spezifiziert. Die Ausführungsbeispiele hierzu enthalten alle sowohl Nickel als auch Nitrat. Das Schwergewicht dieser Anmeldung liegt darauf, daß chloratfreie Phosphatierverfahren zur Verfügung gestellt werden. Ähnliches lehrt die EP-A-544 650.EP-A-228 151 also describes phosphating baths which are essential Cations contain zinc and manganese. The phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzenesulfonate, m-nitrobenzoate or p-nitrophenol. In dependent claims the nitrate content to 5 to about 15 g / l and an optional nickel content specified between 0.4 and 4 g / l. The exemplary embodiments contain this all nickel and nitrate. The main focus of this application is due to the fact that chlorate-free phosphating processes are provided will. EP-A-544 650 teaches something similar.
Nitratfrei arbeitet das in WO-A-86/04931 offengelegte Phosphatierverfahren. Hier beruht das Beschleunigersystem auf einer Kombination von 0,5 - 1 g/l Bromat und 0,2 - 0,5 g/l m-Nitrobenzolsulfonat. Als essentielles mehrwertiges Kation wird lediglich Zink, als weitere fakultative Kationen Nickel, Mangan oder Kobalt angegeben. Vorzugsweise enthalten die Phosphatierlösungen neben Zink mindestens 2 dieser fakultativen Metalle. EP-A-36689 lehrt die Verwendung von vorzugsweise 0,03 - 0,2 Gew.-% Nitrobenzolsulfonat in Kombination mit vorzugsweise 0,1 - 0,5 Gew.-% Chlorat in Phosphatierbädern, deren Mangangehalt 5-33 Gew.-% des Zinkgehalts beträgt.The phosphating process disclosed in WO-A-86/04931 works without nitrates. Here the accelerator system is based on a combination of 0.5 - 1 g / l Bromate and 0.2-0.5 g / l m-nitrobenzenesulfonate. As an essential multi-value Cation becomes only zinc, as further optional cations nickel, Manganese or cobalt specified. The phosphating solutions preferably contain in addition to zinc, at least 2 of these optional metals. EP-A-36689 teaches the use of preferably 0.03-0.2% by weight of nitrobenzenesulfonate in Combination with preferably 0.1-0.5% by weight chlorate in phosphating baths, whose manganese content is 5-33% by weight of the zinc content.
WO-A-90/12901 offenbart ein chlorat- und nitritfreies Verfahren zur Herstellung
von nickel- und manganhaltigen Zinkphosphatschichten auf Stahl, Zink
und/oder deren Legierungen durch Spritzen, Spritztauchen und/oder Tauchen
mit einer wäßrigen Lösung enthaltend
DE-A-40 13 483 macht Phosphatierverfahren bekannt, mit denen ähnlich gute Korrosionsschutzeigenschaften wie mit den Trikation-Verfahren erzielt werden können. Diese Verfahren verzichten auf Nickel und verwenden statt dessen Kupfer in niedrigen Konzentrationen, 0,001 bis 0,03 g/l. Zur Oxidation des bei der Beizreaktion von Stahloberflächen gebildeten zweiwertigen Eisens in die dreiwertige Stufe dienen Sauerstoff und/oder andere gleichwirkende Oxidationsmittel. Als solche werden Nitrit, Chlorat, Bromat, Peroxi-Verbindungen sowie organische Nitroverbindungen, wie Nitrobenzolsulfonat, angegeben. Die deutsche Patentanmeldung mit dem Aktenzeichen P 42 10 513.7 modifiziert diesen Prozeß dadurch, daß als modifizierendes Agens für die Morphologie der gebildeten Phosphatkristalle Hydroxylamin, dessen Salze oder Komplexe in einer Menge von 0,5 bis 5 g/l Hydroxylamin zugegeben werden.DE-A-40 13 483 discloses phosphating processes with which similarly good ones Corrosion protection properties as achieved with the trication process can. These processes do without nickel and use instead Copper in low concentrations, 0.001 to 0.03 g / l. For oxidation of the divalent iron formed in the pickling reaction of steel surfaces Oxygen and / or other equivalent functions serve in the trivalent stage Oxidizing agent. As such are nitrite, chlorate, bromate, peroxy compounds and organic nitro compounds, such as nitrobenzenesulfonate, specified. The German patent application with the file number P 42 10 513.7 modifies this process in that as a modifying agent for the Morphology of the phosphate crystals formed hydroxylamine, its salts or complexes are added in an amount of 0.5 to 5 g / l hydroxylamine.
Die Verwendung von Hydroxylamin und/oder seinen Verbindungen zum Beeinflussen der Form der Phosphatkristalle ist aus einer Reihe von Offenlegungsschriften bekannt. Die EP-A-315 059 gibt als besonderen Effekt der Verwendung von Hydroxylamin in Phosphatierbädern die Tatsache an, daß auf Stahl auch dann noch die Phosphatkristalle in einer erwünschten säulen- oder knollenartigen Form entstehen, wenn die Zinkkonzentration im Phosphatierbad den für Niedrig-Zink-Verfahren üblichen Bereich übersteigt. Hierdurch wird es möglich, die Phosphatierbäder mit Zinkkonzentrationen bis zu 2 g/l und mit Gewichtsverhältnissen Phosphat zu Zink bis hinab zu 3,7 zu betreiben. Über vorteilhafte Kationenkombinationen dieser Phosphatierbäder werden keine näheren Aussagen gemacht, in den Patentbeispielen wird jedoch in allen Fällen Nickel eingesetzt. Ebenfalls werden in den Patentbeispielen Nitrate und Salpetersäure verwendet, auch wenn in der Beschreibung von der Anwesenheit von Nitrat in größeren Mengen abgeraten wird.The use of hydroxylamine and / or its compounds to influence The shape of the phosphate crystals is from a number of published publications known. EP-A-315 059 gives the as a special effect Use of hydroxylamine in phosphating baths indicates the fact that Steel then still the phosphate crystals in a desired column or tuberous form arise when the zinc concentration in the phosphating bath exceeds the range customary for low-zinc processes. This makes it possible to use phosphate baths with zinc concentrations up to 2 g / l and with weight ratios of phosphate to zinc down to 3.7 to operate. About advantageous cation combinations of these phosphating baths no further statements are made in the patent examples however, nickel is used in all cases. Also in the Patent examples nitrates and nitric acid used, even if in the Description of the presence of nitrate in large quantities is discouraged becomes.
EP-A-321 059 lehrt Zink-Phosphatierbäder, die neben 0,1 bis 2,0 g/l Zink und einem Beschleuniger außerdem 0,01 bis 20 g/l Wolfram in Form einer löslichen Wolframverbindung, vorzugsweise Alkalimetall- oder Ammoniumwolframat oder -silicowolframat, Erdalkalimetallsilicowolframat oder Boro- oder Silicowolframsäure. Der Beschleuniger ist ausgewählt aus Nitrit, m-Nitrobenzolsulfonat oder Wasserstoffperoxid. Als fakultative Bestandteile werden unter anderem Nickel in Mengen von 0,1 - 4 g/l und Nitrat in Mengen von 0,1 - 15 g/l angegeben. EP-A-321 059 teaches zinc phosphating baths which contain 0.1 to 2.0 g / l zinc and an accelerator also 0.01 to 20 g / l tungsten in the form of a soluble tungsten compound, preferably alkali metal or ammonium tungstate or silicotungstate, alkaline earth metal silicotungstate or boro- or silicotungstic acid. The accelerator is selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide. As optional components Among other things, nickel in quantities of 0.1 - 4 g / l and nitrate in quantities 0.1 - 15 g / l.
DE-C-27 39 006 beschreibt ein Phosphatierverfahren für Oberflächen aus Zink oder Zinklegierungen, das frei von Nitrat und Ammoniumionen ist. Neben einem essentiellen Gehalt an Zink in Mengen zwischen 0,1 und 5 g/l sind 1 bis 10 Gewichtsteile Nickel und/oder Kobalt pro Gewichtsteil Zink erforderlich. Als Beschleuniger wird Wasserstoffperoxid verwendet. Aus der Sicht der Arbeitsplatzhygiene und des Umweltschutzes stellt Kobalt keine Alternative zu Nickel dar.DE-C-27 39 006 describes a phosphating process for surfaces Zinc or zinc alloys that are free of nitrate and ammonium ions. Next an essential content of zinc in amounts between 0.1 and 5 g / l are 1 to 10 parts by weight of nickel and / or cobalt per part by weight of zinc required. Hydrogen peroxide is used as an accelerator. From the From the point of view of workplace hygiene and environmental protection, cobalt is not one Alternative to nickel.
Die Erfindung stellt sich die Aufgabe, Phosphatierbäder zur Verfügung zu stellen, die frei sind von dem aus Umwelt- und arbeitsplatzhygienischen Gründen bedenklichen Nickel oder dem ähnlich bedenklichen Kobalt, kein Nitrit enthalten und gleichzeitig einen stark verminderten Nitratgehalt aufweisen und vorzugsweise frei sind von Nitrat. Desweiteren sollen die Phosphatierbäder frei von Kupfer sein, dessen Dosierung im laut DE-A-40 13 483 wirksamen Konzentrationsbereich von 1 - 30 ppm problematisch ist.The object of the invention is to provide phosphating baths positions that are free from environmental and workplace hygiene Reasonably questionable nickel or the similarly questionable cobalt, no Contain nitrite and at the same time a greatly reduced nitrate content have and are preferably free of nitrate. Furthermore, the Phosphating baths should be free of copper, the dosage of which according to DE-A-40 13 483 effective concentration range of 1 - 30 ppm is problematic.
Diese Aufgabe wird gelöst durch ein Verfahren zur Phosphatierung von Metalloberflächen
mit wäßrigen, sauren Phosphatierlösungen, die Zink-, Mangan-
und Phosphationen und als Beschleuniger Hydroxylamin oder eine Hydroxylaminverbindung
und/oder m-Nitrobenzosulfonsäure oder deren wassserlösliche
Salze enthalten, dadurch gekennzeichnet, daß man die Metalloberflächen
mit einer Phosphatierlösung in Berührung bringt, die frei von
Nickel, Kobalt, Kupfer, Nitrit und Oxo-Anionen von Halogenen
in dem Sinne ist, daß diese Elemente beziehungsweise Ionen dem Bad nicht bewußt
zugesetzt werden und die Nickelkonzentration unter 0,01 g/l liegt und die
Daß die Phosphatierbäder frei von Nickel, Kupfer, Nitrit und Oxo-Anionen von Halogenen sein sollen, bedeutet dabei, daß diese Elemente bzw. Ionen den Phosphatierbädern nicht bewußt zugesetzt werden. Es ist jedoch in der Praxis nicht auszuschließen, daß solche Bestandteile über das zu behandelnde Material, das Ansatzwasser oder die Umgebungsluft in Spuren in die Phosphatierbäder eingetragen werden. Insbesondere ist es nicht auszuschließen, daß bei der Phosphatierung von mit Zink-Nickel-Legierungen beschichtetem Stahl Nickelionen in die Phosphatierlösung eingetragen werden. Jedoch wird an die erfindungsgemäßen Phosphatierbäder die Erwartung gestellt, daß unter technischen Bedingungen die Nickelkonzentration in den Bädern unter 0,01 g/l, insbesondere unter 0,0001 g/l liegt. Vorzugsweise wird den Bädern kein Nitrat zugesetzt. Es ist jedoch nicht auszuschließen, daß die Bäder den Nitratgehalt des lokal verfügbaren Trinkwassers (gemäß Trinkwasserverordnung in Deutschland maximal 50 mg/l) oder durch Verdunstung bedingte höhere Nitratgehalte aufweisen. Die erfindungsgemäßen Bäder sollen jedoch einen maximalen Nitratgehalt von 0,5 g/l aufweisen und enthalten vorzugsweise weniger als 0,1 g/l Nitrat.That the phosphating baths are free of nickel, copper, nitrite and oxo anions Halogens mean that these elements or ions not deliberately added to the phosphating baths. However, it is in the Practice does not rule out that such components are beyond what is to be treated Material, the preparation water or the ambient air in traces in the Phosphating baths are entered. In particular, it cannot be ruled out that in the phosphating of coated with zinc-nickel alloys Steel nickel ions are introduced into the phosphating solution. However, the expectation is placed on the phosphating baths according to the invention that that under technical conditions the nickel concentration in the Baths is below 0.01 g / l, in particular below 0.0001 g / l. Preferably no nitrate is added to the baths. However, it cannot be ruled out that the baths contain the nitrate content of the locally available drinking water (according to Drinking water regulation in Germany maximum 50 mg / l) or by evaporation have higher nitrate levels due to The invention However, baths should have a maximum nitrate content of 0.5 g / l and preferably contain less than 0.1 g / l nitrate.
Hydroxylamin kann als freie Base, als Hydroxylaminkomplex oder in Form von Hydroxylammoniumsalzen eingesetzt werden. Fügt man freies Hydroxylamin dem Phosphatierbad oder einem Phosphatierbad-Konzentrat zu, wird es aufgrund des sauren Charkters dieser Lösungen weitgehend als Hydroxylammonium-Kation vorliegen. Bei einer Verwendung als Hydroxylammonium-Salz sind die Sulfate sowie die Phosphate besonders geeignet. Im Falle der Phosphate sind aufgrund der besseren Löslichkeit die sauren Salze bevorzugt. Hydroxylamin oder seine Verbindungen werden dem Phosphatierbad in solchen Mengen zugesetzt, daß die rechnerische Konzentration des freien Hydroxylamins zwischen 0,1 und 5 g/l, insbesondere zwischen 0,4 und 2 g/l liegt. Es hat sich als günstig erwiesen, die Hydroxylaminkonzentration so zu wählen, daß das Verhältnis der Summe der Konzentrationen von Zink und Mangan zur Konzentration des Hydroxylamins, jeweils in g/l, 1,0 bis 6,0, vorzugsweise 2,0 bis 4,0 beträgt.Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of Hydroxylammonium salts are used. If you add free hydroxylamine Phosphating bath or a phosphating bath concentrate too, it is due of the acidic character of these solutions largely as a hydroxylammonium cation available. When used as a hydroxylammonium salt Sulfates and the phosphates are particularly suitable. In the case of the phosphates the acidic salts are preferred because of their better solubility. Hydroxylamine or its compounds in the phosphating bath in such Amounts added that the calculated concentration of free hydroxylamine is between 0.1 and 5 g / l, in particular between 0.4 and 2 g / l. It has proven to be beneficial to choose the hydroxylamine concentration so that the ratio of the sum of the concentrations of zinc and manganese for the concentration of the hydroxylamine, in each case in g / l, 1.0 to 6.0, preferably Is 2.0 to 4.0.
Ähnlich wie in der EP-A-321 059 beschrieben bringt auch in den erfindungsgemäßen, Hydroxylamin oder Hydroxylaminverbindungen enthaltenden Phosphatierbädern die Gegenwart löslicher Verbindungen des sechswertigen Wolframs Vorteile hinsichtlich Korrosionswiderstand und Lackhaftung, obwohl bei den erfindungsgemäßen Phosphatierverfahren, im Gegensatz zur Lehre der EP-A-321 059, auf die Beschleuniger Nitrit oder Wasserstoffperoxid verzichtet werden kann. In den erfindungsgemäßen Phosphatierverfahren können Phosphatierlösungen Verwendung finden, die zusätzlich 20 bis 800 mg/l, vorzugsweise 50 bis 600 mg/l Wolfram in Form wasserlöslicher Wolframate, Silicowolframate und/oder Borowolframate enthalten. Dabei können die genannten Anionen in Form ihrer Säuren und/ oder ihrer Ammonium-, Alkalimetall- und/oder Erdalkalimetallsalze eingesetzt werden.Similar to that described in EP-A-321 059, the inventive Phosphating baths containing hydroxylamine or hydroxylamine compounds the presence of soluble compounds of hexavalent tungsten Advantages in terms of corrosion resistance and paint adhesion, although with the Phosphating method according to the invention, in contrast to the teaching of EP-A-321 059, without the accelerators nitrite or hydrogen peroxide can be. In the phosphating process according to the invention Phosphating solutions are used that additionally 20 to 800 mg / l, preferably 50 to 600 mg / l tungsten in the form of water-soluble tungstates, Silicotungstates and / or borotungstates contain. The mentioned anions in the form of their acids and / or their ammonium, Alkali metal and / or alkaline earth metal salts are used.
m-Nitrobenzolsulfonat kann als freie Säure oder in Form wasserlöslicher Salze eingesetzt werden. Als "wasserlöslich" werden hierbei solche Salze bezeichnet, die sich in den Phosphatierbädern soweit auflösen, daß die erforderlichen Konzentrationen von 0,2 bis 2 g/l m-Nitrobenzolsulfonat erreicht werden. Hierfür kommen besonders die Alkalimetallsalze, vorzugsweise die Natriumsalze, in Betracht. Bevorzugterweise enthalten die Phosphatierbäder 0,4 bis 1 g/l m-Nitrobenzolsulfonat.m-Nitrobenzenesulfonate can be used as a free acid or in the form of water-soluble Salts are used. Such salts become "water-soluble" referred to, which dissolve in the phosphating baths so far that the required concentrations of 0.2 to 2 g / l m-nitrobenzenesulfonate can be achieved. The alkali metal salts are particularly suitable for this the sodium salts. The phosphating baths preferably contain 0.4 to 1 g / l m-nitrobenzenesulfonate.
Ein Verhältnis von 1 : 10 bis 10 : 1 zwischen dem eher reduktiv wirkenden Hydroxylamin und dem eher oxidativ wirkenden m-Nitrobenzolsulfonat kann zu besonderen Vorteilen hinsichtlich Schichtausbildung führen, insbesondere hinsichtlich der Form der gebildeten Kristalle. Es ist jedoch auch möglich und zur vereinfachten Badsteuerung vorzuziehen, daß die Phosphatierbäder entweder Hydroxylamin oder m-Nitrobenzolsulfonsäure enthalten.A ratio of 1:10 to 10: 1 between the more reductive Hydroxylamine and the more oxidative m-nitrobenzenesulfonate can lead to special advantages with regard to layer formation, in particular regarding the shape of the crystals formed. However, it is also possible and preferred for simplified bath control that the phosphating baths contain either hydroxylamine or m-nitrobenzenesulfonic acid.
Bei Phosphatierbädern, die für unterschiedliche Substrate geeignet sein sollen, ist es üblich, freies und/oder komplexgebundenes Fluorid in Mengen bis zu 2,5 g/l Gesamtfluorid, davon bis zu 800 mg/l freies Fluorid zuzusetzen. Die Anwesenheit solcher Fluoridmengen ist auch für die erfindungsgemäßen Phosphatierbäder von Vorteil. Bei Abwesenheit von Fluorid soll der Aluminiumgehalt des Bades 3 mg/l nicht überschreiten. Bei Gegenwart von Fluorid werden infolge der Komplexbildung höhere Al-Gehalte toleriert, sofern die Konzentration des nicht komplexierten Al 3 mg/l nicht übersteigt.For phosphating baths that are suitable for different substrates it is common to use free and / or complex-bound fluoride in quantities up to 2.5 g / l total fluoride, of which up to 800 mg / l free fluoride. The presence of such amounts of fluoride is also for those of the invention Phosphating baths are an advantage. In the absence of fluoride, the The aluminum content of the bath should not exceed 3 mg / l. In the presence of Due to the complex formation, fluoride, higher Al contents are tolerated, provided the concentration of the non-complexed Al does not exceed 3 mg / l.
Das Gewichtsverhältnis Phosphationen zu Zinkionen in den Phosphatierbädern kann in weiten Grenzen schwanken, sofern es im Bereich zwischen 3,7 und 30 liegt. Ein Gewichtsverhältnis zwischen 10 und 20 ist besonders bevorzugt. Als weitere Parameter zur Steuerung von Phosphatierbädern sind dem Fachmann die Gehalte an freier Säure und an Gesamtsäure bekannt. Die in dieser Schrift verwendete Bestimmungsmethode dieser Parameter ist im Beispielteil angegeben. Werte der freien Säure zwischen 0,3 und 1,5 Punkten bei Teilephosphatierung, bei Bandphosphatierung bis zu 2,5 Punkten und der Gesamtsäure zwischen etwa 15 und etwa 25 Punkten liegen im technisch üblichen Bereich und sind im Rahmen dieser Erfindung geeignet.The weight ratio of phosphate ions to zinc ions in the phosphating baths can fluctuate within wide limits, provided it is in the range between 3.7 and 30 lies. A weight ratio between 10 and 20 is particularly preferred. Those skilled in the art are further parameters for controlling phosphating baths the free acid and total acid contents are known. The one in this Font used determination method of this parameter is in the example part specified. Free acid values between 0.3 and 1.5 points for partial phosphating, with band phosphating up to 2.5 points and the total acidity between about 15 and about 25 points are in the usual technical range Range and are suitable in the context of this invention.
Der Mangangehalt des Phosphatierbades soll zwischen 0,3 und 4 g/l liegen, da bei geringeren Mangangehalten der positive Einfluß auf das Korrosionsverhalten der Phosphatschichten nicht mehr gegeben ist und bei höheren Mangangehalten kein weiterer positiver Effekt eintritt. Gehalte zwischen 0,3 und 2 g/l und insbesondere zwischen 0,5 und 1,5 g/l sind bevorzugt. Den Zinkgehalt stellt man bei Phosphatierbäder, die als Beschleuniger nur Hydroxylamin enthalten, gemäß EP-A-315 059 vorzugsweise auf Werte zwischen 0,45 und 1,1 g/l, bei Phosphatierbäder, die als Beschleuniger nur m-Nitrobenzolsulfonat enthalten, vorzugsweise auf Werte zwischen 0,6 und 1,4 g/l ein. Infolge des Beizabtrages bei der Phosphatierung zinkhaltiger Oberflächen ist es jedoch möglich, daß der aktuelle Zinkgehalt des arbeitenden Bades auf bis zu 2 g/l ansteigt. Dabei ist darauf zu achten, daß der Mangangehalt mindestens 50 % des Zinkgehaltes beträgt, da anderenfalls unzureichende Korrosionsschutzeigenschaften resultieren. In welcher Form die Zink- und Mangan ionen in die Phosphatierbäder eingebracht werden, ist prinzipiell ohne Belang. Um den erfindungsgemäßen Bedingungen zu genügen, sind jedoch die Nitrite, Nitrate, sowie Salze mit Oxo-Anionen von Halogenen dieser Kationen nicht einsetzbar. Es bietet sich insbesondere an, als Zink- und/oder Manganquelle die Oxide und/ oder die Karbonate zu verwenden. Außer den genannten zweiwertigen Kationen enthalten Phosphatierbäder üblicherweise Natrium-, Kalium- und/oder Ammoniumionen, die zum Einstellen der Parameter freie Säure und Gesamtsäure herangezogen werden. Ammoniumionen können auch durch Abbau des Hydroxylamins gebildet werden.The manganese content of the phosphating bath should be between 0.3 and 4 g / l, since the lower the manganese content, the positive influence on the corrosion behavior the phosphate layers no longer exist and at higher ones Manganese content no further positive effect occurs. Keep between 0.3 and 2 g / l and in particular between 0.5 and 1.5 g / l are preferred. The zinc content is set in phosphating baths, which only act as accelerators Contain hydroxylamine, according to EP-A-315 059 preferably to values between 0.45 and 1.1 g / l, for phosphating baths, which only accelerate m-nitrobenzenesulfonate contain, preferably to values between 0.6 and 1.4 g / l a. As a result of the pickling removal in the phosphating of zinc-containing surfaces However, it is possible that the current zinc content of the worker Bath increases up to 2 g / l. It is important to ensure that the manganese content is at least 50% of the zinc content, otherwise it is insufficient Corrosion protection properties result. In what form the Zinc and manganese ions are introduced into the phosphating baths basically irrelevant. In order to meet the conditions according to the invention, however, are the nitrites, nitrates, and salts with oxo anions of halogens these cations cannot be used. It is particularly useful as Zinc and / or manganese source to use the oxides and / or carbonates. In addition to the divalent cations mentioned, they contain phosphating baths usually sodium, potassium and / or ammonium ions to adjust the parameters free acid and total acid are used. Ammonium ions can also be formed by degradation of the hydroxylamine.
Bei der Anwendung des Phosphatierverfahrens auf Stahloberflächen geht Eisen in Form von Eisen(II)-Ionen in Lösung. Da die erfindungsgemäßen Phosphatierbäder keine Substanzen enthalten, die gegenüber Eisen(II) stark oxidierend wirken, geht das zweiwertige Eisen vornehmlich in Folge von Luftoxidation in den dreiwertigen Zustand über, so daß es als Eisen(III)-Phosphat ausfallen kann. Daher können sich in den erfindungsgemäßen Phosphatierbädern Eisen(II)-Gehalte aufbauen, die deutlich über den Gehalten liegen, die Oxidationsmittel-haltige Bäder enthalten. In diesem Sinne sind Eisen(II)-Konzentrationen bis zu 50 ppm normal, wobei kurzfristig im Produktionsablauf auch Werte bis zu 500 ppm auftreten können. Für das erfindungsgemäße Phosphatierverfahren sind solche Eisen(II)-Konzentrationen nicht schädlich. Bei Ansatz in hartem Wasser können die Phosphatierbäder weiterhin die Härtebildner-Kationen Mg(II) und Ca(II) in einer Gesamtkonzentration von bis zu 7 mmol/l enthalten.When using the phosphating process on steel surfaces, iron goes in the form of iron (II) ions in solution. Since the phosphating baths according to the invention do not contain substances that are strong compared to iron (II) have an oxidizing effect, the divalent iron mainly goes off in succession Air oxidation into the trivalent state, so that it is called ferric phosphate can fail. Therefore, in the phosphating baths according to the invention Build up iron (II) levels that are well above the levels which contain baths containing oxidizing agents. With that in mind Iron (II) concentrations up to 50 ppm normal, with short-term in the production process Values up to 500 ppm can also occur. For the invention Phosphating processes are such iron (II) concentrations not harmful. The phosphating baths can be used in hard water also the hardness cations Mg (II) and Ca (II) in a total concentration up to 7 mmol / l.
Das erfindungsgemäße Verfahren ist geeignet zur Phosphatierung von Oberflächen aus Stahl, verzinktem oder legierungsverzinktem Stahl, Aluminium, aluminiertem oder legierungsaluminiertem Stahl. Hydroxylaminhaltige Bäder sind insbesondere konzipiert zur Behandlung von ein- oder beidseitig verzinktem, vorzugsweise elektrolytisch verzinktem Stahl.The method according to the invention is suitable for phosphating surfaces made of steel, galvanized or alloy galvanized steel, aluminum, aluminized or alloy aluminized steel. Baths containing hydroxylamine are especially designed for the treatment of galvanized on one or both sides, preferably electrolytically galvanized steel.
Die genannten Materialien können - wie es im Automobilbau zunehmend üblich wird - auch nebeneinander vorliegen. Das Verfahren ist für die Anwendung im Tauch-, Spritz- oder Spritz/Tauchverfahren geeignet. Es kann insbesondere im Automobilbau eingesetzt werden, wo Behandlungszeiten zwischen 1 und 8 Minuten üblich sind. Der Einsatz bei der Bandphosphatierung im Stahlwerk, wobei die Behandlungszeiten zwischen 5 und 12 Sekunden liegen, ist jedoch ebenfalls möglich. Wie bei anderen Phosphatierbädern des Standes der Technik ebenfalls üblich, liegen die geeigneten Badtemperaturen zwischen 30 und 70 °C, wobei der Temperaturbereich zwischen 40 und 60 °C bevorzugt wird.The materials mentioned can - as is increasingly common in automotive engineering will also exist side by side. The procedure is for the application suitable in immersion, spray or spray / immersion processes. It can be used in particular in the automotive industry, where treatment times between 1 and 8 minutes are common. Use in tape phosphating in the steel mill, with treatment times between 5 and 12 seconds, is also possible. As with other phosphating baths of the Suitable bath temperatures are also common in the prior art between 30 and 70 ° C, the temperature range between 40 and 60 ° C is preferred.
Das erfindungsgemäße Phosphatierverfahren ist zur Erzeugung einer Gleitschicht für Umformungen und insbesondere zur Behandlung der genannten Metalloberflächen vor einer Lackierung, beispielsweise vor einer kathodischen Elektrotauchlackierung gedacht, wie sie im Automobilbau üblich ist. Das Phosphatierverfahren ist als Teilschritt der technisch üblichen Vorbehandlungskette zu sehen. In dieser Kette sind der Phosphatierung üblicherweise die Schritte Reinigen/Entfetten, Zwischenspülen und Aktivieren vorgeschaltet, wobei die Aktivierung üblicherweise mit Titanphosphat-haltigen Aktiviermitteln erfolgt. Der erfindungsgemäßen Phosphatierung kann, gegebenenfalls nach einer Zwischenspülung, eine passivierende Nachbehandlung folgen. Für eine solche passivierende Nachbehandlung sind Chromsäure-haltige Behandlungsbäder weit verbreitet. Aus Gründen des Arbeits- und Umweltschutzes sowie aus Entsorgungsgründen besteht jedoch die Tendenz, diese chromhaltigen Passivierbäder durch chromfreie Behandlungsbäder zu ersetzen. Hierfür sind rein anorganische Badlösungen, insbesondere auf der Basis von Zirkonverbindungen, oder auch organisch-reaktive Badlösungen, beispielsweise auf Basis von Polyvinylphenolen, bekannt. Zwischen dieser Nachpassivierung und der sich üblicherweise anschließenden Elektrotauchlackierung wird in der Regel eine Zwischenspülung mit vollentsalztem Wasser durchgeführt. The phosphating process according to the invention is used to produce a sliding layer for forming and in particular for treating the metal surfaces mentioned before painting, for example before a cathodic one Electro-dip coating thought as it is common in automotive engineering. The phosphating process is part of the technically usual pretreatment chain to see. In this chain, phosphating is common the steps cleaning / degreasing, rinsing and activating upstream, the activation usually with titanium phosphate-containing Activating agents are carried out. The phosphating according to the invention can if necessary after an intermediate rinse, a passivating after-treatment consequences. Chromic acid-containing ones are used for such a passivating aftertreatment Treatment baths widely used. For the sake of work and Environmental protection and disposal reasons, however, there is a tendency these chromium-containing passivation baths through chrome-free treatment baths replace. For this purely inorganic bath solutions, especially on the Basis of zirconium compounds, or also organic reactive bath solutions, for example based on polyvinylphenols. Between this Post passivation and the usually subsequent electro dip painting is usually an intermediate rinse with deionized water carried out.
Die erfindungsgemäßen Phosphatierverfahren unter Verwendung von Hydroxylaminverbindungen
sowie Vergleichsverfahren wurden an Stahlblechen (St
1405) und an beidseitig elektrolytisch verzinkten Stahlblechen (ZE), wie
sie im Automobilbau Verwendung finden, überprüft. Dabei wurde folgender in
der Karosseriefertigung gebräuchlicher Verfahrensgang (im Tauch- bzw.
Spritzverfahren) ausgeführt:
Unter der Punktzahl der freien Säure wird der Verbrauch in ml an 0,1-normaler Natronlauge verstanden, um 10 ml Badlösung bis zu einem pH-Wert von 3,6 zu titrieren. Analog gibt die Punktzahl der Gesamtsäure den Verbrauch in ml bis zu einem pH-Wert von 8,2 an.
The free acid score is understood to mean the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution up to a pH of 3.6. Similarly, the total acid score indicates consumption in ml up to a pH of 8.2.
Die flächenbezogene Masse ("Schichtgewicht") wurde durch Ablösen in 5
%-iger Chromsäurelösung bestimmt gemäß DIN 50942, Tabelle 6. Korrosionprüfungen
erfolgten nach dem VDA-Wechselklimatest 621-415 mit KTL-Grundierung
(KTL-hellgrau der Firma BASF, FT 85-7042); teilweise auch mit einem kompletten
Lackaufbau (Decklack: alpinweiß, VW). Bewertet wurden nach jeweils
10 einwöchigen Prüfzyklen die Lackunterwanderung (mm) gemäß DIN 53167 und
die Steinschlag-Kennwerte nach VW-Prüfvorschrift (K-Werte: bester Wert K =
1, schlechtester Wert K = 10). Die Ergebnisse sind in Tabelle 2 enthalten.
(Materialien und Definition von freier Säure und Gesamtsäure wie Beispiele 1 bis 7).(Materials and definition of free acid and total acid as examples 1 to 7).
Schichtgewichte wurden durch Ablösen in 5 %-iger Chromsäurelösung bestimmt.
Korrosionprüfungen erfolgten nach dem VDA-Wechselklimatest 621-415
sowohl nur mit KTL-Grundierung (ED 12 MB der Firma PPG) als auch mit einem
kompletten Lackaufbau (KTL wie vorstehend, Füller: 1-Komponenten Highsolid
PU-Füller grau, Decklack: DB 744 metallic Basecoat und Clearcoat).
Bewertet wurde nach jeweils 10 einwöchigen Prüfzyklen die Lackunterwanderung
(mm). Weiterhin erfolgte eine Kugelstoßprüfung nach Mercedes-Benz
Norm analog DIN 53 230 (6 bar entsprechend 250 km/h), Auswertung bei Substrattemperatur
-20 °C. Bewertet wurde die Schadensfläche in mm2 (Mercedes-Benz
Norm: max. 5) und der Rostgrad (bester Wert = 0, schlechtester
Wert = 5, Mercedes-Benz Norm: max. 2). Die Ergebnisse sind in Tabelle 4
enthalten.
Die erfindungsgemäßen Phosphatierverfahren unter Verwendung von m-Nitrobenzolsulfonat
sowie Vergleichsverfahren wurden an Stahlblechen und an
beidseitig elektrolytisch verzinkten Stahlblechen (ZE), wie sie im Automobilbau
Verwendung finden, überprüft. Dabei wurde folgender in der Karosseriefertigung
gebräuchlicher Verfahrensgang im Tauchverfahren ausgeführt:
Unter der Punktzahl der freien Säure wird der Verbrauch in ml an 0,1-normaler Natronlauge verstanden, um 10 ml Badlösung bis zu einem pH-Wert von 3,6 zu titrieren. Analog gibt die Punktzahl der Gesamtsäure den Verbrauch in ml bis zu einem pH-Wert von 8,5 an.
The free acid score is understood to mean the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution up to a pH of 3.6. Similarly, the total acid score indicates consumption in ml up to a pH of 8.5.
Die flächenbezogene Masse ("Schichtgewicht") wurde durch Ablösen in 5
%-iger Chromsäurelösung bestimmt gemäß DIN 50942. Korrosionprüfungen erfolgten
nach dem VDA-Wechselklimatest 621-415 mit KTL-Grundierung (KTL-hellgrau
der Firma BASF, FT 85-7042). Bewertet wurden nach jeweils 10 einwöchigen
Prüfzyklen die Lackunterwanderung (mm) gemäß DIN 53167 und die
Steinschlag-Kennwerte nach VW-Prüfvorschrift VW-P3.17.1 (K-Werte: bester
Wert K = 1, schlechtester Wert K = 10). Die Ergebnisse sind in Tabelle 5
enthalten.
Claims (16)
- A process for phosphating metal surfaces with aqueous acidic phosphating solutions containing zinc, manganese and phosphate ions and, as accelerator, hydroxylamine or a hydroxylamine compound and/or m-nitrobenzenesulfonic acid or water-soluble salts thereof, characterized in that the metal surfaces are contacted with a phosphating solution which is free from nickel, cobalt, copper, nitrite and oxo-anions of halogens in a sense that these elements or ions are not purposely added to the bath and that the nickel concentration is below 0,01 g/l and which contains 0.3 to 2 g/l of Zn(II), 0.3 to 4 g/l of Mn(II), 5 to 40 g/l of phosphate ions, 0.1 to 5 g/l of hydroxylamine in free or complexed form and/or 0.2 to 2 g/l of m-nitrobenzenesulfonate and at most 0.5 g/l of nitrate ions, the Mn content amounting to at least 50% of the Zn content.
- A process as claimed in claim 1, characterized in that the phosphating solution contains less than 0.1 g/l of nitrate.
- A process as claimed in one or both of claims 1 and 2, characterized in that the phosphating solution additionally contains fluoride in free and/or complexed form in quantities of up to 2.5 g of total fluoride/l, including up to 800 mg of free fluoride/l.
- A process as claimed in one or more of claims 1 to 3, characterized in that the phosphating solution has a ratio by weight of phosphate ions to zinc ions of 3.7 to 30:1 and preferably 10 to 20:1.
- A process as claimed in one or more of claims 1 to 4, characterized in that the phosphating solution has an Mn(II) content of 0.3 to 2 g/l and preferably 0.5 to 1.5 g/l.
- A process as claimed in one or more of claims 1 to 5, characterized in that the phosphating solution contains m-nitrobenzenesulfonate in the form of the free acid or a water-soluble salt, more especially the sodium salt, and the concentration of m-nitrobenzenesulfonate is preferably 0.4 to 1 g/l.
- A process as claimed in one or more of claims 1 to 6, characterized in that the total acid content is between 15 and 25 points while the free acid content is between 0.3 and 1.5 points in the phosphating of parts and between 0.3 and 2.5 points in coil phosphating.
- A process as claimed in one or more of claims 1 to 7, characterized in that the phosphating solution contains hydroxylamine in free or complexed form or in the form of its salts, more particularly in the form of its sulfates or phosphates.
- A process as claimed in claim 8, characterized in that the phosphating solution has a content of hydroxylamine in free form, in salt form or in complexed form of 0.4 to 2 g/l, expressed as hydroxylamine.
- A process as claimed in one or both of claims 8 and 9, characterized in that the ratio of the sum of the zinc and manganese concentrations to the hydroxylamine concentration in g/l is 1.0 to 6.0:1 and preferably 2.0 to 4.0:1.
- A process as claimed in one or more of claims 8 to 10, characterized in that the phosphating solution additionally contains 20 to 800 mg/l and preferably 50 to 600 mg/l of tungsten in the form of water-soluble tungstates, silicotungstates and/or borotungstates in the form of their acids and/or their ammonium, alkali metal and/or alkaline earth metal salts.
- A process as claimed in one or more of claims 1 to 11, characterized in that the phosphating solution contains either hydroxylamine or m-nitrobenzenesulfonic acid.
- A process as claimed in one or more of claims 1 to 12 for the treatment of surfaces of steel, galvanized or alloy-galvanized steel, aluminium, aluminized or alloy-aluminized steel.
- A process as claimed in claim 13, characterized in that the metal surface is contacted with the phosphating solution by spraying, dipping or spraying/dipping for treatment times of 5 seconds to 8 minutes.
- A process as claimed in claim 14, characterized in that the temperature of the phosphating solution is between 30 and 70°C.
- A process as claimed in claim 15 for the treatment of metal surfaces before lacquering, more particularly before cathodic electrocoating.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4330104 | 1993-09-06 | ||
| DE4330104A DE4330104A1 (en) | 1993-09-06 | 1993-09-06 | Nickel- and copper-free phosphating process |
| DE4341041 | 1993-12-02 | ||
| DE19934341041 DE4341041A1 (en) | 1993-12-02 | 1993-12-02 | Phosphating solns contg hydroxylamine and/or nitrobenzene sulphonate |
| PCT/EP1994/002848 WO1995007370A1 (en) | 1993-09-06 | 1994-08-29 | Nickel-free phosphatization process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0717787A1 EP0717787A1 (en) | 1996-06-26 |
| EP0717787B1 true EP0717787B1 (en) | 1998-01-14 |
Family
ID=25929280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94925483A Expired - Lifetime EP0717787B1 (en) | 1993-09-06 | 1994-08-29 | Nickel-free phosphatization process |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5792283A (en) |
| EP (1) | EP0717787B1 (en) |
| JP (1) | JP3348856B2 (en) |
| KR (1) | KR100327287B1 (en) |
| CN (1) | CN1041001C (en) |
| AT (1) | ATE162233T1 (en) |
| AU (1) | AU678284B2 (en) |
| BR (1) | BR9407485A (en) |
| CA (1) | CA2171180A1 (en) |
| CZ (1) | CZ286514B6 (en) |
| DE (1) | DE59405046D1 (en) |
| ES (1) | ES2111949T3 (en) |
| WO (1) | WO1995007370A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184444A (en) * | 2013-03-29 | 2013-07-03 | 柳州煜华科技有限公司 | Phosphating solution suitable for metal fastening piece |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5653790A (en) * | 1994-11-23 | 1997-08-05 | Ppg Industries, Inc. | Zinc phosphate tungsten-containing coating compositions using accelerators |
| DE19511573A1 (en) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Process for phosphating with metal-containing rinsing |
| DE19639596A1 (en) * | 1996-09-26 | 1998-04-02 | Henkel Kgaa | Process for phosphating steel strips |
| DE19756735A1 (en) * | 1997-12-19 | 1999-06-24 | Henkel Kgaa | Phosphating one-side galvanized steel strip on the galvanized side only |
| DE19808440C2 (en) | 1998-02-27 | 2000-08-24 | Metallgesellschaft Ag | Aqueous solution and method for phosphating metallic surfaces and use of the solution and method |
| DE19808755A1 (en) | 1998-03-02 | 1999-09-09 | Henkel Kgaa | Layer weight control for strip phosphating |
| DE19834796A1 (en) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Process for phosphating, rinsing and cathodic electrocoating |
| WO2000039357A1 (en) * | 1998-12-23 | 2000-07-06 | Henkel Corporation | Composition and process for heavy zinc phosphating |
| JP2001342575A (en) * | 2000-05-31 | 2001-12-14 | Nippon Dacro Shamrock Co Ltd | Aqueous metal surface treatment agent |
| DE10110833B4 (en) * | 2001-03-06 | 2005-03-24 | Chemetall Gmbh | Process for applying a phosphate coating and use of the thus phosphated metal parts |
| DE10155666A1 (en) * | 2001-11-13 | 2003-05-22 | Henkel Kgaa | Phosphating process accelerated with hydroxylamine and organic nitrogen compounds |
| KR100554740B1 (en) * | 2001-12-17 | 2006-02-24 | 주식회사 포스코 | A method for manufacturing a electro-galvanized steel sheet having the phosphated film formed thereon |
| BRPI0811201A2 (en) * | 2007-06-07 | 2014-10-29 | Henkel Ag & Co Kgaa | COMPOSITION OF LIQUID MATTER FOR THE FORMATION OF A PHOSPHATE CONVERSION COATING ON A METAL SUBSTRATE, PROCESS FOR THE PRODUCTION OF A PHOSPHATE CONVERSION COATING, AND, MANUFACTURING ARTICLE. |
| DE102010001686A1 (en) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Composition for the alkaline passivation of zinc surfaces |
| PL2503025T3 (en) | 2011-03-22 | 2013-12-31 | Henkel Ag & Co Kgaa | Multi-step corrosion-resistant treatment of metallic workpieces having at least partially zinc or zinc alloy surfaces |
| CN102703889B (en) * | 2012-05-28 | 2014-06-04 | 武汉永正科技发展有限公司 | Low-temperature single-component zinc series phosphating solution and preparation method thereof |
| CN104651820A (en) * | 2015-02-16 | 2015-05-27 | 天津大学 | Ultrasonic phosphating solution for carbon steel, preparation method thereof and method for phosphating carbon steel by adopting phosphating solution |
| KR102689368B1 (en) * | 2015-04-07 | 2024-07-30 | 케메탈 게엠베하 | How to specifically adjust the electrical conductivity of a conversion coating |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5339945A (en) * | 1976-09-25 | 1978-04-12 | Nippon Packaging Kk | Surface treatment of zinc or zinc alloy |
| GB2072225B (en) * | 1980-03-21 | 1983-11-02 | Pyrene Chemical Services Ltd | Process and composition for coating metal surfaces |
| JPS57152472A (en) * | 1981-03-16 | 1982-09-20 | Nippon Paint Co Ltd | Phosphating method for metallic surface for cation type electrodeposition painting |
| ES8606528A1 (en) * | 1985-02-22 | 1986-04-01 | Henkel Iberica | Process for the phosphating of metal surfaces. |
| SG52645A1 (en) * | 1985-08-27 | 1998-09-28 | Henkel Corp | A process for phosphate-coating metal surfaces |
| US4865653A (en) * | 1987-10-30 | 1989-09-12 | Henkel Corporation | Zinc phosphate coating process |
| NL8703050A (en) * | 1987-12-16 | 1989-07-17 | Johannes Schuitemaker | FEEDER INPUT MECHANISM. |
| AU610313B2 (en) * | 1987-12-18 | 1991-05-16 | Nippon Paint Co., Ltd. | Process for phosphating metal surfaces |
| JP2636919B2 (en) * | 1989-01-26 | 1997-08-06 | 日本パーカライジング株式会社 | Lubrication treatment method for cold plastic working of steel |
| US5232523A (en) * | 1989-03-02 | 1993-08-03 | Nippon Paint Co., Ltd. | Phosphate coatings for metal surfaces |
| DE3913089A1 (en) * | 1989-04-21 | 1990-10-25 | Henkel Kgaa | CHLORATE- AND NITRITE-FREE METHOD FOR THE PRODUCTION OF NICKEL- AND MANGANE-CONTAINING ZINC PHOSPHATE LAYERS |
| JPH0696773B2 (en) * | 1989-06-15 | 1994-11-30 | 日本ペイント株式会社 | Method for forming zinc phosphate film on metal surface |
| DE3920296A1 (en) * | 1989-06-21 | 1991-01-10 | Henkel Kgaa | METHOD FOR PRODUCING ZINC PHOSPHATE CONTAINING MANGANE AND MAGNESIUM |
| US5268041A (en) * | 1990-04-27 | 1993-12-07 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
| DE4013483A1 (en) * | 1990-04-27 | 1991-10-31 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METAL SURFACES |
| DE4210513A1 (en) * | 1992-03-31 | 1993-10-07 | Henkel Kgaa | Nickel-free phosphating process |
-
1994
- 1994-08-29 CN CN94193230A patent/CN1041001C/en not_active Expired - Fee Related
- 1994-08-29 CZ CZ1996673A patent/CZ286514B6/en not_active IP Right Cessation
- 1994-08-29 DE DE59405046T patent/DE59405046D1/en not_active Expired - Lifetime
- 1994-08-29 AT AT94925483T patent/ATE162233T1/en not_active IP Right Cessation
- 1994-08-29 ES ES94925483T patent/ES2111949T3/en not_active Expired - Lifetime
- 1994-08-29 JP JP50842695A patent/JP3348856B2/en not_active Expired - Fee Related
- 1994-08-29 CA CA002171180A patent/CA2171180A1/en not_active Abandoned
- 1994-08-29 KR KR1019960701115A patent/KR100327287B1/en not_active IP Right Cessation
- 1994-08-29 US US08/612,925 patent/US5792283A/en not_active Expired - Lifetime
- 1994-08-29 BR BR9407485A patent/BR9407485A/en not_active IP Right Cessation
- 1994-08-29 AU AU75373/94A patent/AU678284B2/en not_active Ceased
- 1994-08-29 WO PCT/EP1994/002848 patent/WO1995007370A1/en active IP Right Grant
- 1994-08-29 EP EP94925483A patent/EP0717787B1/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184444A (en) * | 2013-03-29 | 2013-07-03 | 柳州煜华科技有限公司 | Phosphating solution suitable for metal fastening piece |
| CN103184444B (en) * | 2013-03-29 | 2016-08-03 | 柳州煜华科技有限公司 | A kind of Phosphating Solution being applicable to metal fastenings |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960705076A (en) | 1996-10-09 |
| BR9407485A (en) | 1996-06-25 |
| JPH09502224A (en) | 1997-03-04 |
| CN1129961A (en) | 1996-08-28 |
| KR100327287B1 (en) | 2002-11-22 |
| WO1995007370A1 (en) | 1995-03-16 |
| US5792283A (en) | 1998-08-11 |
| CN1041001C (en) | 1998-12-02 |
| AU678284B2 (en) | 1997-05-22 |
| DE59405046D1 (en) | 1998-02-19 |
| CA2171180A1 (en) | 1995-03-16 |
| AU7537394A (en) | 1995-03-27 |
| CZ67396A3 (en) | 1996-12-11 |
| ATE162233T1 (en) | 1998-01-15 |
| EP0717787A1 (en) | 1996-06-26 |
| ES2111949T3 (en) | 1998-03-16 |
| CZ286514B6 (en) | 2000-05-17 |
| JP3348856B2 (en) | 2002-11-20 |
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