EP0717787A1 - Procede de phosphatage sans nickel - Google Patents
Procede de phosphatage sans nickelInfo
- Publication number
- EP0717787A1 EP0717787A1 EP94925483A EP94925483A EP0717787A1 EP 0717787 A1 EP0717787 A1 EP 0717787A1 EP 94925483 A EP94925483 A EP 94925483A EP 94925483 A EP94925483 A EP 94925483A EP 0717787 A1 EP0717787 A1 EP 0717787A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- hydroxylamine
- free
- phosphating solution
- steel
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 64
- 230000008569 process Effects 0.000 title claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 28
- 239000010959 steel Substances 0.000 claims abstract description 28
- 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 22
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-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
- 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 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
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 4
- 239000008397 galvanized steel Substances 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 35
- 229910052725 zinc Inorganic materials 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 28
- 229910002651 NO3 Inorganic materials 0.000 claims description 23
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 23
- 239000011572 manganese Substances 0.000 claims description 21
- -1 hydroxylamine compound Chemical class 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 235000021317 phosphate Nutrition 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000010422 painting Methods 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 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 3
- 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
- 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
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000003973 paint Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000013459 approach Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 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
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000009189 diving Effects 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
- 238000004519 manufacturing process Methods 0.000 description 4
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 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
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 150000002443 hydroxylamines Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 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
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYTCXRKBVWKEBW-UHFFFAOYSA-N 1-nitrocyclohexa-2,4-diene-1-sulfonic acid Chemical compound OS(=O)(=O)C1([N+]([O-])=O)CC=CC=C1 RYTCXRKBVWKEBW-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 239000002585 base Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change 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
- 239000000470 constituent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001627 detrimental effect Effects 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
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000009863 impact test Methods 0.000 description 1
- 150000002500 ions Chemical class 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
- 229910000399 iron(III) phosphate Inorganic materials 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 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
- MXFJRKYYYAKTIS-UHFFFAOYSA-N nitrobenzene;sulfuric acid Chemical compound OS(O)(=O)=O.[O-][N+](=O)C1=CC=CC=C1 MXFJRKYYYAKTIS-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 239000002244 precipitate 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
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 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
-
- 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 processes for phosphating metal surfaces with aqueous, acidic phosphating solutions which contain zinc, manganese and phosphate ions and hydroxyls in free or bound form and / or m-nitrobenzenesulfonic acid or its water-soluble salts, and their use as Pretreatment of the metal surfaces for a subsequent painting, especially an electro dip painting.
- the method can be used for the treatment of surfaces made of steel, galvanized or alloy-galvanized steel, aluminum, aluminized or alloy-aluminized steel, in particular for the treatment of steel that is galvanized on one or both sides, preferably electrolytically galvanized.
- the phosphating of metals pursues the goal of producing firmly adhered metal phosphate layers on the metal surface which already improve the corrosion resistance and, in conjunction with paints and other organic coatings, lead to a substantial increase in paint adhesion and resistance to infiltration when exposed to corrosion contribution.
- Such phosphating processes have long been known.
- An important parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the range> 8 and can take values up to 30.
- DE-A-3920296 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, in addition to 0.2 to 10 g / 1 nitrate ions, further oxidizing agents which act as accelerators, selected from nitrite, chlorate or an organic oxidizing agent.
- EP-A-60 716 discloses low-zinc phosphating baths which contain zinc and manganese as essential cations and which can contain nickel as an optional component.
- the necessary accelerator is preferably selected from nitrite, nitrobenzenesulfonate or hydrogen peroxide.
- the use of 1 to 10 g / 1 Ni ⁇ step is specified; all examples of the invention contain 4 g / 1 nitrate.
- EP-A-228 151 also describes phosphating baths which contain zinc and manganese as essential cations.
- the phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzene sulfate fonate, m-nitrobenzoate or p-nitrophenol.
- the nitrate content is specified at 5 to about 15 g / 1 and an optional nickel content between 0.4 and 4 g / 1.
- the main focus of this application is that chlorate-free phosphating processes are made available.
- EP-A-544650 teaches something similar.
- the phosphating process disclosed in WO 86/04931 works without nitrates.
- the accelerator system is based on a combination of 0.5 - 1 g / 1 bromate and 0.2 - 0.5 g / 1 m-nitrobenzenesulfonate.
- zinc is stated as the essential multivalent cation, nickel, manganese or cobalt as further optional cations.
- the phosphating solutions preferably contain 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 of chlorate in phosphating baths whose manganese content is 5-33% by weight. -% of the zinc content.
- W090 / 12901 discloses a chlorate- and nitrite-free process for the manufacture of nickel and manganese-containing zinc phosphate layers on steel, zinc and / or their alloys by spraying, splash-dipping and / or dipping with an aqueous solution containing 0.3 to 1.5 g / 1 zinc (II), 0.01 to 2.0 g / 1 manganese (II), 0.01 to 0.8 g / 1 iron (II), 0.3 to 2.0 g / 1 nickel (II ), 10.0 to 20.0 g / 1 phosphate ions, 2.0 to 10.0 g / 1 nitrate ions and
- aqueous solution having a free acid content of 0.5 to 1.8 points and a total acid content of 15 to 35 points and Na + is present in the amount necessary to adjust the free acid.
- organic oxidizing agent for example m-nitrobenzenesulfonate
- DE-A-40 13 483 discloses phosphating processes with which good corrosion protection properties are achieved as with the trication processes. that can. These methods dispense with nickel and use instead of copper in low concentrations, 0.001 to 0.03 g / l. Oxygen and / or other oxidizing agents having the same effect are used to oxidize the divalent iron formed in the pickling reaction of steel surfaces to the trivalent stage. Nitrite, chlorate, broat, peroxy compounds and organic nftro compounds such as nitrobenzenesulfonate are specified as such.
- German patent application with the file number P 42 10513.7 modifies this process by adding hydroxylamine, its salts or complexes in an amount of 0.5 to 5 g / 1 hydroxylamine as a modifying agent for the morphology of the phosphate crystals formed.
- EP-A-321 059 teaches zinc phosphating baths which, in addition to 0.1 to 2.0 g / 1 zinc and an accelerator, also 0.01 to 20 g / 1 tungsten in the form of a soluble tungsten compound, preferably alkali metal or ammonium tungstate or -s licotungstate, alkaline earth metal silicotungstate or boro- or silicotungstic acid.
- the accelerator is selected from nitrite, nitrobenzenesulfonate or hydrogen peroxide.
- Optional components include nickel in amounts of 0.1 - 4 g / 1 and nitrate in amounts of 0.1 - 15 g / 1.
- DE-C-27 39 006 describes a phosphating process for surfaces made of zinc or zinc alloys which is free of nitrate and ammonium ions.
- an essential zinc content in amounts between 0.1 and 5 g / 1, 1 to 10 parts by weight of nickel and / or cobalt are required per part by weight of zinc.
- Hydrogen peroxide is used as an accelerator. From the point of view of workplace hygiene and environmental protection, cobalt is not an alternative to nickel.
- the object of the invention is to provide phosphating baths which are free from nickel or the similarly harmful cobalt, which is harmful for environmental and workplace hygiene reasons, do not contain nitrite and at the same time have a greatly reduced nitrate content and are preferably free of nitrate. Furthermore, the phosphating baths should be free of copper, the metering of which is problematic in the effective concentration range of 1-30 ppm according to DE-A-40 13 483.
- This object is achieved by a process for phosphating metal surfaces with aqueous, acidic phosphating solutions, the zinc, manganese and phosphate ions and, as an accelerator, hydroxylamine or a hydroxylamine compound and / or m-nitrobenzosulfonic acid or its water-soluble salts contain, characterized in that the metal surfaces are brought into contact with a phosphating solution which is free of nickel, cobalt, copper, nitrite and oxo anions of halogens and which
- the phosphating baths should be free of nickel, copper, nitrite and oxo anions from halogens means that these elements or ions not deliberately added to the phosphating baths. In practice, however, it cannot be ruled out that such constituents may be traced into the phosphating baths via the material to be treated, the preparation water or the ambient air. In particular, it cannot be ruled out that during the phosphating of steel coated with zinc-nickel alloys, nickel ions are introduced into the phosphating solution.
- the phosphating baths according to the invention are subject to the expectation that under technical conditions the nickel concentration in the baths is below 0.01 g / 1, in particular below 0.0001 g / 1.
- the baths Preferably, no nitrate is added to the baths.
- the baths have the nitrate content of the locally available drinking water (according to the Drinking Water Ordinance in Germany a maximum of 50 mg / 1) or higher nitrate contents due to evaporation.
- the baths according to the invention should have a maximum nitrate content of 0.5 g / 1 and preferably contain less than 0.1 g / 1 nitrate.
- Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating bath or a phosphating bath concentrate, it will largely exist as a hydroxylammonium cation due to the acid character of these solutions. When used as a hydroxylammonium salt, the sulfates and the phosphates are particularly suitable. In the case of the phosphates, the acid salts are preferred due to the better solubility. Hydroxylamine or its compounds are added to the phosphating bath in amounts such that the calculated concentration of the free hydroxylamine is between 0.1 and 5 g / 1, in particular between 0.4 and 2 g / 1.
- hydroxylamine concentration such that the ratio of the sum of the concentrations of zinc and manganese to the concentration of the hydroxyla ins, in each case in g / l, 1.0 to 6.0, preferably 2 , Is 0 to 4.0.
- the presence of soluble compounds of hexavalent tungsten in the inventive phosphate baths containing hydroxylamine or hydroxylamine compounds also has advantages in terms of corrosion resistance and paint adhesion, although in the case of the In contrast to the teaching of EP-A-321 058, the phosphating process according to the invention, on which accelerators nitrite or hydrogen peroxide can be dispensed with.
- Phosphating solutions which additionally contain 20 to 800 mg / l, preferably 50 to 600 mg / l tungsten in the form of water-soluble tungstates, silicotungstates and / or borotungstates can be used in the phosphating processes according to the invention.
- the anions mentioned can be used in the form of their acids and / or their ammonium, alkali metal and / or alkaline earth metal salts.
- m-Nitrobenzenesulfonate can be used as free acid or in the form of water-soluble salts. Salts are referred to as "water-soluble” if they dissolve in the phosphating baths to such an extent that the required concentrations of 0.2 to 2 g / 1 m-nitrobenzenesulfonate are achieved.
- the alkali metal salts preferably the sodium salts, are particularly suitable for this.
- the phosphating baths preferably contain 0.4 to 1 g / 1 m-nitrobenzenesulfonate.
- a ratio of 1:10 to 10: 1 between the more reductive hydroxylamine and the more oxidative m-nitrobenzenesulfonate can lead to particular advantages with regard to layer formation, especially with regard to the shape of the crystals formed.
- the phosphating baths contain either hydroxylamine or m-nitrobenzenesulfonic acid.
- phosphating baths which are said to be suitable for different substrates, it is customary to add free and / or complex-bound fluoride in amounts of up to 2.5 g / 1 total fluoride, of which up to 800 mg / 1 free fluoride.
- the presence of such amounts of fluoride is also advantageous for the phosphating baths according to the invention.
- the aluminum content of the bath should not exceed 3 mg / 1.
- higher Al contents are tolerated as a result of the complex formation, provided the concentration of the non-complexed Al does not exceed 3 mg / l.
- the weight ratio of phosphate ions to zinc ions in the phosphating baths can vary within a wide range, provided it is in the range between 3.7 and 30 lies. A weight ratio between 10 and 20 is particularly preferred.
- the free acid and total acid contents are known to the person skilled in the art. The method of determining these parameters used in this document is given in the example section. Values of the free acid between 0.3 and 1.5 points in the case of partial phosphating, in the case of band phosphating up to 2.5 points and the total acid between about 15 and about 25 points are within the industrially customary range and are suitable for the purposes of this invention .
- the manganese content of the phosphating bath should be between 0.3 and 4 g / l, since with lower manganese contents the positive influence on the corrosion behavior of the phosphate layers is no longer given and with higher manganese contents there is no further positive effect. Contents between 0.3 and 2 g / 1 and in particular between 0.5 and 1.5 g / 1 are preferred.
- the zinc content is preferably set to values between 0.45 and 1.1 g / l according to EP-A-315059, and preferably in phosphating baths which contain only m-nitrobenzenesulfonate as accelerators to values between 0.6 and 1.4 g / 1.
- the current zinc content of the working bath rises to up to 2 g / l. Care must be taken to ensure that the mana content is at least 50% of the zinc content, since otherwise inadequate corrosion protection properties result.
- the form in which the zinc and manganese ions are introduced into the phosphating baths is in principle irrelevant. In order to meet the conditions according to the invention, however, the nitrites, nitrates and salts with oxo anions of halogens of these cations cannot be used. It is particularly useful to use the oxides and / or the carbonates as the zinc and / or manganese source.
- phosphating baths usually contain sodium, potassium and / or ammonium ions, which are used to set the free acid and total acid parameters. Ammonium ions can also be formed by degrading the hydroxylamine.
- iron in the form of iron (II) ions dissolves. Since the phosphating baths according to the invention contain no substances which are strong compared to iron (II) Having an oxidizing effect, the divalent iron changes to the trivalent state primarily as a result of air oxidation, so that it can precipitate out as iron (III) phosphate. Therefore, iron (II) contents can be built up in the phosphating baths according to the invention which are significantly higher than the contents which contain baths containing oxidizing agents. In this sense, iron (II) concentrations of up to 50 ppm are normal, although values of up to 500 ppm can also occur briefly in the production process.
- the phosphating baths may further contain the hardness-forming cations Mg (II) and Ca (II) in a total concentration of up to 7 mmol / l.
- the method according to the invention is suitable for phosphating surfaces made of steel, galvanized or galvanized alloy steel, aluminum, aluminized or alloy-aluminized steel.
- Baths containing hydroxylamine are especially designed for the treatment of steel that is galvanized on one or both sides, preferably electrolytically galvanized.
- the materials mentioned can - as is becoming increasingly common in automotive engineering - also exist side by side.
- the method is suitable for use in the immersion, spray or spray / immersion process. It can be used in particular in automobile construction, where treatment times between 1 and 8 minutes are common. However, use in strip phosphating in the steel mill, with treatment times between 5 and 12 seconds, is also possible.
- the suitable bath temperatures are between 30 and 70 ° C., the temperature range between 40 and 60 ° C. being preferred.
- the phosphating process according to the invention is intended for producing a sliding layer for forming and in particular for treating the metal surfaces mentioned before painting, for example before cathodic electrocoating, as is customary in automobile construction.
- the phosphating process is to be seen as a sub-step of the technically customary pretreatment chain. In this chain, the steps of cleaning / degreasing, rinsing and activating are usually the phosphating upstream, the activation usually being carried out with titanium phosphate-containing activating agents.
- the phosphating according to the invention can, if appropriate after an intermediate rinse, be followed by a passivating aftertreatment. Treatment baths containing chromic acid are widely used for such a passivating aftertreatment.
- 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. Analogously, the total acid score indicates consumption in ml up to a pH of 8.2.
- 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.
- the phosphating processes according to the invention using m-nitrobenzenesulfonate and comparative processes were checked on steel sheets and on steel sheets electrolytically galvanized on both sides (ZE), as are used in automobile construction.
- the following process step used in body production was carried out in the immersion process:
- 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.
- Example 9 Example 10
- Example 11 Example 12 Comp. 5 cf. 6 cf. 7 electrolytically galvanized Sheet steel
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Catalysts (AREA)
- Electroplating Methods And Accessories (AREA)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4330104 | 1993-09-06 | ||
| DE4330104A DE4330104A1 (de) | 1993-09-06 | 1993-09-06 | Nickel- und Kupfer-freies Phosphatierverfahren |
| DE19934341041 DE4341041A1 (de) | 1993-12-02 | 1993-12-02 | Nickelfreies Phosphatierverfahren mit m-Nitrobenzolsulfonat |
| DE4341041 | 1993-12-02 | ||
| PCT/EP1994/002848 WO1995007370A1 (fr) | 1993-09-06 | 1994-08-29 | Procedes de phosphatage sans nickel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0717787A1 true EP0717787A1 (fr) | 1996-06-26 |
| EP0717787B1 EP0717787B1 (fr) | 1998-01-14 |
Family
ID=25929280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94925483A Expired - Lifetime EP0717787B1 (fr) | 1993-09-06 | 1994-08-29 | Procede de phosphatage sans nickel |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5792283A (fr) |
| EP (1) | EP0717787B1 (fr) |
| JP (1) | JP3348856B2 (fr) |
| KR (1) | KR100327287B1 (fr) |
| CN (1) | CN1041001C (fr) |
| AT (1) | ATE162233T1 (fr) |
| AU (1) | AU678284B2 (fr) |
| BR (1) | BR9407485A (fr) |
| CA (1) | CA2171180A1 (fr) |
| CZ (1) | CZ286514B6 (fr) |
| DE (1) | DE59405046D1 (fr) |
| ES (1) | ES2111949T3 (fr) |
| WO (1) | WO1995007370A1 (fr) |
Families Citing this family (19)
| 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 (de) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Verfahren zur Phosphatierung mit metallhaltiger Nachspülung |
| DE19639596A1 (de) * | 1996-09-26 | 1998-04-02 | Henkel Kgaa | Verfahren zur Phosphatierung von Stahlband |
| DE19756735A1 (de) * | 1997-12-19 | 1999-06-24 | Henkel Kgaa | Phosphatierung von einseitig verzinktem Stahlband |
| DE19808440C2 (de) * | 1998-02-27 | 2000-08-24 | Metallgesellschaft Ag | Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen sowie eine Verwendung der Lösung und des Verfahrens |
| DE19808755A1 (de) * | 1998-03-02 | 1999-09-09 | Henkel Kgaa | Schichtgewichtsteuerung bei Bandphosphatierung |
| DE19834796A1 (de) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung |
| AU2348500A (en) * | 1998-12-23 | 2000-07-31 | Henkel Corporation | Composition and process for heavy zinc phosphating |
| JP2001342575A (ja) * | 2000-05-31 | 2001-12-14 | Nippon Dacro Shamrock Co Ltd | 水性金属表面処理剤 |
| DE10110833B4 (de) * | 2001-03-06 | 2005-03-24 | Chemetall Gmbh | Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile |
| DE10155666A1 (de) * | 2001-11-13 | 2003-05-22 | Henkel Kgaa | Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren |
| KR100554740B1 (ko) * | 2001-12-17 | 2006-02-24 | 주식회사 포스코 | 인산피막이 형성된 전기아연 도금강판 제조방법 |
| WO2009017535A2 (fr) * | 2007-06-07 | 2009-02-05 | Henkel Ag & Co. Kgaa | Phosphatation au manganèse, zinc et modifiée au cobalt |
| DE102010001686A1 (de) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Zusammensetzung für die alkalische Passivierung von Zinkoberflächen |
| ES2428290T3 (es) | 2011-03-22 | 2013-11-06 | Henkel Ag & Co. Kgaa | Tratamiento anticorrosivo de varios pasos para componentes metálicos, que por lo menos parcialmente presentan superficies de cinc o de aleaciones de cinc |
| CN102703889B (zh) * | 2012-05-28 | 2014-06-04 | 武汉永正科技发展有限公司 | 低温单组份锌系磷化液及其制备方法 |
| CN103184444B (zh) * | 2013-03-29 | 2016-08-03 | 柳州煜华科技有限公司 | 一种适用于金属紧固件的磷化液 |
| CN104651820A (zh) * | 2015-02-16 | 2015-05-27 | 天津大学 | 一种碳钢超声磷化液及制备方法以及采用磷化液对碳钢磷化的方法 |
| EP3280830B1 (fr) * | 2015-04-07 | 2021-03-31 | Chemetall GmbH | Procédé permettant d'ajuster de manière ciblée la conductivité électrique de couches de conversion |
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| 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 (es) * | 1985-02-22 | 1986-04-01 | Henkel Iberica | Procedimiento para el fosfatado de superficies metalicas, especialmente ferreas |
| ATE160592T1 (de) * | 1985-08-27 | 1997-12-15 | Henkel Corp | Verfahren zur phosphatierung von metalloberflächen |
| US4865653A (en) * | 1987-10-30 | 1989-09-12 | Henkel Corporation | Zinc phosphate coating process |
| NL8703050A (nl) * | 1987-12-16 | 1989-07-17 | Johannes Schuitemaker | Invoermechanisme voor een opraapwagen. |
| ES2092983T3 (es) * | 1987-12-18 | 1996-12-16 | Nippon Paint Co Ltd | Procedimiento para fosfatar con zinc una superficie metalica. |
| JP2636919B2 (ja) * | 1989-01-26 | 1997-08-06 | 日本パーカライジング株式会社 | 鉄鋼の冷間塑性加工用潤滑処理方法 |
| US5232523A (en) * | 1989-03-02 | 1993-08-03 | Nippon Paint Co., Ltd. | Phosphate coatings for metal surfaces |
| DE3913089A1 (de) * | 1989-04-21 | 1990-10-25 | Henkel Kgaa | Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten |
| JPH0696773B2 (ja) * | 1989-06-15 | 1994-11-30 | 日本ペイント株式会社 | 金属表面のリン酸亜鉛皮膜形成方法 |
| DE3920296A1 (de) * | 1989-06-21 | 1991-01-10 | Henkel Kgaa | Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatueberzuegen |
| DE4013483A1 (de) * | 1990-04-27 | 1991-10-31 | Metallgesellschaft Ag | Verfahren zur phosphatierung von metalloberflaechen |
| US5268041A (en) * | 1990-04-27 | 1993-12-07 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
| DE4210513A1 (de) * | 1992-03-31 | 1993-10-07 | Henkel Kgaa | Nickel-freie Phosphatierverfahren |
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1994
- 1994-08-29 JP JP50842695A patent/JP3348856B2/ja not_active Expired - Fee Related
- 1994-08-29 CN CN94193230A patent/CN1041001C/zh not_active Expired - Fee Related
- 1994-08-29 CZ CZ1996673A patent/CZ286514B6/cs not_active IP Right Cessation
- 1994-08-29 AU AU75373/94A patent/AU678284B2/en not_active Ceased
- 1994-08-29 US US08/612,925 patent/US5792283A/en not_active Expired - Lifetime
- 1994-08-29 AT AT94925483T patent/ATE162233T1/de not_active IP Right Cessation
- 1994-08-29 WO PCT/EP1994/002848 patent/WO1995007370A1/fr active IP Right Grant
- 1994-08-29 ES ES94925483T patent/ES2111949T3/es not_active Expired - Lifetime
- 1994-08-29 CA CA002171180A patent/CA2171180A1/fr not_active Abandoned
- 1994-08-29 DE DE59405046T patent/DE59405046D1/de not_active Expired - Lifetime
- 1994-08-29 EP EP94925483A patent/EP0717787B1/fr not_active Expired - Lifetime
- 1994-08-29 KR KR1019960701115A patent/KR100327287B1/ko not_active IP Right Cessation
- 1994-08-29 BR BR9407485A patent/BR9407485A/pt not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9507370A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1041001C (zh) | 1998-12-02 |
| ATE162233T1 (de) | 1998-01-15 |
| CZ67396A3 (en) | 1996-12-11 |
| KR100327287B1 (ko) | 2002-11-22 |
| CZ286514B6 (cs) | 2000-05-17 |
| JPH09502224A (ja) | 1997-03-04 |
| EP0717787B1 (fr) | 1998-01-14 |
| DE59405046D1 (de) | 1998-02-19 |
| CA2171180A1 (fr) | 1995-03-16 |
| BR9407485A (pt) | 1996-06-25 |
| US5792283A (en) | 1998-08-11 |
| AU7537394A (en) | 1995-03-27 |
| WO1995007370A1 (fr) | 1995-03-16 |
| CN1129961A (zh) | 1996-08-28 |
| AU678284B2 (en) | 1997-05-22 |
| JP3348856B2 (ja) | 2002-11-20 |
| ES2111949T3 (es) | 1998-03-16 |
| KR960705076A (ko) | 1996-10-09 |
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