EP3918108B1 - Alternative zusammensetzung und alternatives verfahren zur effektiven phosphatierung von metallischen oberflächen - Google Patents
Alternative zusammensetzung und alternatives verfahren zur effektiven phosphatierung von metallischen oberflächen Download PDFInfo
- Publication number
- EP3918108B1 EP3918108B1 EP20700942.4A EP20700942A EP3918108B1 EP 3918108 B1 EP3918108 B1 EP 3918108B1 EP 20700942 A EP20700942 A EP 20700942A EP 3918108 B1 EP3918108 B1 EP 3918108B1
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- Prior art keywords
- composition according
- accelerator
- phosphating
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- 239000000203 mixture Substances 0.000 title claims description 77
- 238000000034 method Methods 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 title description 16
- 239000002184 metal Substances 0.000 title description 16
- 239000002253 acid Substances 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- -1 1-hydroxypropyl Chemical group 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 16
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- OLQJQHSAWMFDJE-UHFFFAOYSA-N 2-(hydroxymethyl)-2-nitropropane-1,3-diol Chemical compound OCC(CO)(CO)[N+]([O-])=O OLQJQHSAWMFDJE-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001453 nickel ion Inorganic materials 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 5
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000001282 organosilanes Chemical class 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 230000003115 biocidal effect Effects 0.000 claims description 4
- 239000003139 biocide Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002161 passivation Methods 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004761 hexafluorosilicates Chemical class 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 150000003755 zirconium compounds Chemical class 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 20
- 235000021317 phosphate Nutrition 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000010452 phosphate Substances 0.000 description 18
- 238000005246 galvanizing Methods 0.000 description 16
- 239000003973 paint Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 150000002222 fluorine compounds Chemical class 0.000 description 9
- 230000008595 infiltration Effects 0.000 description 9
- 238000001764 infiltration Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 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 8
- 229910000165 zinc phosphate Inorganic materials 0.000 description 8
- 229910001335 Galvanized steel Inorganic materials 0.000 description 6
- 239000008397 galvanized steel Substances 0.000 description 6
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010422 painting Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 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 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity 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
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000001283 organosilanols Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-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
- C23C22/07—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
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel 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
- C23C22/365—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 containing also zinc and nickel 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
-
- 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
- C23C22/78—Pretreatment of the material to be coated
Definitions
- the present invention relates to an alternative composition for the effective phosphating of metallic surfaces, a method for producing such a composition and an alternative method for phosphating metallic surfaces.
- Phosphate coatings on metallic surfaces are known from the prior art. Such coatings serve to protect the metallic surfaces from corrosion and also as an adhesion promoter for subsequent layers of paint or as a forming aid.
- WO 97/30189 A1 discloses phosphate coatings produced using compositions containing nitro compounds or nitrate ions in addition to zinc ions, manganese ions and phosphate ions.
- These coatings are also referred to as conversion layers, since cations released from the metallic surface are used to build up the layer.
- Such phosphate coatings are mainly used in the automotive industry and in general industry.
- the subsequent coats of paint are mainly cathodic electro-dip coatings (KTL).
- phosphate coatings are also used as a forming aid under a subsequently applied layer of lubricant for cold forming or as protection for a short storage period before painting.
- accelerators which are added to the baths in the form of liquid additives, are usually used in phosphating baths. These accelerators support the deposition of the phosphate layer by remove the hydrogen formed on the metallic surface from the equilibrium by oxidation and thus promote the formation of the pH gradient.
- the object of the present invention was therefore to provide an alternative composition or an alternative method with which metallic surfaces, in particular those which, in addition to surfaces made of zinc, also contain those made of aluminum and possibly iron, can be effectively phosphated
- metallic surfaces in particular those which, in addition to surfaces made of zinc, also contain those made of aluminum and possibly iron, can be effectively phosphated
- the aforementioned disadvantages of the accelerator nitroguanidine are avoided and paint adhesion and corrosion protection results are achieved which are comparable to phosphating using nitroguanidine.
- an acidic, aqueous composition according to the invention for the phosphating of metallic surfaces which, in addition to zinc ions, manganese ions, phosphate ions and preferably nickel ions, contains at least one accelerator of the following formula (I) R 1 R 2 R 3 C-NO 2 (I) wherein each of the substituents R 1 , R 2 and R 3 on the carbon atom is independently selected from the group consisting of hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl , 1-hydroxy-1-methylethyl and 2-hydroxy-1-methylethyl.
- Said object is also achieved by a method according to the invention for phosphating metallic surfaces, in which a metallic surface, optionally after cleaning and/or activation, is treated with the composition according to the invention and then optionally rinsed and/or dried.
- an uncoated metallic surface on the other hand, an already conversion-coated, for example pre-phosphated, metallic surface can be treated with the method according to the invention.
- a metallic surface is mentioned below, it should therefore always also include a metallic surface that has already been conversion-coated.
- aqueous composition refers to a composition which at least partly, preferably predominantly, i.e. more than 50% by weight, contains water as the solvent or dispersing medium. In addition to dissolved components, it can also include dispersed, i.e. emulsified and/or suspended components. The same applies to an "aqueous additive".
- phosphating bath composition an acidic, aqueous composition for phosphating metallic surfaces.
- phosphate ions also means hydrogen phosphate, dihydrogen phosphate and phosphoric acid.
- pyrophosphoric acid and polyphosphoric acid and all of their partially and fully deprotonated forms are intended to be included.
- aluminum also includes its alloys.
- zinc also includes zinc alloys, for example zinc-magnesium alloys, as well as galvanized steel and alloy-galvanized steel, while the mention of "iron” also includes iron alloys, in particular steel.
- galvanized or alloy-galvanized steel it can are in turn hot-dip galvanized or electrolytically galvanized steel. Alloys of the aforementioned metals have a proportion of foreign atoms of less than 50% by weight.
- composition according to the invention and the method according to the invention are particularly suitable for multimetal applications.
- the treated metallic surface is therefore in particular one which, in addition to areas made of zinc, also contains areas made of aluminum and, if appropriate, areas made of iron.
- an acidic, neutral, alkaline or strongly alkaline cleaning composition can be used for this purpose, but optionally also an acidic or neutral pickling composition.
- An alkaline or strongly alkaline cleaning composition has proven to be particularly advantageous.
- the aqueous cleaning composition can optionally also contain a cleaning structure, e.g. a water-soluble silicate, and/or other additives such as e.g. complexing agents, phosphates and/or borates.
- a cleaning structure e.g. a water-soluble silicate, and/or other additives such as e.g. complexing agents, phosphates and/or borates.
- an activating cleaner is also possible.
- the metallic surface is then advantageously at least rinsed with water, it also being possible for an additive dissolved in water, such as a nitrite or surfactant, to be added to the water.
- an additive dissolved in water such as a nitrite or surfactant
- the activation composition serves to deposit a large number of very fine phosphate particles as seed crystals on the metallic surface. These help in the subsequent process step, in contact with the composition according to the invention - preferably without intermediate rinsing - to form a particularly crystalline phosphate layer with the highest possible number of fine phosphate crystals arranged densely or a largely closed phosphate layer.
- Alkaline compositions based on titanium phosphate and/or zinc phosphate are particularly suitable as activation compositions.
- activating agents in particular titanium phosphate and/or zinc phosphate, to the cleaning composition, ie to carry out cleaning and activation in one step.
- the at least one accelerator of the formula (II) is very particularly preferably 2-hydroxymethyl-2-nitro-1,3-propanediol.
- the at least one accelerator of the formula (I) - in particular of the formula (II) - is preferably present in a concentration which is in the range from 0.25 to 4.0 g/l, more preferably from 0.50 to 3.3 g/l and particularly preferably from 0.75 to 2.5 g/l - calculated as 2-hydroxymethyl-2-nitro-1,3-propanediol.
- concentration which is in the range from 0.25 to 4.0 g/l, more preferably from 0.50 to 3.3 g/l and particularly preferably from 0.75 to 2.5 g/l - calculated as 2-hydroxymethyl-2-nitro-1,3-propanediol.
- “Calculated as 2-hydroxymethyl-2-nitro-1,3-propanediol” is to be understood as meaning the fiction that all molecules of the at least one accelerator to be 2-hydroxymethyl-2-nitro-1,3-propanediol.
- a phosphating bath composition according to the invention which therefore contains at least one accelerator of the formula (I) - in particular of the formula (II) - also has a comparable stability of the accelerator to a phosphating bath composition which contains nitroguanidine with regard to decomposition without the treatment of metal surfaces.
- those that have been treated with the phosphating bath composition according to the invention have comparable or even better paint adhesion and comparable or even better corrosion protection (against corrosive infiltration) after painting.
- the phosphating bath composition according to the invention also applies to the comparison of the phosphating bath composition according to the invention with a nitrite-containing phosphating bath composition.
- the phosphating composition according to the invention has a significantly higher stability of the accelerator than one containing the hazardous substance nitrite.
- inventive Composition preferably the following components in the following preferred and particularly preferred concentration ranges: Zn 0.3 to 3.0 g/l 0.5 to 2.0 g/l Mn 0.3 to 2.0 g/l 0.5 to 1.5 g/l no 0.3 to 2.0 g/L 0.5 to 1.5 g/L Phosphate (calculated as P) 3.5 to 10.9 g/l 4.3 to 7.8 g/l
- phosphate coatings are usually applied using a nickel-containing phosphating solution.
- the nickel deposited elementally or as an alloy component, e.g. Zn/Ni, ensures suitable conductivity of the coating during subsequent electrophoretic painting.
- a content of at least one complex fluoride in the composition according to the invention has also proven to be advantageous.
- the at least one complex fluoride is preferably tetrafluoroborate (BF 4 - ) and/or hexafluorosilicate (SiF 6 2- ), the content of complex fluoride in the composition according to the invention preferably being in the range from 0.5 to 5 g/l, more preferably from 0.5 to 3 g/l.
- composition according to the invention has a content of free fluoride in addition to a content of complex fluoride--in particular in the aforementioned ranges.
- the free fluoride content is preferably in the range from 20 to 250 mg/l, more preferably from 30 to 180 mg/l, can be determined using a fluoride-sensitive electrode and is added to the composition according to the invention in particular as simple fluoride, i.e. not as complex fluoride. admitted.
- Hydrofluoric acid, sodium fluoride, sodium hydrogen difluoride and ammonium hydrogen difluoride are particularly suitable as simple fluorides.
- Al 3+ is a bath poison in phosphating systems and can be limited by adding sodium ions and simple fluoride, ie its concentration can be brought below 100 mg/l, preferably below 50 mg/l and particularly preferably below 25 mg/l. It is preferred here to precipitate cryolite (Na 3 AlF 6 ), which has a very low solubility in water.
- Complex fluorides have a fluoride buffer effect, so that it is possible to catch a reduction in the free fluoride content in the phosphating bath in the event of a short-term increase in the throughput of aluminum-containing metallic surfaces due to increased release of free fluoride from the complex, without the bath having to be cleaned by adding simple fluoride must be adjusted on a case-by-case basis.
- the free fluoride supports the pickling attack on the metallic surface and thus the formation of the phosphate layer there, which in turn leads to improved paint adhesion and corrosion protection - not only on metallic surfaces containing zinc or aluminium.
- a possible embodiment corresponds to the preferred embodiment described above with the difference that the composition according to the invention is essentially free of nickel (nickel-free phosphating).
- Essentially nickel-free means that the content of nickel ions does not result from an intentional addition to the composition according to the invention results. It is possible, for example, that a content of nickel ions, albeit a small one, is leached out of the metallic surface. In this case, however, the content of nickel ions is preferably only at most 10 mg/l, more preferably at most 1 mg/l.
- nickel ions are no longer desirable as a component of treatment solutions and should therefore be avoided if possible or at least reduced in their content.
- the composition according to the invention contains hydrogen peroxide (H 2 O 2 ) as a further accelerator in addition to the at least one accelerator of the formula (I)—in particular of the formula (II).
- H 2 O 2 hydrogen peroxide
- This is preferably present in a concentration in the range from 10 to 100 mg/l, more preferably from 15 to 50 mg/l.
- the surface to be treated also includes areas containing iron, in particular steel, an accumulation of Fe(II) in the phosphating bath composition and thus a slowing down of the layer formation can be avoided by using H 2 O 2 as a further accelerator: H 2 O 2 becomes Fe (II) oxidized to Fe(III) and precipitated as ferric phosphate.
- the composition of the invention is essentially free of nitroguanidine, i.e. no nitroguanidine has been intentionally added to the composition. If it does contain nitroguanidine, this is only present as an impurity, i.e. in small or very small amounts.
- concentration of nitroguanidine is preferably below 10 mg/l, particularly preferably below 1 mg/l.
- composition according to the invention can be characterized by the following preferred and particularly preferred parameter ranges: FS or FS-KCI 0.3 to 2.5 0.7 to 1.6 FS (edited) 0.5 to 8 1 to 6 GSF 10 to 28 14 to 26 GS or GS-KCI 12 to 45 18 to 35 S value 0.01 to 0.2 0.03 to 0.15 temperature 30 to 58oC 35 to 55 °C
- FS stands for free acid or - if complex fluorides are present in the phosphating bath - for free acid-KCl
- FS (diluted) for free acid (diluted)
- GSF for total acid according to Fischer
- GS for Total acid or - if complex fluorides are present in the phosphating bath - for total acid KCl
- S value for acid value.
- the free acid KCl 10 ml of the composition according to the invention are pipetted into a suitable vessel, for example a 300 ml Erlenmeyer flask, and diluted with 50 ml deionized water. If the composition according to the invention contains complex fluorides, the sample is instead diluted with 50 ml of 2 M KCl solution. Then, using a pH meter and electrode, titrate with 0.1 M NaOH to pH 4.0. The amount of 0.1 M NaOH consumed in ml per 10 ml of the composition gives the value of the free acid (FA) or the free acid-KCl (FA-KCl) in points.
- a suitable vessel for example a 300 ml Erlenmeyer flask
- the diluted composition according to the invention After addition of potassium oxalate solution, is titrated using a pH meter and an electrode with 0.1 M NaOH to a pH value of 8.9. The consumption of 0.1 M NaOH in ml per 10 ml of the diluted composition gives the total Fischer acidity (TSF) in points.
- TSF total Fischer acidity
- GS Total acid
- GS-KCI total acid-KCI
- the total acid or - if complex fluorides are present in the phosphating bath - the total acid-KCI is the sum of the contained divalent cations as well as free and bound phosphoric acids (the latter are phosphates). It is determined by consuming 0.1M NaOH using a pH meter and electrode. For this purpose, 10 ml of the composition according to the invention are pipetted into a suitable vessel, for example a 300 ml Erlenmeyer flask, and diluted with 50 ml of deionized water. If the composition according to the invention contains complex fluorides, the sample is instead diluted with 50 ml of 2 M KCl solution. Then with 0.1 M NaOH to a pH of 8.9 titrated. The consumption in ml per 10 ml of the diluted composition corresponds to the number of points for the total acid (TA) or the total acid KCI (TA-KCI).
- S value stands for the ratio FA : GSF or FA-KCI : GSF and is obtained by dividing the value of the free acid (FA) or the free acid KCl (FA-KCI) by the value the total acidity according to Fischer (GSF).
- the metallic surface is treated with the composition according to the invention preferably for 30 to 480, particularly preferably for 60 to 300 and very particularly preferably for 90 to 240 seconds, preferably by dipping or spraying.
- the following preferred and particularly preferred zinc phosphate layer weights are achieved on the metallic surface, depending on the treated surface (determined with RFA, ie X-ray fluorescence analysis): Treated surface Zinc phosphate coating weight (g/m 2 )* steel 0.5 to 6 1.0 to 5 hot-dip galvanizing 0.5 to 6 1.0 to 5 electrolytic galvanizing 0.5 to 6 1.0 to 5 aluminum 0.5 to 6 1.0 to 5 *) calculated as Zns(PO 4 ) 2 4 H 2 O
- the additive is preferably diluted to such an extent that the at least one accelerator of the formula (I) - in particular of the formula (II) - is present in the phosphating bath composition in a concentration which is in the range from 0.25 to 4 0 g/l, more preferably from 0.50 to 3.3 g/l and particularly preferably from 0.75 to 2.5 g/l - calculated as 2-hydroxymethyl-2-nitro-1,3-propanediol .
- the metallic surface is optionally rinsed and/or dried after treatment with the composition according to the invention.
- an acidic, aqueous passivation can then follow, in particular based on at least one titanium and/or zirconium compound and optionally at least one organosilane, with the term “organosilane” also including the associated hydrolysis and condensation products , i.e. the corresponding organosilanols and organosiloxanes.
- organosilane also including the associated hydrolysis and condensation products , i.e. the corresponding organosilanols and organosiloxanes.
- a preferably alkaline, aqueous after-rinse based on at least one organosilane and/or at least one other organic compound can alternatively follow.
- the metallic surface which has already been treated with an essentially nickel-free composition according to the invention and optionally rinsed and/or dried is treated with an aqueous after-rinse composition, in particular with one which contains at least one type of metal ion and/or at least one electrically conductive one Polymer includes, where "metal ion" is either a metal cation, a complex metal cation or a complex metal anion, preferably molybdate to understand.
- a cathodic electro-dip coating KTL
- a powder coating of the phosphate-coated and optionally passivated or rinsed metallic surface can be carried out and a paint structure (powder or wet paint) can be applied.
- the method according to the invention can also include further steps, in particular further rinsing or drying steps.
- the phosphate-coated metallic surface produced using the process according to the invention and optionally provided with a cathodic electrodeposition paint and a paint structure are used primarily in the areas of automobile construction, automobile components or general industry.
- the phosphate coatings produced with the method according to the invention can serve not only as an adhesion promoter for subsequent layers of paint, but also as a forming aid under a subsequently applied layer of lubricant for cold forming or as corrosion protection for a short storage period before painting.
- Test panels made from various metallic substrates were first cleaned.
- test panels treated with phosphating solutions No. 6 and No. 7 were not passivated.
- the sheets were then rinsed with deionized water (conductivity ⁇ 20 ⁇ S/cm) and dried at 110 to 120° C. in a drying cabinet.
- the average zinc phosphate layer weights listed in Tab. 2 could be determined on the various phosphated test panels using RFA (X-ray fluorescence analysis).
- test sheets were subjected to a cathodic electro-dip coating (KTL) using CathoGuard® 800 (BASF, Germany).
- KTL cathodic electro-dip coating
- CathoGuard® 800 BASF, Germany
- MB Mercedes Benz automotive paint system
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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)
- Chemically Coating (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP19154196 | 2019-01-29 | ||
| PCT/EP2020/051585 WO2020156913A1 (de) | 2019-01-29 | 2020-01-23 | Alternative zusammensetzung und alternatives verfahren zur effektiven phosphatierung von metallischen oberflächen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3918108A1 EP3918108A1 (de) | 2021-12-08 |
| EP3918108B1 true EP3918108B1 (de) | 2023-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP20700942.4A Active EP3918108B1 (de) | 2019-01-29 | 2020-01-23 | Alternative zusammensetzung und alternatives verfahren zur effektiven phosphatierung von metallischen oberflächen |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20220119957A1 (zh) |
| EP (1) | EP3918108B1 (zh) |
| JP (1) | JP2022523717A (zh) |
| KR (1) | KR20210116498A (zh) |
| CN (1) | CN113366147A (zh) |
| BR (1) | BR112021012507A2 (zh) |
| ES (1) | ES2946018T3 (zh) |
| MX (1) | MX2021009075A (zh) |
| WO (1) | WO2020156913A1 (zh) |
| ZA (1) | ZA202106147B (zh) |
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| KR102655555B1 (ko) | 2023-11-20 | 2024-04-11 | 한국전력기술 주식회사 | 심층 강화학습을 활용한 해상풍력단지 정비 플래닝 시스템 및 방법 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19606018A1 (de) * | 1996-02-19 | 1997-08-21 | Henkel Kgaa | Zinkphosphatierung mit geringen Gehalten an Nickel- und/oder Cobalt |
| DE19621184A1 (de) * | 1996-05-28 | 1997-12-04 | Henkel Kgaa | Zinkphosphatierung mit integrierter Nachpassivierung |
| BR112017021409B1 (pt) * | 2015-04-07 | 2023-02-28 | Chemetall Gmbh | Método para fosfatação de uma superfície metálica, e, superfície metálica revestida com fosfato |
-
2020
- 2020-01-23 ES ES20700942T patent/ES2946018T3/es active Active
- 2020-01-23 EP EP20700942.4A patent/EP3918108B1/de active Active
- 2020-01-23 MX MX2021009075A patent/MX2021009075A/es unknown
- 2020-01-23 JP JP2021544333A patent/JP2022523717A/ja active Pending
- 2020-01-23 US US17/425,042 patent/US20220119957A1/en active Pending
- 2020-01-23 CN CN202080011352.0A patent/CN113366147A/zh active Pending
- 2020-01-23 BR BR112021012507-8A patent/BR112021012507A2/pt unknown
- 2020-01-23 WO PCT/EP2020/051585 patent/WO2020156913A1/de unknown
- 2020-01-23 KR KR1020217023667A patent/KR20210116498A/ko unknown
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| Publication number | Publication date |
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| ZA202106147B (en) | 2024-03-27 |
| US20220119957A1 (en) | 2022-04-21 |
| JP2022523717A (ja) | 2022-04-26 |
| CN113366147A (zh) | 2021-09-07 |
| ES2946018T3 (es) | 2023-07-11 |
| WO2020156913A1 (de) | 2020-08-06 |
| EP3918108A1 (de) | 2021-12-08 |
| KR20210116498A (ko) | 2021-09-27 |
| BR112021012507A2 (pt) | 2021-09-14 |
| MX2021009075A (es) | 2021-09-10 |
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