EP3280830A1 - Verfahren zur gezielten einstellung der elektrischen leitfähigkeit von konversionsbeschichtungen - Google Patents
Verfahren zur gezielten einstellung der elektrischen leitfähigkeit von konversionsbeschichtungenInfo
- Publication number
- EP3280830A1 EP3280830A1 EP16717585.0A EP16717585A EP3280830A1 EP 3280830 A1 EP3280830 A1 EP 3280830A1 EP 16717585 A EP16717585 A EP 16717585A EP 3280830 A1 EP3280830 A1 EP 3280830A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aqueous composition
- ions
- metallic surface
- conversion
- treated
- 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 33
- 238000007739 conversion coating Methods 0.000 title claims abstract description 32
- -1 polyimines Polymers 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 37
- 239000011733 molybdenum Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229920000768 polyamine Polymers 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000767 polyaniline Polymers 0.000 claims abstract description 9
- 229920000123 polythiophene Polymers 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 239000010931 gold Substances 0.000 claims abstract description 8
- 239000011135 tin Substances 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 13
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 150000001282 organosilanes Chemical class 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000009501 film coating Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000007859 condensation product Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 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 claims description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 4
- YGSCDVQTKKMYBS-UHFFFAOYSA-N 3-[2-aminoethyl(hydroxy)silyl]propan-1-amine Chemical compound NCC[SiH](O)CCCN YGSCDVQTKKMYBS-UHFFFAOYSA-N 0.000 claims description 3
- JVRHDWRSHRSHHS-UHFFFAOYSA-N 3-hydroxysilylpropan-1-amine Chemical compound NCCC[SiH2]O JVRHDWRSHRSHHS-UHFFFAOYSA-N 0.000 claims description 3
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910001432 tin ion Inorganic materials 0.000 abstract description 3
- 229910001439 antimony ion Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 71
- 239000000243 solution Substances 0.000 description 71
- 238000012360 testing method Methods 0.000 description 66
- 239000012487 rinsing solution Substances 0.000 description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000002253 acid Substances 0.000 description 22
- 229910052759 nickel Inorganic materials 0.000 description 21
- 229910001335 Galvanized steel Inorganic materials 0.000 description 14
- 239000008397 galvanized steel Substances 0.000 description 14
- 239000003973 paint Substances 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000004922 lacquer Substances 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 7
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 238000002161 passivation Methods 0.000 description 7
- 229920002873 Polyethylenimine Polymers 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 150000004761 hexafluorosilicates Chemical class 0.000 description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 230000000284 resting effect Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000207836 Olea <angiosperm> Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 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
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005580 one pot reaction Methods 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
- 238000010422 painting Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—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
- C23C22/05—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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Definitions
- the present invention relates to a method for the specific adjustment of the electrical conductivity of a conversion coating on a metallic surface by means of an aqueous composition and to a corresponding aqueous composition and a corresponding conversion coating.
- Conversion coatings on metallic surfaces are known from the prior art. Such coatings serve to protect the corrosion of the metallic surfaces and also as adhesion promoters for subsequent paint layers.
- lacquer layers are mainly cathodically deposited electrodeposition paints (KTL). Since during the deposition of KTL a current must flow between the metallic surface and the treatment bath, it is important to set a defined electrical conductivity of the conversion coating in order to ensure an efficient and homogeneous deposition.
- KTL cathodically deposited electrodeposition paints
- conversion coatings are usually applied by means of a nickel-containing phosphating solution.
- the nickel ions thus incorporated into the conversion coating or the elementally deposited nickel provide for a suitable conductivity of the coating in the subsequent electrodeposition coating.
- nickel ions are no longer desirable as part of treatment solutions because of their high toxicity and environmental toxicity, and should therefore be avoided or at least reduced in content as much as possible.
- nickel-free or nickel-poor systems are thin-film coatings which are, for example, thin coatings of zirconium oxide and optionally at least one organosiloxane and / or at least one organic polymer. Again, however, the targeted adjustment of the electrical conductivity for subsequent electrocoating is still unsatisfactory. Thus, in many cases more or less pronounced inhomogeneities of the deposited cathods can not be avoided (so-called mapping). Moreover, in the case of the abovementioned nickel-poor or nickel-free systems, unfavorable KTL deposition conditions can lead to poor corrosion and lacquer adhesion values due to a not optimally adjusted electrical conductivity of the conversion coating.
- the object of the present invention was therefore to provide a method by means of which the electrical conductivity of a conversion coating on a metallic surface can be adjusted in a targeted manner and in which, in particular, the disadvantages known from the prior art are avoided.
- a metallic surface or a conversion-coated metallic surface is treated with an aqueous composition according to the invention which comprises at least one type of metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold , Palladium, tin and antimony and / or at least one electrically conductive polymer selected from the group consisting of the polymer classes of the polyamines, polyanilines, polyimines, polythiophenes and polypryrenes.
- metal ion is meant either a metal cation, a complex metal cation or a complex metal anion.
- an “aqueous composition” is meant a composition which contains predominantly, ie, more than 50% by weight, water as the solvent, and may comprise, in addition to dissolved constituents, also dispersed, ie emulsified and / or suspended constituents.
- an uncoated metallic surface on the other hand, an already conversion-coated metallic surface can be treated by the method according to the invention.
- the aqueous composition may on the one hand itself be a treatment solution for producing a conversion coating (so-called one-pot process), but on the other hand may also be used as a rinsing solution for the treatment of an already generated conversion coating.
- an aqueous composition according to the invention as a treatment solution for producing a conversion coating and then a second composition according to the invention - same or different composition - as rinsing solution for the treatment of the conversion coating thus produced.
- the aqueous composition according to the invention comprises at least one kind of metal ion selected from the group consisting of the ions of the following metals in the following preferred, particularly preferred and most preferred concentration ranges (all calculated as corresponding metal): Mo 1 to 1000 mg / l 10 to 500 mg / l 20 to 225 mg / l
- the metal ions contained in the aqueous composition are deposited either in the form of a salt which preferably contains the corresponding metal cation (eg molybdenum or tin) in at least two oxidation states - in particular in the form of an oxide hydroxide, a hydroxide, a spinel or a defect spinel - or elemental on the surface to be treated (eg copper, silver, gold or palladium).
- a salt which preferably contains the corresponding metal cation (eg molybdenum or tin) in at least two oxidation states - in particular in the form of an oxide hydroxide, a hydroxide, a spinel or a defect spinel - or elemental on the surface to be treated (eg copper, silver, gold or palladium).
- the metal ions are molybdenum ions. These are preferably added as molybdate, more preferably as ammonium heptamolybdate and more preferably as ammonium heptamolybdate x 7 H 2 O of the aqueous composition.
- molybdenum ions can also be added to the aqueous composition, for example in the form of at least one salt containing molybdenum cations, such as molybdenum chloride, and then oxidized to molybdate by a suitable oxidizing agent, for example by the accelerators described below.
- a suitable oxidizing agent for example by the accelerators described below.
- the aqueous composition contains molybdenum ions in combination with copper ions, tin ions or zirconium ions.
- a polymer or copolymer in particular selected from the group consisting of the polymer classes of polyamines, polyanilines, polyimines, polythiophenes and polypryrenes and mixtures and copolymers thereof and polyacrylic acid, wherein the content of molybdenum ions and Zirconium each in the range of 10 to 500 mg / l (calculated as metal) is.
- the content of molybdenum ions is preferably in the range from 20 to 225 mg / l, particularly preferably from 50 to 225 mg / l and very particularly preferably from 100 to 225 mg / l and the content of zirconium ions in the range from 30 to 300 mg / l, more preferably from 50 to 200 mg / l.
- the metal ions are copper ions.
- the rinsing solution then contains these in a concentration of 5 to 225 mg / l, more preferably from 150 to 225 mg / l.
- the aqueous composition according to the invention contains at least one electrically conductive polymer selected from the group consisting of the polymer classes of the polyamines, polyanilines, polyimines, polythiophenes and polypryoles. Preference is given to using a polyamine and / or polyimine, more preferably a polyamine.
- the polyamine is preferably a polyethyleneamine, the polyimine is a polyethylenimine.
- the at least one electrically conductive polymer is preferably in a concentration in the range from 0.1 to 5.0 g / l, more preferably from 0.2 to 3.0 g / l and particularly preferably in the range from 0.5 to 1 , 5 g / l (calculated as pure polymer).
- electrically conductive polymers cationic polymers such as e.g. Polyamines or polyethyleneimines used.
- the aqueous composition according to the invention comprises at least one kind of metal ions selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin and antimony and at least one electrically conductive polymer selected from the group consisting of the polymer classes Polyamines, polyanilines, polyimines, polythiophenes and polypryrenes.
- aqueous compositions according to the invention which are less than 1.5 g / l, more preferably less than 1 g / l, more preferably less than 0.5 g / l, more preferably less than 0.1 g / l, and most preferably less than 0.01 g / l nickel ions. If a treatment solution or aqueous composition according to the invention contains less than 0.01 g / l of nickel ions, it should be considered at least essentially nickel-free.
- Suitable conversion coatings which are produced or treated by means of the aqueous composition according to the invention, are, in particular, phosphate coatings and thin-film coatings.
- the thin-film coatings are, for example, thin coatings of zirconium oxide and optionally at least one organosiloxane and / or at least one organic polymer.
- Such conversion coatings are applied by means of a corresponding phosphating solution or conversion / passivating solution.
- phosphating solutions and conversion / passivating solutions which are aqueous compositions according to the invention.
- the aqueous compositions according to the invention are therefore themselves treatment solutions for producing a conversion coating, and the phosphating solutions and conversion / passivation solutions described below always have the features of the aqueous composition according to the invention described above.
- the phosphating solution may be an aqueous zinc phosphate solution or an aqueous alkali metal phosphate solution.
- zinc phosphate solution preferably comprises the following components in the following preferred and particularly preferred concentration ranges:
- a concentration in the range from 0.3 to 2.5 g / l has already been found to be advantageous with regard to the free fluoride, a concentration in the range from 10 to 250 mg / l.
- the complex fluoride is preferably tetrafluoroborate (BF " ) and / or hexafluorosilicate (SiF 6 2 ⁇ ).
- the complex fluoride is a combination of tetrafluoroborate (BF “ ) and hexafluorosilicate (SiF 6 2 ⁇ ), the concentration of tetrafluoroborate (BF “ ) being in the range up to 3 g / l, preferably from 0, 2 to 2 g / l, and the concentration of hexafluorosilicate (SiF 6 2 ⁇ ) in the range to 3 g / l, preferably from 0.2 to 2 g / l, is.
- the complex fluoride is hexafluorosilicate (SiF 6 2 ⁇ ) having a concentration in the range from 0.2 to 3 g / l, preferably from 0.5 to 2 g / l.
- the complex fluoride is tetrafluoroborate (BF " ) having a concentration in the range from 0.2 to 3 g / l, preferably from 0.5 to 2 g / l.
- the phosphating solution preferably contains at least one accelerator selected from the group consisting of the following compounds in the following preferred and particularly preferred concentration ranges:
- a concentration in the range of 0.1 to 3.0 g / l has already been found to be advantageous with respect to the H2O2, a concentration in the range from 5 to 200 mg / l.
- FS stands for free acid
- FS (verd.) For free acid (diluted)
- GSF for total acid according to Fischer
- GS for total acid
- S value for acid value
- a suitable vessel for example a 300 ml Erlenmeyer flask. contains the phosphating solution complex fluoride, 2-3 g of potassium chloride are added to the sample. Then, using a pH meter and an electrode, it is titrated with 0.1 M NaOH to a pH of 3.6. The consumed amount of 0.1 M NaOH in ml per 10 ml of the phosphating solution gives the value of the free acid (FS) in points.
- a suitable vessel for example a 300 ml Erlenmeyer flask. contains the phosphating solution complex fluoride, 2-3 g of potassium chloride are added to the sample. Then, using a pH meter and an electrode, it is titrated with 0.1 M NaOH to a pH of 3.6. The consumed amount of 0.1 M NaOH in ml per 10 ml of the phosphating solution gives the value of the free acid (FS) in points.
- FS free acid
- the free acid (diluted) 10 ml of the phosphating solution are pipetted into a suitable vessel, for example into a 300 ml Erlenmeyer flask. Subsequently, 150 ml of deionized water are added. Using a pH meter and an electrode, titrate with 0.1 M NaOH to a pH of 4.7. The consumed amount of 0.1 M NaOH in ml per 10 ml of the diluted phosphating solution gives the value of the free acid (diluted) (FS (dil.)) In points. About the difference to the free acid (FS) the content of complex fluoride can be determined. If this difference is multiplied by a factor of 0.36, the content of complex fluoride is SiF 6 2 ⁇ in g / l.
- the dilute phosphating solution is titrated to pH 8.9 after addition of potassium oxalate solution using a pH meter and electrode with 0.1 M NaOH.
- the consumption of 0.1 M NaOH in ml per 10 ml of the dilute phosphating gives in this case the total Fischer acid (GSF) in points. If this value is multiplied by 0.71, the total content of phosphate ions is calculated as P2O 5 (see W. Rausch: "The Phosphatization of Metals.” Eugen G. Leuze- Verlag 2005, 3rd edition, pp. 332 ff) , Total Acid (GS):
- the total acid (GS) is the sum of the divalent cations present as well as free and bound phosphoric acids (the latter being phosphates). It is determined by the consumption of 0.1 M NaOH using a pH meter and an electrode. For this purpose, 10 ml of the phosphating solution are pipetted into a suitable vessel, for example a 300 ml Erlenmeyer flask and diluted with 25 ml of deionized water. It is then treated with 0.1 M NaOH to a pH of 9 titrated. The consumption in ml per 10 ml of the diluted Phosphatierlosung corresponds to the total acid score (GS).
- S value stands for the ratio FS: GSF and is obtained by dividing the value of the free acid (FS) by the value of the total acid according to Fischer (GSF).
- the conversion / passivation solution is aqueous and always comprises 10 to 500 mg / l, preferably 30 to 300 mg / l and particularly preferably 50 to 200 mg / l of Ti, Zr and / or Hf in complexed form (calculated as metal). These are preferably fluoro complexes.
- the conversion / passivation solution always comprises 10 to 500 mg / l, preferably 15 to 100 mg / l and particularly preferably 15 to 50 mg / l of free fluoride.
- It preferably contains 10 to 500 mg / l, more preferably 30 to 300 mg / l and particularly preferably 50 to 200 mg / l of Zr in complexed form (calculated as metal).
- it additionally contains at least one organosilane and / or at least one hydrolysis product thereof and / or at least one condensation product thereof in a concentration range from 5 to 200 mg / l, more preferably from 10 to 100 mg / l and particularly preferably from 20 to 80 mg / l (calculated as Si).
- the at least one organosilane preferably has at least one amino group. Particularly preferably it is one which can be hydrolyzed to an aminopropylsilanol and / or to 2-aminoethyl-3-amino-propyl-silanol and / or a bis (trimethoxysilylpropyl) amine.
- the conversion / passivation solution may also contain the following components in the following concentration ranges and preferred concentration ranges: Zn 0 to 5 g / l 0.05 to 2 g / l
- the aqueous composition according to the invention can, as stated, not only be a treatment solution for producing a conversion coating but also a rinsing solution for the treatment of an already conversion-coated metallic surface.
- such a rinse solution contains, in addition to water, at least one kind of metal ion selected from the group consisting of the ions of the following metals in the following preferred, particularly preferred and most preferred concentration ranges (all calculated as corresponding metal):
- the metal ions are molybdenum ions. These are preferably added as molybdate, more preferably as ammonium heptamolybdate and particularly preferably as ammonium heptamolybdate x 7 H 2 O to the rinsing solution.
- molybdenum ions can also be added to the post-rinse solution, for example in the form of at least one salt containing molybdenum cations such as molybdenum chloride, and then oxidized to molybdate by a suitable oxidizing agent, for example by the accelerators described above. More preferably, the rinsing solution contains molybdenum ions in combination with copper ions, tin ions or zirconium ions.
- a polymer or copolymer in particular selected from the group consisting of the polymer classes of polyamines, polyanilines, polyimines, polythiophenes and polypryrenes, and mixtures and copolymers thereof and polyacrylic acid, the content of molybdenum ions and zirconium ions each in the range of 10 to 500 mg / l (calculated as metal).
- the content of molybdenum ions is preferably in the range from 20 to 225 mg / l, particularly preferably from 50 to 225 mg / l and very particularly preferably from 100 to 225 mg / l and the content of zirconium ions in the range from 30 to 300 mg / l. l, more preferably from 50 to 200 mg / l.
- the metal ions are copper ions.
- the rinsing solution then contains these in a concentration of 5 to 225 mg / l, more preferably from 150 to 225 mg / l.
- the rinsing solution contains at least one electrically conductive polymer selected from the group consisting of the polymer classes of polyamines, polyanilines, polyimines, polythiophenes and polypryoles. Preference is given to using a polyamine and / or polyimine, more preferably a polyamine.
- the polyamine is preferably a polyethyleneamine, the polyimine is a polyethylenimine.
- the at least one electrically conductive polymer is preferably in a concentration in the range from 0.1 to 5.0 g / l, more preferably from 0.2 to 3.0 g / l and particularly preferably in the range from 0.5 to 1 , 5 g / l (calculated as pure polymer).
- Cationic polymers such as polyamines or polyethyleneimines are preferably used as electrically conductive polymers.
- the rinsing solution contains at least one type of metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin and antimony and at least one electrically conductive polymer selected from the group consisting of the polymer classes of polyamines, Polyanilines, polyimines, polythiophenes and polypryrenes.
- the rinsing solution preferably additionally comprises 10 to 500 mg / l, more preferably 30 to 300 mg / l and particularly preferably 50 to 200 mg / l of Ti, Zr and / or Hf in complexed form (calculated as metal). These are preferably fluoro complexes.
- the rinsing solution preferably comprises 10 to 500 mg / l, more preferably 15 to 100 mg / l and particularly preferably 15 to 50 mg / l of free fluoride.
- the rinsing solution contains Zr in complexed form (calculated as metal) and at least one kind of metal ions selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin and antimony, preferably of molybdenum.
- a rinsing solution comprising Ti, Zr and / or Hf in complexed form preferably additionally contains at least one organosilane and / or at least one hydrolysis product thereof and / or at least one condensation product thereof in a concentration range from 5 to 200 mg / l, more preferably from 10 to 100 mg / l and more preferably from 20 to 80 mg / l (calculated as Si).
- the at least one organosilane preferably has at least one amino group. Particularly preferably it is one which can be hydrolyzed to an aminopropylsilanol and / or to 2-aminoethyl-3-amino-propyl-silanol and / or a bis (trimethoxysilylpropyl) amine.
- the pH of the rinsing solution is preferably in the acidic range, more preferably in the range of 3 to 5, particularly preferably in the range of 3.5 to 5.
- a metallic surface is first treated with an at least largely nickel-free zinc phosphate solution, thus forming an at least largely nickel-free phosphate coating on the metallic surface.
- the thus coated metallic surface is treated with a rinsing solution according to the invention and thus obtain an at least largely nickel-free phosphate coating having a defined electrical conductivity.
- an electrocoating lacquer is deposited cathodically on the metallic surface coated in this way.
- a metallic surface is first treated with a conversion / passivating solution containing 10 to 500 mg / l Zr in complexed form (calculated as metal) and optionally at least one organosilane and / or at least one hydrolysis product thereof and / or at least one condensation product thereof in a concentration range of 5 to 200 mg / l (calculated as Si), and thus forming a corresponding thin film coating on the metallic surface.
- a conversion / passivating solution containing 10 to 500 mg / l Zr in complexed form (calculated as metal) and optionally at least one organosilane and / or at least one hydrolysis product thereof and / or at least one condensation product thereof in a concentration range of 5 to 200 mg / l (calculated as Si), and thus forming a corresponding thin film coating on the metallic surface.
- the thus coated metallic surface is treated with a rinsing solution according to the invention and in this way a thin-film coating having a defined electrical conductivity is
- a metallic surface is first treated with a conversion / passivation solution according to the invention which contains 10 to 500 mg / l Zr in complexed form (calculated as metal) and optionally at least one organosilane and / or at least one hydrolysis product thereof and / or at least one condensation product thereof in a concentration range of 5 to 200 mg / l (calculated as Si), and thus forming a corresponding thin film coating having a defined electrical conductivity on the metallic surface.
- an electrodeposition coating is cathodically deposited on the thus coated metallic surface.
- the electrical conductivity of a conversion coating can be adjusted specifically. In this case, the conductivity can either be greater than, equal to or less than that of a corresponding nickel-containing conversion coating.
- the electrical conductivity of a conversion coating set with the method according to the invention can be influenced by varying the concentration of a given metal ion or electrically conductive polymer.
- the present invention also relates to a concentrate which gives an aqueous composition according to the invention by diluting with water by a factor between 1 and 100, preferably between 5 and 50, and if necessary adding a pH-modifying substance.
- the present invention also relates to a conversion-coated metallic surface obtainable by the process according to the invention.
- a test plate made of electrolytically galvanized steel (ZE) was coated by means of a 1 g / l nickel-containing phosphating solution. No rinsing was done. Subsequently, the current density i in A / cm 2 was compared with the vs. a voltage applied to silver / silver chloride (Ag / AgCl) electrode E is measured in V (see FIG. 1: ZE_Variation1 1_2: curve 3). The measurement was carried out by means of so-called linear sweep voltammetry (potential range: -1, 1 to -0.2 V ref , scan rate: 1 mV / s).
- the measured current density i is dependent on the electrical conductivity of the conversion coating.
- a direct measurement of the electrical conductivity in pS / cm, as is possible in liquid media, can not be carried out in the case of conversion coatings.
- the current density i measured in the case of a nickel-containing conversion coating always serves as a reference point for statements about the electrical conductivity of a given conversion coating.
- a test plate according to Comparative Example 1 was coated by means of a nickel-free phosphating without rinsing and then the current density i over the voltage E according to Comparative Example 1 measured (see Fig. 1. ZE_Variation1_1: curve 1, ZE_Variation1_3: curve 2).
- a test panel according to Comparative Example 1 was nickel-free Phosphating coated. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4. The current density i across the voltage E was measured according to Comparative Example 1 (see FIG. 2. ZE_Variation6_1: curve 1; ZE_Variation6_2: curve 2). Compared with Comparative Example 1 (Fig. 2: ZE_Variation1 1_2: curve 3).
- a test plate according to Comparative Example 1 was coated by means of a nickel-free phosphating solution. Subsequently, the test plate coated in this way was treated with a rinsing solution containing about 220 mg / l copper ions and having a pH of about 4. The current density i across the voltage E was measured according to Comparative Example 1 (see FIG. 3. ZE_Variation2_1: curve 1; ZE_Variation2_2: curve 2). Compared again with Comparative Example 1 (FIG. 3: ZE_Variation1 1_2: curve 3). As can be seen from FIG.
- Example 3 the resting potential of the nickel-free system when using a rinsing solution containing copper ions (Example 1) corresponds to that of the nickel-containing system (Comparative Example 1).
- the conductivity of this nickel-free system is slightly increased over that of the nickel-containing system.
- a test plate according to Comparative Example 1 was coated by means of a nickel-free phosphating solution. Subsequently, the test plate thus coated was treated with a rinsing solution which contained about 1 g / l (calculated on the pure polymer) of electrically conductive polyamine (Lupamin® 9030, manufacturer BASF) and had a pH of about 4.
- the current density i across the voltage E was measured according to Comparative Example 1 (see FIG. 4.
- FIG. 4 FIG. ZE_Variation1 1_2: curve 3).
- the quiescent potential of the nickel-free system when using an after-rinsing solution containing an electrically conductive polymer corresponds to that of the nickel-containing system (Comparative Example 1).
- the electrical conductivity of the nickel-free system is somewhat reduced compared to the nickel-containing system.
- a hot dip galvanized steel (EA) test plate was coated with a phosphating solution containing 1 g / l nickel. Subsequently, the thus-coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) with a pH of about 4, and then the current density i in A / cm 2 was compared with the voltage. a voltage applied to silver / silver chloride (Ag / AgCl) electrode E was measured in V (see FIG. 5: EA 173: curve 1). The measurement was carried out by means of so-called linear sweep voltammetry. Comparative Example 4
- a test plate according to Comparative Example 3 was coated by means of a nickel-free phosphating without rinsing and then the current density i over the voltage E according to Comparative Example 3 measured (see Fig. 5.
- the resting potential of the nickel-free system (Comparative Example 4) is shifted to the right compared to that of the nickel-containing system (Comparative Example 3).
- the electrical conductivity is significantly lower in the case of the nickel-containing system, which is attributable to the passivation by means of the rinsing solution containing ZrF 6 2 ⁇ .
- a test panel according to Comparative Example 3 was coated by means of a nickel-free phosphating solution. Subsequently, the thus coated test plate was treated with a rinsing solution containing about 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 220 mg / l molybdenum ions with a pH of about 4. The current density i over the voltage E was measured according to Comparative Example 1 (see Fig. 6. EA 178: curve 3, EA 178 2: curve 2). Comparison is made with Comparative Example 3 (FIG. 6: EA 173: curve 1).
- FIG. 6 corresponds to the rest potential of the nickel-free system in the use of a ZrF 6 2 ⁇ and molybdenum ion-containing rinsing solution (Example 3) that of the nickel-containing system (Comparative Example 3).
- the addition of molybdenum ions (Example 3) to the post-rinse solution containing ZrF 6 2 (Comparative Example 3) markedly increased the conductivity at the substrate surface.
- Hot-dip galvanized (HDG) or electrolytically galvanized (EG) steel test panels were sprayed with an aqueous cleaning solution containing a surfactant and having a pH of 10.8 for 180 seconds at 60 ° C.
- the cleaning solution was then rinsed off the test panels by first spraying it with city water for 30 seconds and then with deionized water for 20 seconds.
- the cleaned test plates were then immersed for 175 seconds in a conversion / passivation solution containing 40 mg / l of Si, 140 mg / l of Zr, 2 mg / l of Cu and 30 mg / l of free fluoride and having a pH of 4, 8 and a temperature of 30 ° C had.
- the aqueous conversion / passivating solution was then rinsed off the test panels by immersing them in dionized water for 50 seconds and then spraying with deionized water for 30 seconds.
- the pretreated test plates were then cathodically dip coated either with a first special KTL lacquer (KTL 1) or with a second special KTL lacquer (KTL 2).
- Hot-dip galvanized (HDG) or electrolytically galvanized (EG) steel test plates were treated according to Comparative Example 5 with the difference that the aqueous conversion / passivating solution additionally contained 100 mg / l Mo (calculated as metal) added in the form of ammonium heptamolybdate.
- test panels according to Comparative Example 5 (VB5) and Examples 4 to 6 (B4 to B6) were then subjected to a paint adhesion test of the automobile manufacturer PSA (Cataplasmatest).
- This method describes a short electrochemical test carried out on defined, damaged, coated steel sheets.
- the principle of an electrostatic holding test is used to test how well the coating of the test sheet resists the process of corrosive infiltration.
- the cell is filled with approx. 400 ml of 0.1 M sodium sulfate solution. Thereafter, the terminals are connected as follows: green blue terminal on working electrode (sheet), orange-red terminal on counter electrode (electrode with parallel bars), white terminal on reference electrode (in Haber- Lugginkapillare).
- the cathodic polarization is then started via the control software (control unit with software) and a current of 20 mA is set on the test plate over a period of 24 hours. During this time, the measuring cell is tempered with the aid of the thermostat to 40 ° C +/- 0.5 degrees. During the 24-hour loading period, hydrogen develops at the cathode (test plate) and oxygen at the counter electrode.
- the sheet is immediately removed to avoid secondary corrosion, rinsed with deionised water and dried in air. With the help of a blunt knife, the detached lacquer layer is removed. Other detached lacquer areas can be removed with a strong textile adhesive tape (e.g., Tesaband 4657 gray). Thereafter, the exposed area is evaluated ruler, possibly magnifying glass).
- a strong textile adhesive tape e.g., Tesaband 4657 gray
- the width of the detached surface is determined at an interval of 5 mm with an accuracy of 0.5 mm.
- the average width of the softening is calculated according to the following equations:
- n number of individual values
- w width of the scribe in mm
- d mean width of the delamination, infiltration width in mm
- Tab. 2 reveals the poor results of VB2 and in particular VB3 in each case after loading, while B1 (copper ions) and B2 (electrically conductive polyamine) give good - VB1 (nickel - containing phosphating) comparable results.
- a test plate according to Comparative Example 1 was coated by means of a nickel-free phosphating solution. Subsequently, the thus coated test plate was treated with a rinsing solution which about 1 g / l (calculated on the pure polymer) electrically conductive polyimine having a number average molecular weight of 5000 g / mol (Lupasol® G 100, manufacturer BASF) and a pH Value of about 4 had.
- a rinsing solution which about 1 g / l (calculated on the pure polymer) electrically conductive polyimine having a number average molecular weight of 5000 g / mol (Lupasol® G 100, manufacturer BASF) and a pH Value of about 4 had.
- a test plate according to Comparative Example 1 was coated by means of a nickel-free phosphating solution.
- the thus coated test plate was then treated with a rinsing solution containing 130 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 20 mg / l molybdenum ions, which additionally contained 1.2 g / l (calculated on the pure polymer) of polyacrylic acid with a number average Molecular weight of 60,000 g / mol and had a pH of about 4.
- a hot dip galvanized steel (EA) test plate was coated with a nickel-free phosphating solution. Subsequently, the thus coated test plate was treated with a rinsing solution which about 1 g / l (calculated on the pure polymer) electrically conductive polyimine having a number average molecular weight of 5000 g / mol (Lupasol® G 100, manufacturer BASF) and a pH Value of about 4 had.
- a hot dip galvanized steel (EA) test plate was coated with a nickel-free phosphating solution.
- the thus coated test plate was then treated with a rinsing solution containing 130 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 20 mg / l molybdenum ions, which additionally contained 1.2 g / l (calculated on the pure polymer) of polyacrylic acid with a number average Molecular weight of 60,000 g / mol and had a pH of about 4.
- Comparative Example 9 corresponds to Comparative Example 1 with the difference that a steel test plate is used. Comparative Example 9
- a steel test plate was coated with a nickel-free phosphating solution. Subsequently, the test plate thus coated was treated with a rinsing solution containing 230 mg / l copper ions and having a pH of about 4.
- a test plate of electrolytically galvanized steel (ZE) was coated by means of a nickel-free phosphating solution containing 1 g / l BF " and 0.2 g / l SiF 6 2.” Subsequently, the thus coated test plate was treated with a 160 mg / l ZrF 6 2 ⁇ (calculated as Zr) and rinsing solution containing 240 mg / l molybdenum ions treated with a pH of about 4.
- the phosphating solution 1 g / l BF " and 0.2 g / l SiF 6 2 ⁇ contains and after phosphating with a with a 120 mg / l ZrF 6 2 ⁇ (calculated as Zr) rinsing solution is treated with a pH of about 4.
- a hot dip galvanized steel (EA) test plate was coated with a nickel-free phosphating solution containing 1 g / L BF " and 0.2 g / L SiF 6" 2. Then, the thus-coated test plate was treated with 160 mg / L ZrF 6 O 2 (calculated as Zr) and rinsing solution containing 240 mg / l molybdenum ions having a pH of about 4 treated.
- a test plate of electrolytically galvanized steel (ZE) was coated by means of a nickel-free phosphating solution containing 1 g / l of SiF 6 2 ⁇ . Subsequently, the thus coated test plate was treated with a 160 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 240 mg / l molybdenum ions rinsing solution having a pH of about 4.
- the phosphating 1 g / l SiF 6 2 ⁇ contains and after phosphating with a with about 120 mg / l ZrF 6 2 ⁇ calculated ( as Zr) containing rinsing solution with a pH of about 4 is treated.
- Example 15 Corresponds to Comparative Example 2 with the difference that a test plate made of hot-dip galvanized steel (EA) is used and the phosphating solution contains 1 g / l SiF 6 2 ⁇ .
- EA hot-dip galvanized steel
- a test plate of hot-dip galvanized steel (EA) was coated by means of a nickel-free phosphating solution containing 1 g / l of SiF 6 2 ⁇ . Subsequently, the thus coated test plate was treated with a 160 mg / l ZrF 6 2 ⁇ (calculated as Zr) and 240 mg / l molybdenum ions rinsing solution having a pH of about 4.
- Test plates according to Comparative Examples 1, 2, 6 and 7 (VB1, VB2, VB6 and VB7) and Examples 7 to 10 (B7 to B10) were KTL-coated.
- Four programs were used, which differed in terms of (a) the ramp duration - ie the time until reaching the maximum voltage -, (b) the maximum voltage and / or (c) the duration of application of the maximum voltage:
- the layer thickness of the deposited KTL coating measured in each case by means of a Fischer DUALSCOPE, can be taken from Table 3.
- Test plates according to Comparative Examples 8 to 17 (VB8 to VB17) and Examples 1 to 15 (B1 1 to B15) were subjected to X-ray fluorescence analysis (RFA).
- Tab. 4 shows the specific content of copper or zirconium and molybdenum (calculated in each case as metal) in the surface. Subsequently, the said test plates were KTL-coated.
- the following programs were used with regard to (a) the ramp duration, ie the time until the maximum voltage was reached, (b) the maximum voltage and / or (c) the duration of the contact the maximum voltage differ:
- VB8, VB9, B1 1 (a) 30 sec. (B) 250 V (c) 240 sec.
- B15 - 10 10 21, 7 Tab. 3 shows in each case a clear decrease in the layer thickness of the KTL lacquer in the case of nickel-free phosphating in comparison to nickel-containing phosphating (VB2 vs. VB1, VB7 vs. VB6).
- the layer thickness obtained with nickel-free phosphating can be increased again (B7 and B8 vs. VB2, B9 and B10 vs. VB6) - in the case of B7 and B9 even beyond the level of nickel-containing phosphating.
- zirconium-containing and molybdenum-containing rinsing solutions (after nickel-free phosphating) according to the invention results in the incorporation of molybdenum into the surface of the test plates, which again brings the KTL deposition (approximately) to the level of nickel-containing phosphating (B12 vs. VB10; vs VB12, B14 vs. VB14, B15 vs. VB16).
Abstract
Description
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PCT/EP2016/057620 WO2016162422A1 (de) | 2015-04-07 | 2016-04-07 | Verfahren zur gezielten einstellung der elektrischen leitfähigkeit von konversionsbeschichtungen |
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EP16717585.0A Active EP3280830B1 (de) | 2015-04-07 | 2016-04-07 | Verfahren zur gezielten einstellung der elektrischen leitfähigkeit von konversionsbeschichtungen |
EP17703041.8A Pending EP3440235A1 (de) | 2015-04-07 | 2017-01-18 | Verbessertes verfahren zur nickelfreien phosphatierung von metallischen oberflächen |
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EP (3) | EP3280831A1 (de) |
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CN (3) | CN107735511B (de) |
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DE (2) | DE102016205814A1 (de) |
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JP6810704B2 (ja) | 2015-04-07 | 2021-01-06 | ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | 化成コーティングの導電性を厳密に調節するための方法 |
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KR20200045487A (ko) | 2017-08-31 | 2020-05-04 | 케메탈 게엠베하 | 금속 표면을 니켈-무함유 인산염처리하는 개선된 방법 |
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