EP2145031B1 - Prétraitement de métallisation de surfaces de zinc - Google Patents
Prétraitement de métallisation de surfaces de zinc Download PDFInfo
- Publication number
- EP2145031B1 EP2145031B1 EP08749904.2A EP08749904A EP2145031B1 EP 2145031 B1 EP2145031 B1 EP 2145031B1 EP 08749904 A EP08749904 A EP 08749904A EP 2145031 B1 EP2145031 B1 EP 2145031B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- cations
- compounds
- galvanized
- acid
- 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.)
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- 238000011282 treatment Methods 0.000 title claims description 29
- 239000011701 zinc Substances 0.000 title description 46
- 229910052725 zinc Inorganic materials 0.000 title description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 33
- 238000000034 method Methods 0.000 claims description 129
- 229910052751 metal Inorganic materials 0.000 claims description 80
- 239000002184 metal Substances 0.000 claims description 80
- 230000008569 process Effects 0.000 claims description 67
- 239000011248 coating agent Substances 0.000 claims description 61
- 238000000576 coating method Methods 0.000 claims description 49
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 150000001768 cations Chemical class 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 39
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 35
- 239000008397 galvanized steel Substances 0.000 claims description 35
- 239000003973 paint Substances 0.000 claims description 31
- 239000008139 complexing agent Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- -1 copper(II) cations Chemical class 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
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- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 230000001603 reducing effect Effects 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
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- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 claims description 2
- SDOFMBGMRVAJNF-UHFFFAOYSA-N 6-aminohexane-1,2,3,4,5-pentol Chemical compound NCC(O)C(O)C(O)C(O)CO SDOFMBGMRVAJNF-UHFFFAOYSA-N 0.000 claims description 2
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
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- DSLZVSRJTYRBFB-UHFFFAOYSA-N Galactaric acid Natural products OC(=O)C(O)C(O)C(O)C(O)C(O)=O DSLZVSRJTYRBFB-UHFFFAOYSA-N 0.000 claims description 2
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- FATUQANACHZLRT-KMRXSBRUSA-L calcium glucoheptonate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)C([O-])=O FATUQANACHZLRT-KMRXSBRUSA-L 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229940048195 n-(hydroxyethyl)ethylenediaminetriacetic acid Drugs 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 150000008163 sugars Chemical class 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000000049 pigment Substances 0.000 description 51
- 238000005260 corrosion Methods 0.000 description 30
- 230000007797 corrosion Effects 0.000 description 29
- 239000000203 mixture Substances 0.000 description 28
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
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- KCTSXBFNNAXQFG-UHFFFAOYSA-N [hydroxy(oxido)phosphaniumyl]phosphinic acid Chemical compound OP(=O)P(O)=O KCTSXBFNNAXQFG-UHFFFAOYSA-N 0.000 description 1
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- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
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- 239000004222 ferrous gluconate Substances 0.000 description 1
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- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000013925 ferrous lactate Nutrition 0.000 description 1
- 239000004225 ferrous lactate Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
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- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Images
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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
-
- 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
-
- 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the present invention relates to a process for the metallizing pretreatment of galvanized and / or alloy-galvanized steel surfaces or assembled metallic components, which at least partially comprise surfaces of zinc, in a surface treatment comprising a plurality of process steps.
- a metallic layer deposit of in particular not more than 100 mg / m 2 of iron is produced on the treated zinc surfaces.
- Such metallized zinc surfaces are outstandingly suitable as starting material for subsequent passivation and coating steps ( illustration 1 , Process II-V) and cause a significantly higher efficiency of the anti-corrosion coating, in particular after the pretreatment of galvanized metal surfaces according to the invention.
- the application of the process on galvanized steel strip prevents corrosive paint infiltration, especially at the cutting edges.
- the invention therefore comprises an uncoated or subsequently coated metallic component which has been given a metallizing pretreatment according to the invention, as well as the use of such a component in vehicle body construction in automobile manufacturing, shipbuilding, construction and for the production of white goods.
- car bodies consist of a large number of sheet-metal parts which are joined together by spot welding.
- corrosion protection which must be able to mitigate both the consequences of bimetallic corrosion and cut edge corrosion.
- metallic zinc coatings which are applied to the steel strip by electrolytic or hot-dip processes, provide a cathodic protection which prevents active dissolution of the more noble core material at cut edges and mechanically induced damage to the zinc coating, ligation is equally important for ensuring the material properties of the core material the corrosion rate itself.
- Correspondingly high are the requirements for the corrosion protection coating consisting mostly of an inorganic conversion layer and an organic barrier layer.
- the galvanic coupling between core material and metallic coating brings about an active, unimpeded local dissolution of the coating material, which in turn constitutes an activation point for the corrosive infiltration of the organic barrier layer.
- the phenomenon of paint peeling or "blistering" is especially observed at the cut edges where unimpeded corrosion of the less noble coating material takes place.
- the local activation of such a "defect" cut edge, damage in the metallic coating, spot welding point
- the corrosive paint release resulting from these "defects” is all the more pronounced the greater the electrical potential difference between the metals in direct contact.
- the prior art describes various pretreatments that address the problem of edge protection.
- An essential strategy is to improve the paint adhesion of the organic barrier layer on the surface-treated steel strip.
- the closest prior art is the German Offenlegungsschrift DE19733972 which deals with a process for the alkaline passivating pretreatment of galvanized and alloy-galvanized steel surfaces in strip lines.
- the surface-treated steel strip is brought into contact with an alkaline treatment agent containing magnesium ions, iron (III) ions and a complexing agent.
- the zinc surface is passivated thereby forming the corrosion protection layer.
- Such a passivated surface offers according to the teaching of DE19733972 already a paint adhesion, which is comparable to nickel and cobalt-containing processes.
- this pretreatment can be followed by further treatment steps such as chromium-free post-passivation to improve the corrosion protection before the paint system is applied. Nevertheless, it appears that this pretreatment system can not satisfactorily suppress the paint peeling caused by the corrosion at the cut edges.
- pretreatment refers to the passivation by means of inorganic barrier layers (eg phosphating, chromating) or a process step preceding the lacquer coating for conditioning the cleaned metallic surface.
- inorganic barrier layers eg phosphating, chromating
- Such conditioning of the surface results in an improvement of the corrosion protection and the paint adhesion for the entire layer system resulting at the end of a process chain for corrosion-protecting surface treatment.
- FIG 1 are typical process chains summarized in the sense of the present invention, which benefit in particular from the pretreatment according to the invention.
- the specifying designation of the pretreatment as "metallising” is to be understood as meaning a pretreatment process which directly entails a metallic deposition of Metal cations (A) effected on the zinc surface, wherein after the metallizing pretreatment at least 50 at .-% of the element (A) according to the method defined in the example part of this application on the zinc surface in the metallic state.
- the redox potential E redox is measured directly on average (1) on a metal electrode of the metal (A) in relation to a standard commercial reference electrode, eg silver-silver chloride electrode.
- the agent (1) according to the invention comprising cations and / or compounds of the metal (A)
- E Zn which is determined at a zinc electrode in the middle (2), which differs from the agent (1) only by the absence of cations and / or compounds of the metal (A), compared to a standard commercial reference electrode: e zn in volts : Ag / AgCl / 1 M KCl / / Zn / M 2
- the method according to the invention is characterized in that a metallizing pretreatment of the zinc surface takes place when the redox potential E redox is more anodic than the electrode potential E Zn . This is the case when E Redox -E Zn > 0.
- the redox potential E redox of the cations and / or compounds of the metal (A) in the aqueous medium (1) is at least +50 mV, preferably at least +100 mV and particularly preferably at least +300 mV, but at most +800 mV anodic than the electrode potential E Zn of the zinc surface in contact with the aqueous agent (2). If the EMF is less than +50 mV, sufficient metallization of the galvanized surface can not be achieved in technically relevant contact times, so that in a subsequent passivating conversion treatment the metal deposit of the metal (A) is completely removed from the galvanized surface and the effect of the pretreatment therewith will be annulled.
- an excessively high EMF of more than +800 mV in short times can lead to a complete and massive occupation of the galvanized surface with the metal (A), so that the desired formation of an inorganic corrosion-inhibiting and adhesion-promoting layer does not occur or at least in a subsequent conversion treatment is hindered.
- the metallization is particularly effective when the concentration of cations and / or compounds of the metal (A) is at least 0.01 M, but does not exceed 0.2 M, preferably 0.1 M.
- Further cations and / or compounds of a metal, which are deposited on the galvanized surface according to the pretreatment in the metallic state, can be contained and are selected from cations and / or compounds of molybdenum, tungsten, cobalt, nickel, lead, and / or tin ,
- iron (II) ions and / or iron (II) compounds for example, iron (II) sulfate can be used.
- the organic salts iron (II) lactate and / or iron (II) gluconate are particularly preferred because of the lower corrosivity of the anions as a source of iron (II) cations.
- the redox potential E redox of the metal (A) must be determined individually and in the absence of the other metals in the aqueous medium.
- particular preference is given to those agents (1) in which only cations and / or compounds of the metal (A) and thus no cations and / or compounds of the aforementioned selection of metals are contained.
- such cations and / or compounds of the metal (A) are included which on the average (1) satisfy both the electromotive force (EMF) condition described above and a standard potential E 0 Me of the metal (A) cathodic located as the Normalpotenial e 0 H2 standard hydrogen electrode (SHE), wherein the standard potential e 0 Me of the metal (a) to the reversible redox reaction Me 0 ⁇ Me n + + ne - in an aqueous solution of the metal cation Me n + with Activity 1 at 25 ° C relates.
- EMF electromotive force
- SHE Normalpotenial e 0 H2 standard hydrogen electrode
- accelerators having a reducing action are added to the aqueous agent (1).
- Possible accelerators are oxo acids of phosphorus and salts thereof, where at least one phosphorus atom must be present in a middle oxidation state.
- Such accelerators are, for example, hypophosphoric acid, hypodiphosphonic acid, diphosphorus (III, V) acid, Phosphonic acid, diphosphonic acid and particularly preferably phosphinic acid and salts thereof.
- the molar ratio of accelerator to the concentration of the cations and / or compounds of the metal (A) in the aqueous medium (1) is preferably not greater than 2: 1, more preferably not greater than 1: 1.
- the aqueous agent (1) in the process according to the invention additionally contain small amounts of copper (II) cations, which can also be deposited metallically on the galvanized surface simultaneously with the cations and / or compounds of the metal (A).
- the aqueous agent (1) should additionally contain not more than 50 ppm, preferably not more than 10 ppm, but at least 0.1 ppm of copper (II) cations.
- the aqueous agent (1) for the metallizing pretreatment may additionally contain surfactants which are able to liberate the metallic surface from impurities without itself inhibiting the surface by forming compact adsorbate layers for the metallization.
- Nonionic surfactants with average HLB values of at least 8 and at most 14 may be used for this purpose.
- the pH of the aqueous agent is not less than 2 and not greater than 6, preferably not greater than 4, in order, on the one hand, to over-stain the galvanized steel surface low pH levels prevent this inhibits the metallization of the surface, and on the other hand to ensure the stability of the iron (II) ions in the treatment solution.
- the iron (II) -containing treatment solution may also contain chelating complexing agents with oxygen and / or nitrogen ligands for stabilization. Such a treatment solution is additionally useful for increasing the EMF for metallization since iron (II) ions are less complexed by such ligands than zinc (II) ions.
- the increase in the emf via the addition of the complexing agents is important for the setting of a shorter treatment time and an optimal iron coverage of the galvanized surface.
- Suitable chelating complexing agents are especially those which are selected from triethanolamine, diethanolamine, monoethanolamine, monoisopropanolamine, aminoethylethanolamine, 1-amino-2,3,4,5,6-pentahydroxyhexane, N- (hydroxyethyl) ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, tartaric acid, lactic acid, mucic acid, gallic acid, gluconic acid and / or glucoheptonic acid and their salts and stereoisomers as well as sorbitol, glucose and glucamine and their stereoisomers.
- a particularly effective formulation of the aqueous agent (1) with the aforementioned complexing agents is at a molar ratio of chelating complexing agent to the concentration of cations and / or bivalent iron compounds of not greater than 5: 1, preferably not greater than 2: 1, but given at least 1: 5.
- Lower molar ratios than 1: 5 change the EMF for metallization only insignificantly.
- higher molar ratios than 5: 1 in which a high proportion of free complexing agent is present, so that the EMF for metallization remains virtually unaffected and results in an uneconomical procedure.
- R 1 represents an alkyl group having not more than 4 carbon atoms
- R 2 represents a substituent of the general formula H (CHOH) m CH 2 - having a number m of hydroxymethylene groups of not more than 5 and not less than 3.
- poly (5-vinyl-2-hydroxy-N-benzyl-N-glucamine) to use because of its pronounced complexing effect.
- a molar ratio of chelating complexing agents defined as the concentration of the monomer units of the water-soluble and / or water-dispersible polymeric compound to the concentration of the cations and / or compounds of the metal (A ), not greater than 5: 1, preferably not greater than 2: 1, but at least 1: 5 particularly effective.
- the application methods customary in strip steel production and strip steel finishing are practicable. These include, in particular, dipping and spraying processes.
- the contact time or pretreatment time with the aqueous agent (1) should be at least 1 second but not longer than 30 seconds, preferably not longer than 10 seconds.
- the metallic layer support is defined as the area-related mass fraction of the element (A) on the galvanized or alloy-galvanized steel surface immediately after the pretreatment according to the invention.
- Both the preferred contact times and layer conditions as well as the preferred application methods also apply to the pretreatment according to the invention of components assembled from a plurality of metallic materials insofar as these at least partially have zinc surfaces.
- the present invention also includes those combinations of alloy-galvanized steel surfaces and aqueous compositions (1) in which an alloying constituent of the galvanized steel surface is the same element (A) as the metal (A) in the form of its cations and / or compounds in the aqueous medium (1).
- an alloying constituent of the galvanized steel surface is the same element (A) as the metal (A) in the form of its cations and / or compounds in the aqueous medium (1).
- hot-dip galvannealed ® -Feinblech according to the invention with a means (1) ferrous ions are pre-treated with the consequence containing that result in a subsequent application of corrosion protective coatings easily improved corrosion and infiltration characteristics.
- the pretreatment process according to the invention is adapted to the subsequent process steps of the surface treatment of galvanized and / or alloy-galvanized steel surfaces with regard to optimized corrosion protection and outstanding paint adhesion, especially at cut edges, surface defects and bimetal contacts. Consequently, the present invention encompasses various aftertreatment processes, ie conversion and lacquer coatings, which, in conjunction with the pretreatment described above, provide the desired results in terms of corrosion protection.
- the illustration 1 illustrates various preferred within the meaning of the present invention process chains for corrosion-protective coating of metallic surfaces in automotive manufacturing, which are already started at the steel producer ("Coil Industry") and continued and completed in the paint shop (“Paint Shop”) at the car manufacturer.
- the invention therefore relates in a further aspect to the production of a passivating conversion coating on the metallized pretreated galvanized and / or alloy-galvanized steel surface with or without intermediate rinsing and / or drying step (US Pat. illustration 1 , Method IIa).
- a chromium-containing or preferably chromium-free conversion solution can be used.
- Preferred conversion solutions with which according to the present invention pretreated metal surfaces can be treated before applying a permanent corrosion protective organic coating the DE-A-199 23 084 and the literature cited herein.
- a chromium-free aqueous conversion agent besides hexafluoro anions of Ti, Si and / or Zr may contain as further active ingredients: phosphoric acid, one or more compounds of Co, Ni, V, Fe, Mn, Mo or W, a water-soluble or water-dispersible film-forming organic polymer or copolymer and organophosphonic acids that have complexing properties.
- phosphoric acid one or more compounds of Co, Ni, V, Fe, Mn, Mo or W
- organophosphonic acids that have complexing properties.
- water-soluble and / or water-dispersible polymeric complexing agents with oxygen and / or nitrogen ligands based on Mannich addition products of polyvinylphenols with formaldehyde and aliphatic amino alcohols may be present.
- Such polymers are in the patent US 5,298,289 disclosed.
- the process parameters for a conversion treatment in the context of this invention are to be chosen such that a conversion layer is produced, the per m 2 surface at least 0.05, preferably at least 0.2, but not more than 3, Contains 5, preferably not more than 2.0 and more preferably not more than 1.0 mmol of the metal M, which is the essential component of the conversion solution.
- metals M are Cr (III), B, Si, Ti, Zr, Hf.
- the coverage of the zinc surface with the metal M can be determined, for example, by an X-ray fluorescence method.
- the chromium-free conversion medium additionally contains copper ions.
- the molar ratio of Metal atoms M selected from zirconium and / or titanium to copper atoms in such a conversion agent is preferably chosen such that this generates a conversion layer in which at least 0.1, preferably at least 0.3, but not more than 2 mmol of copper are additionally included ,
- a method (IIa), in which the metallizing pretreatment is followed by a conversion treatment to form a thin amorphous inorganic coating may also include a method (IIa).
- the metallizing pretreatment and the subsequent conversion treatment usually include further process steps for application additional layers, in particular organic paints or coating systems ( illustration 1 , Method III-V).
- Component a) is a fully reacted polycondensation product of epichlorohydrin and a bisphenol. This essentially has no epoxide groups as reactive groups more.
- the polymer is then in the form of a hydroxyl-containing polyether, which can undergo crosslinking reactions with, for example, polyisocyanates via these hydroxyl groups.
- the bisphenol component of this polymer can be selected, for example, from bisphenol A and bisphenol F.
- the average molar mass (according to the manufacturer, for example determinable by gel permeation chromatography) is preferably in the range from 20,000 to 60,000, in particular in the range from 30,000 to 50,000.
- the OH number is preferably in the range from 170 to 210 and in particular in the range from 180 to 200.
- polymers are preferred whose hydroxyl content based on the Estherharz in the range of 5 to 7 wt .-%.
- the aliphatic polyisocyanates b) and c) are preferably based on HDI, in particular on HDI trimer.
- blocking agents in the blocked aliphatic polyisocyanate b) can the usual polyisocyanate blocking agents be used. Examples which may be mentioned are: butanone oxime, dimethylpyrazole, malonate, diisopropylamine / malonic ester, diisopropylamine / triazole and ⁇ -caprolactam.
- a combination of malonic ester and diisopropylamine is used as the blocking agent.
- the content of blocked NCO groups of component b) is preferably in the range from 8 to 10% by weight, in particular in the range from 8.5 to 9.5% by weight.
- the equivalent weight is preferably in the range of 350 to 600, in particular in the range of 450 to 500 g / mol.
- the non-blocked aliphatic polyisocyanate c) preferably has an equivalent weight in the range of 200 to 250 g / mol and an NCO content in the range of 15 to 23 wt%.
- an aliphatic polyisocyanate can be selected which has an equivalent weight in the range of 200 to 230 g / mol, in particular in the range of 210 to 220 g / mol and an NCO content in the range of 18 to 22 wt .-%, preferably in the range from 19 to 21% by weight.
- Another suitable aliphatic polyisocyanate has for example an equivalent weight in the range of 220 to 250 g / mol, in particular in the range of 230 to 240 g / mol and an NCO content in the range of 15 to 20 wt .-%, preferably in the range of 16 , 5 to 19 wt .-%.
- Each of these aliphatic polyisocyanates mentioned may be component c). However, a mixture of these two polyisocyanates can also be present as component c). If a mixture of the two mentioned polyisocyanates is used, the ratio of the first-mentioned polyisocyanate to the last-mentioned polyisocyanate for component c) is preferably in the range from 1: 1 to 1: 3.
- Component d) is selected from hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates.
- a hydroxyl-containing poly (meth) acrylate having an acid number in the range of 3 to 12, in particular in the range of 4 to 9 mg KOH / g can be used.
- the content of hydroxyl groups is preferably in the range of 1 to 5 and in particular in the range of 2 to 4 wt .-%.
- the equivalent weight is preferably in the range of 500 to 700, in particular in the range of 550 to 600 g / mol.
- a hydroxyl-containing polyester is used as component d
- a branched polyester having an equivalent weight in the range from 200 to 300, in particular in the range from 240 to 280 g / mol can be selected for this purpose.
- a weakly branched polyester having an equivalent weight in the range of 300 to 500, in particular in the range of 350 to 450 g / mol is suitable.
- These different types of polyester can each individually or as a mixture form the component d).
- a mixture of hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates may also be present as component d).
- the coating composition (1) in process (III) according to the invention thus contains both a blocked aliphatic polyisocyanate b) and an unblocked aliphatic polyisocyanate c).
- the hydroxyl-containing components a) and d) are available. Possible reaction of each of components a) and d) with each of components b) and c) produces a complex polymer network of polyurethanes during curing of the agent (2).
- hydroxyl-containing poly (meth) acrylates are used as component d)
- further crosslinking via the double bonds of these components occur.
- component d) consists at least partially of hydroxyl-containing poly (meth) acrylates.
- the coating composition (1) is cured in the process (III) according to the invention, it is to be expected that initially the non-blocked aliphatic polyisocyanate c) reacts with one or both of components a) and d). If the hydroxyl groups of the components d) are more reactive than those of the component a), during curing, first of all, a reaction of the component c) with the component d) occurs.
- the coating composition (1) contains, in addition to the components a) to d), a conductive pigment or a mixture of conductive pigments. These may have a relatively low density, such as carbon black and graphite, or a relatively high density, such as metallic iron.
- the absolute content of the coating composition (1) of the conductivity pigments depends on their density, since it depends less on the mass fraction than on the volume fraction of the conductive pigment in the cured coating for the effect as a conductive pigment.
- the coating composition (1) based on the total mass of the composition, contains (0.8 to 8) .pHW .-% of conductive pigment, where p is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 means.
- the coating composition (1) preferably contains (2 to 6), based on its total mass, ⁇ % by weight of conductive pigment.
- the coating composition (1) contains only graphite having a density of 2.2 g / cm 2 as the conductive pigment, then it preferably contains at least 1.76, in particular at least 4.4, and preferably not more than 17 , 6, in particular not more than 13.2 wt .-% graphite.
- the coating composition (1) based on its total mass, preferably contains at least 6.32, in particular at least 15.8 wt .-% and not more than 63 , 2, in particular not more than 47.4 wt .-% Accordingly, the Gew.-proportions are calculated, if as a conductive pigment, for example, exclusively MoS 2 with a density of 4.8 g / cm3, aluminum with a density of 2.7 g / cm 3 or zinc with a density of 7.1 g / cm 3 is used.
- the coating composition (1) contains not only a single conductive pigment but a mixture of at least two conductive pigments, which then differ greatly in their density.
- a mixture can be used in which the first mixing partner is a light conductive pigment such as carbon black, graphite or aluminum and the second partner of the mixture is a heavy conductive pigment such as zinc or iron.
- the average density of the mixture is used, which can be calculated from the weight percentages of the components in the mixture and from their respective density.
- a specific embodiment of a coating agent (1) in process (IIIb) is characterized in that it contains both a conductive pigment having a density of less than 3 g / cm 3 and a conductive pigment having a density of greater than 4 g / cm 3 , Wherein the total amount of conductive pigment, based on the total mass of the composition (2), is (0.8 to 8) ⁇ ⁇ % by Weight, Where ⁇ is the average density of the mixture of the conductive pigments in g / cm 3 .
- the coating agent (1) as a conductive pigment, a mixture of carbon black or graphite on the one hand and iron powder on the other hand.
- the weight ratios of carbon black and / or graphite on the one hand and iron on the other hand can be in the range from 1: 0.1 to 1:10, in particular in the range from 1: 0.5 to 1: 2.
- the coating composition (1) may therefore contain aluminum flakes, graphite and / or carbon black as a light electrically conductive pigment.
- the use of graphite and / or carbon black is preferred.
- Carbon black, and especially graphite not only provide electrical conductivity of the resultant coating, but also contribute to this layer having a desirable low Mohs hardness of not more than 4 and being readily reshapeable.
- the lubricating effect of graphite contributes to a reduced wear of the forming tools. This effect can be further promoted by additionally using pigments with a lubricating effect such as molybdenum sulfide with.
- the coating agent (1) may contain waxes and / or Teflon.
- the electrically conductive pigment having a specific weight of at most 3 g / cm 3 may be in the form of small spheres or aggregates of such spheres. It is preferred that the balls or the aggregates of these balls have a diameter of less than 2 microns. However, these electrically conductive pigments are preferably in the form of platelets whose thickness is preferably less than 2 ⁇ m.
- the coating composition (1) in process (III) according to the invention comprises at least the resin components described above and also solvents.
- the resin components a) to d) are usually present in their commercial form as a solution or dispersion in organic solvents.
- the coating composition (1) prepared therefrom then also contains these solvents.
- the electrically conductive pigment such as, for example, graphite and optionally further pigments such as, in particular, anticorrosive pigments to set a viscosity which allows the coating agent (1) to be applied to the substrate in the coil coating process.
- additional solvent can be added.
- the chemical nature of the solvents is usually dictated by the choice of raw materials containing the appropriate solvent.
- solvents cyclohexanone, diacetone alcohol, diethylene glycol monobutyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol n-butyl ether, methoxypropyl acetate, n-butyl acetate, Xylene, dimethyl glutarate, dimethyl adipate and / or dimethyl succinate.
- the preferred proportion of solvent on the one hand and organic resin components on the other hand in the coating agent (1) depends on the content of conductive pigment in% by weight in the coating agent (1).
- the preferred weight percentages of solvent and resin components therefore depend on the density ⁇ of the conductivity pigment used or the average density ⁇ of a mixture of conductive pigments.
- the coating composition (1) in the process (III) according to the invention it is preferable that, based on the total mass of the coating composition (1), [(25 to 60). Adjustment factor] Wt%, preferably [(35 to 55) Fitting factor] Wt% organic solvent and [(20 to 45) Fitting factor] Wt%, preferably [(25 to 40) Fitting factor] Wt.
- % organic resin components wherein the sum of the weight percentages of organic resin component and solvent is not greater than [93 * adjustment factor] wt%, preferably not greater than [87 * adaptation factor] wt%, and wherein the adjustment factor [100 -2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
- the coating agent (1) based on the total mass of the coating agent (1), be [(2 to 8) ⁇ adjustment factor]% by weight, preferably [(3 to 5) ⁇ adjustment factor] Wt .-% of the resin component a), wherein the adjustment factor [100-2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 . From the proportion of the resin component a) can be calculated with the above-mentioned preferred ratios of the individual resin components, the preferred proportions of the resin components b) to d) in the coating agent (1).
- the proportion of components b) in the total mass of the coating agent [(2 to 9) adjustment factor] wt .-%, preferably [(3 to 6) adjustment factor] wt%, the proportion of resin components c) [(4 to 18) adjustment factor] wt%, preferably [(6 to 12) adjustment factor] wt% and the proportion of the resin components d) [(7 to 30) ⁇ adjustment factor] wt%, preferably [(10 to 20) ⁇ adjustment factor] wt%.
- the "adaptation factor" has the meaning given above.
- the layer b) additionally contains corrosion inhibitors and / or anticorrosive pigments.
- Corrosion inhibitors or anticorrosive pigments which are known in the prior art for this purpose can be used here. Examples which may be mentioned are: magnesium oxide pigments, in particular in nanoscale form, finely divided and very finely divided barium sulfate or anticorrosive pigments based on calcium silicate.
- the preferred weight fraction of the anticorrosion pigments on the total mass of the coating composition (1) in turn depends on the density of the anticorrosion pigments used.
- the coating composition (1) in the process (III) according to the invention based on the total mass of the coating composition, preferably contains [(5 to 25) adjustment factor]% by weight, in particular [(10 to 20) adjustment factor]% by weight corrosion protection pigment where the adjustment factor is [100-2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
- the mechanical and chemical properties of the coating obtained after the baking of the coating agent (1) in process (III) according to the invention can be further improved by additionally containing fillers.
- these may be selected from silicas or silicas (optionally hydrophobed), alumina (including basic alumina), titania and barium sulfate.
- the coating composition is (1) [(0.1 to 3) adjustment factor]% by weight, preferably [(0.4 to 2) adjustment factor]% by weight filler selected from silicas or Silicon dioxide, aluminum oxide, titanium dioxide and barium sulfate, where the adjustment factor is [100-2.8 p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
- steps (i-vi) are carried out as a strip treatment method, wherein the liquid coating composition (1) is applied in step (vi) in such an amount that, after curing, the desired layer thickness is in the range from 0.5 to 10 receives ⁇ m.
- the coating agent (1) is applied in the so-called coil coating process.
- continuous metal strips are continuously coated.
- the coating agent (1) can be applied by different methods, which are familiar in the prior art. For example, applicator rolls can be used to directly adjust the desired wet film thickness. Alternatively, one can immerse the metal strip in the coating agent (1) or spray it with the coating agent (1), after which the desired wet film thickness is adjusted by means of squeeze rolls.
- step (ii) If metal strips coated immediately before with a metal coating, for example with zinc or zinc alloys, electrolytically or by hot dip coating, it is not necessary to clean the metal surfaces prior to performing the metallizing pretreatment (ii). However, if the metal strips have already been stored and in particular provided with corrosion protection oils, a purification step (i) is necessary before carrying out step (ii).
- the coated sheet is heated to the required drying or crosslinking temperature for the organic coating.
- the treatment agent can also be brought to the corresponding drying or crosslinking temperature by infrared radiation, in particular by near infrared radiation.
- Such pre-coated metal sheets are tailored and converted in the automotive production for the production of bodies accordingly.
- the assembled component or the assembled body shell therefore has unprotected edges, which must be treated in addition corrosion protection.
- the so-called "paint shop” therefore, there is a further corrosion-protective treatment and, ultimately, the realization of the automobile-typical paint structure.
- the present invention therefore relates, in a further aspect, to a process (IV) which extends the process chain (i-vi) of process (III), wherein a crystalline phosphate layer is first deposited on the exposed metal surfaces, in particular on the cut edges, in order to subsequently to provide a final corrosion protection by means of dip paint, in particular protection against infiltration of the paint system at the cutting edges.
- a process (IV) which extends the process chain (i-vi) of process (III), wherein a crystalline phosphate layer is first deposited on the exposed metal surfaces, in particular on the cut edges, in order to subsequently to provide a final corrosion protection by means of dip paint, in particular protection against infiltration of the paint system at the cutting edges.
- the present invention is distinguished by the fact that the zinc surfaces pretreated in a metallizing manner according to the invention in particular excellently prevent edge corrosion.
- a process chain according to the invention which comprises the electrodeposition coating (KTL, ATL) in process (IV) and the application of further paint layers in a process (V), therefore, the amount of deposited dip paint per m 2 of the component consisting of zinc surfaces pretreated according to the invention (US Pat.
- illustration 1 , Method I) and / or the amount of filler to be applied which has the main task of protecting the body panels against stone chipping and compensate for any unevenness of the metal surface, in the secondary coating ( illustration 1 , Method V) are significantly reduced, without a loss of performance in terms of corrosion protection and paint adhesion is the result.
- the present invention relates to the galvanized and / or alloy-galvanized steel surface and the metallic component, which consists at least partially of a zinc surface which has been pretreated by metallizing in accordance with the process according to the invention with the aqueous agent (1) or subsequently this pretreatment with further passivating Conversion layers and / or paints, for example according to the inventive method (II-IV) coated.
- a treated steel surface or treated component is used in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods.
- the measuring chain consists of two galvanic half cells, one half cell containing the agent (1) containing cations and / or compounds of one metal (A), while the other half cell contains the means (2) differing from the agent (1), that it does not have any of cations and / or compounds of a metal (A). Both half-cells are connected to a salt bridge and the voltage difference between a metal electrode of the metal (A) in the middle (1) and a zinc electrode in the middle (2) is measured without current.
- a positive EMF means that the redox potential E redox of the cations and / or compounds of the metal (A) on the average (1) is more anodic than the electrode potential E Zn .
- the EMF is measured according to a measuring chain analogous to Figure 2 documented for an agent (1) containing iron (II) cations, which is suitable for the metallizing pretreatment according to the invention.
- the layer coating of iron on the electrolytically galvanized steel surface can be brought into solution immediately after the process step (ii) wet-chemically in 10 wt .-% hydrochloric acid and determined by atomic absorption spectroscopy (AAS) or alternatively in comparative experiments on pure zinc substrates (99, 9% Zn) by means of X-ray fluorescence analysis (RFA).
- AAS atomic absorption spectroscopy
- RMA X-ray fluorescence analysis
- the process (III) according to the invention is modified in such a way that the process step (ii), ie the metallizing pretreatment, is omitted.
- inventive method (III) is modified in such a way that instead of the process step (ii) an alkaline passivating pretreatment with the commercial product of the applicant (Granodine ® 1303) according to the German laid-open specification DE19733972 (see Tab.1, Ex.1 there) specified formulation based on iron (III) nitrate.
- Tab. 2 shows the results regarding corrosive paint infiltration at the cutting edge after 10 weeks of alternating climate test. Since the coating infiltration progresses differently at different points of the cut edge, Table 2 contains the respective maximum infiltration in mm for the corresponding coating system. Table 2 Infiltration at the cutting edge according to VDA Senstitest (621-415) Examples Infiltration at the cutting edge / mm V1 7.9 V2 6.5 V3 9.4 B1 1.5
- the conversion treatment carried out after an intermediate rinsing with deionized water was carried out in an acidic aqueous composition of 750 ppm Zr as H 2 ZrF 6 20 ppm Cu as Cu (NO 3 ) 2 10 ppm Si as SiO 2 200 ppm Zn as Zn (NO 3 ) 2 at a pH of 4 and a contact time of 90 seconds at a temperature of 20 ° C ( illustration 1 , Method IIa).
- a cathodic dip coating (CathoGuard 500) was applied in a layer thickness of 20 microns and cured sheets in a convection oven at 180 ° C for 30 min before the surface in the center of the sheet along several centimeters down to the steel substrate carved with a scribe's mark to Clemen.
- Table 3 shows the sub-migration values resulting from this experiment at the Ritz after VDA climate change test.
- Table 3 Undercrossing at the Ritz of according to a process chain I ⁇ IIa ⁇ IVa (see illustration 1 ) Coated steel sheets (test sheets Gardobond ®, Fa.
- Figures 6 and 7 again show from the X-ray photoelectronic (XPS) detail spectra of Fe (2p 3/2 ) that the thin iron coating applied in the process according to the invention has a metallic character and significantly more than 50 at% of the iron atoms are present in metallic form. Qualitatively, this is recognizable by the significant shift in the overall peak intensity in favor of peak 1 (FIG. Fig. 7 ) at lower binding energies compared to the intensity of this single peak in alkaline passivation (V2).
- the quantification is done by default using a numerical fit process of the XP detail spectrum using Gaussian single peaks, which allow the determination of the single peak area.
- Table 4 gives quantitatively the chemical bonding state of the iron overlay immediately after the respective exemplary (V2) or inventive (B1) pretreatments.
- Table 4 Percentage Shares of Different Bonding States of Iron on Galvanized Steel Surfaces Determined by X-ray Photoelectron Spectroscopy (XPS) example Fe, metallic / At .-% Fe, oxidic / At .-% V2 28 72 B1 63 37
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Claims (12)
- Procédé de prétraitement par métallisation de surfaces en acier galvanisé avec du zinc ou un alliage du zinc, la surface en acier galvanisé avec du zinc ou un alliage du zinc étant mise en contact avec un milieu aqueux (1) dont la valeur du pH est non inférieure à 2 et non supérieure à 6, caractérisé en ce que le milieu (1) contient(a) des cations et/ou des composés d'un métal (A) qui sont choisis parmi les cations et/ou les composés du fer à une concentration d'au moins 0,001 M,(b) des accélérateurs choisis parmi les oxacides du phosphore et leurs sels, au moins un atome de phosphore étant présent dans une étape d'oxydation intermédiaire,les cations et/ou les composés du métal (A) utilisés étant des ions ferreux et/ou des composés ferreux et le rapport molaire accélérateur sur concentration des cations et/ou des composés du métal (A) ne tombant pas au-dessous de la valeur 1:5 et le potentiel redox ERedox des cations et/ou des composés du métal (A), mesuré sur une électrode métallique de métal (A) à une température de traitement prédéterminée et à une concentration prédéterminée de cations et/ou de composés du métal (A) dans le milieu aqueux (1), étant en contact, de façon plus anodique que le potentiel d'électrode EZN de la surface en acier galvanisé avec du zinc ou un alliage du zinc, avec un milieu aqueux (2) qui ne diffère du milieu (1) que par le fait qu'il ne contient pas de cations et/ou de composés du métal (A).
- Procédé selon la revendication 1, caractérisé en ce que le potentiel redox ERedox des cations et/ou des composés du métal (A) dans le milieu aqueux (1) est en contact avec le milieu aqueux (2) de façon plus anodique d'au moins +50 mV, mais au maximum de +800 mV, que le potentiel d'électrode EZn de la surface en acier galvanisé avec du zinc ou un alliage du zinc.
- Procédé selon l'une des revendications 1 et 2 ou les deux, caractérisé en ce que la concentration de cations et/ou de composés du métal (A) est d'au moins 0,01 M, mais ne dépasse pas 0,2 M.
- Procédé selon la revendication 3, caractérisé en ce que le pH du milieu aqueux est inférieur ou égal à 4.
- Procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le milieu aqueux contient en outre des agents complexants chélateurs comportant des ligands contenant de l'oxygène et/ou de l'azote.
- Procédé selon la revendication 5, caractérisé en ce que les agents complexants chélateurs sont choisis parmi la triéthanolamine, la diéthanolamine, la monoéthanolamine, la mono-isopropanolamine, l'aminoéthyléthanolamine, le I-amino-2,3,4,5,6-pentahydroxyhexane, l'acide N-(hydroxyéthyl)-éthyléne-diaminetriacétique, l'acide éthylènediaminetétraacétique, l'acide diéthylènetriaminepentaacétique, l'acide 1,2-diaminopropanetétraacétique, l'acide 1,3-diaminopropanetétraacétique, l'acide tartrique, l'acide lactique, l'acide mucique, l'acide gluconique et/ou l'acide glucoheptonique et leurs sels et stéréoisomères ainsi que le sorbitol, le glucose et la glucamine et leurs stéréoisomères.
- Procédé selon la revendication 6, caractérisé en ce que le rapport molaire agent complexant chélateur sur concentration de cations et/ou de composés du métal (A) est non supérieur à 5:1, mais d'au moins 1:5.
- Procédé selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce que le milieu aqueux contient en outre des accélérateurs choisis parmi l'hydrazine, l'hydroxylamine, la nitroguanidine, le N-méthylmorpholine-N-oxyde, le glucoheptonate, l'acide ascorbique et les sucres réducteurs.
- Procédé selon l'une ou plusieurs des revendications 1 à 8, caractérisé en ce que le milieu aqueux contient en outre 50 ppm maximum, mais 0,1 ppm minimum, de cations cuivriques.
- Procédé selon l'une ou plusieurs des revendications 1 à 9, caractérisé en ce qu'après la mise en contact de la surface en acier galvanisé avec du zinc ou un alliage du zinc avec le milieu aqueux, on obtient un revêtement métallique de métal (A) avec un placage d'au moins 1 mg/m2, mais de pas plus de 100 mg/m2.
- Procédé selon l'une ou plusieurs des revendications 1 à 10, caractérisé en ce qu'après la mise en contact de la surface en acier galvanisé avec du zinc ou un alliage du zinc avec le milieu aqueux avec ou sans étape de séchage et/ou de rinçage intermédiaire, la surface en acier galvanisé avec du zinc ou un alliage du zinc, qui a subi un prétraitement de métallisation, est soumise à un traitement de conversion-passivation.
- Procédé selon la revendication 11, caractérisé en ce que d'autres étapes de procédé sont mises en oeuvre pour appliquer des couches supplémentaires, en particulier des laques ou des systèmes de laques organiques.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10187987.2A EP2292808B1 (fr) | 2007-05-04 | 2008-04-30 | Prétraitement métallisant de surfaces en zinc |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007021364A DE102007021364A1 (de) | 2007-05-04 | 2007-05-04 | Metallisierende Vorbehandlung von Zinkoberflächen |
PCT/EP2008/055308 WO2008135478A2 (fr) | 2007-05-04 | 2008-04-30 | Prétraitement de métallisation de surfaces de zinc |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10187987.2A Division-Into EP2292808B1 (fr) | 2007-05-04 | 2008-04-30 | Prétraitement métallisant de surfaces en zinc |
EP10187987.2A Division EP2292808B1 (fr) | 2007-05-04 | 2008-04-30 | Prétraitement métallisant de surfaces en zinc |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2145031A2 EP2145031A2 (fr) | 2010-01-20 |
EP2145031B1 true EP2145031B1 (fr) | 2016-03-16 |
Family
ID=39791281
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10187987.2A Active EP2292808B1 (fr) | 2007-05-04 | 2008-04-30 | Prétraitement métallisant de surfaces en zinc |
EP08749904.2A Active EP2145031B1 (fr) | 2007-05-04 | 2008-04-30 | Prétraitement de métallisation de surfaces de zinc |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10187987.2A Active EP2292808B1 (fr) | 2007-05-04 | 2008-04-30 | Prétraitement métallisant de surfaces en zinc |
Country Status (17)
Country | Link |
---|---|
US (1) | US8293334B2 (fr) |
EP (2) | EP2292808B1 (fr) |
JP (2) | JP5917802B2 (fr) |
KR (1) | KR20100028542A (fr) |
CN (1) | CN101675181B (fr) |
AU (1) | AU2008248694B2 (fr) |
BR (1) | BRPI0811537A2 (fr) |
CA (1) | CA2686380C (fr) |
DE (1) | DE102007021364A1 (fr) |
ES (2) | ES2589380T3 (fr) |
HU (2) | HUE030515T2 (fr) |
MX (1) | MX2009011876A (fr) |
PL (2) | PL2292808T3 (fr) |
PT (2) | PT2145031E (fr) |
RU (1) | RU2482220C2 (fr) |
WO (1) | WO2008135478A2 (fr) |
ZA (1) | ZA200907724B (fr) |
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DE102007021364A1 (de) * | 2007-05-04 | 2008-11-06 | Henkel Ag & Co. Kgaa | Metallisierende Vorbehandlung von Zinkoberflächen |
US9574093B2 (en) | 2007-09-28 | 2017-02-21 | Ppg Industries Ohio, Inc. | Methods for coating a metal substrate and related coated metal substrates |
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DE102009047522A1 (de) * | 2009-12-04 | 2011-06-09 | Henkel Ag & Co. Kgaa | Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit Zink- und Eisenoberflächen |
DE102010001686A1 (de) * | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Zusammensetzung für die alkalische Passivierung von Zinkoberflächen |
KR101262497B1 (ko) * | 2011-03-28 | 2013-05-08 | 주식회사 노루코일코팅 | 강판의 흑변 방지용 피막 형성 조성물 및 상기 조성물에 의해 피막이 형성된 강판 및 피막 형성방법 |
DE102011078258A1 (de) | 2011-06-29 | 2013-01-03 | Henkel Ag & Co. Kgaa | Elektrolytische Vereisenung von Zinkoberflächen |
EP2631333A1 (fr) * | 2012-02-24 | 2013-08-28 | Henkel AG & Co. KGaA | Prétraitement de surfaces en zinc avant une passivation |
WO2013160567A1 (fr) | 2012-04-25 | 2013-10-31 | Arcelormittal Investigacion Y Desarrollo, S.L. | Procédé de réalisation d'une tôle prélaquée à revêtements znalmg et tôle correspondante. |
DE102012212598A1 (de) | 2012-07-18 | 2014-02-20 | Henkel Ag & Co. Kgaa | Verzinnende Vorbehandlung von verzinktem Stahl in Gegenwart von Pyrophosphat |
DE102012111066A1 (de) | 2012-11-16 | 2014-06-05 | Salzgitter Flachstahl Gmbh | Beschichtetes Stahlblech mit verbesserten Korrosionseigenschaften und Verfahren zur Herstellung eines solchen Bleches |
CN104338668A (zh) * | 2013-07-30 | 2015-02-11 | 比亚迪股份有限公司 | 一种基材表面自泳涂装的方法以及电子产品外壳 |
RU2591919C1 (ru) * | 2015-04-01 | 2016-07-20 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Установка диффузионного цинкования металлических деталей |
DE102015206812A1 (de) | 2015-04-15 | 2016-10-20 | Henkel Ag & Co. Kgaa | Polymerhaltige Vorspüle vor einer Konversionsbehandlung |
DE102015209910A1 (de) | 2015-05-29 | 2016-12-01 | Henkel Ag & Co. Kgaa | Vorspüle enthaltend ein quartäres Amin zur Konditionierung vor einer Konversionsbehandlung |
DE102015209909A1 (de) | 2015-05-29 | 2016-12-01 | Henkel Ag & Co. Kgaa | Konditionierung vor einer Konversionsbehandlung von Metalloberflächen |
CN105063696A (zh) * | 2015-08-07 | 2015-11-18 | 昆山—邦泰汽车零部件制造有限公司 | 一种耐磨的汽车五金件制造方法 |
JP7035021B2 (ja) | 2016-08-23 | 2022-03-14 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | ジ-又はポリアミンとα,β-不飽和カルボン酸誘導体との反応生成物として得られる接着促進剤の金属表面処理のための使用 |
EP3591092B1 (fr) * | 2017-03-03 | 2024-05-01 | Nissan Motor Co., Ltd. | Élément coulissant de conception élevée |
EP3569734A1 (fr) | 2018-05-18 | 2019-11-20 | Henkel AG & Co. KGaA | Composition de passivation à base de chrome trivalent |
CN109267079A (zh) * | 2018-11-15 | 2019-01-25 | 济南大学 | 一种中性金属表面除锈清洗剂的制备方法 |
FI3663435T3 (fi) | 2018-12-05 | 2024-05-24 | Henkel Ag & Co Kgaa | Fosfori- ja fosfonihappojen seoksiin perustuva passivointikoostumus |
EP3771749A1 (fr) * | 2019-07-29 | 2021-02-03 | Ewald Dörken Ag | Procédé de passivation de substrats métalliques |
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CN110923768B (zh) * | 2019-12-19 | 2022-01-25 | 漳州市福美鑫新材料科技有限公司 | 一种用于三价铬电镀工件后处理工艺的设备 |
CN110983220B (zh) * | 2019-12-30 | 2023-08-18 | 江苏圣大中远电气有限公司 | 核电产品抗磨耐腐蚀表面处理系统 |
WO2021139955A1 (fr) | 2020-01-06 | 2021-07-15 | Henkel Ag & Co. Kgaa | Composition de passivation appropriée pour des surfaces internes de réservoirs d'acier revêtus de zinc stockant des hydrocarbures |
EP3872231A1 (fr) * | 2020-02-28 | 2021-09-01 | voestalpine Stahl GmbH | Procédé de conditionnement de la surface d'un bande métallique revêtu d'une couche de protection contre la corrosion en alliage de zinc |
CN116670236A (zh) | 2021-01-06 | 2023-08-29 | 汉高股份有限及两合公司 | 用于涂锌铝钢的基于Cr(III)的改善钝化 |
GB2603194A (en) | 2021-02-01 | 2022-08-03 | Henkel Ag & Co Kgaa | Improved cr(iii) based dry-in-place coating composition for zinc coated steel |
EP4174211A1 (fr) | 2021-11-02 | 2023-05-03 | Henkel AG & Co. KGaA | Traitement en plusieurs étages permettant d'activer le phosphatation au zinc des composants métalliques pourvus de surfaces en zinc |
CN114108043B (zh) * | 2021-11-19 | 2023-08-11 | 山东省路桥集团有限公司 | 钢结构桥梁锈蚀区域的修复再生预处理方法 |
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-
2007
- 2007-05-04 DE DE102007021364A patent/DE102007021364A1/de not_active Ceased
-
2008
- 2008-04-30 HU HUE10187987A patent/HUE030515T2/en unknown
- 2008-04-30 ES ES10187987.2T patent/ES2589380T3/es active Active
- 2008-04-30 EP EP10187987.2A patent/EP2292808B1/fr active Active
- 2008-04-30 WO PCT/EP2008/055308 patent/WO2008135478A2/fr active Application Filing
- 2008-04-30 RU RU2009144881/02A patent/RU2482220C2/ru not_active IP Right Cessation
- 2008-04-30 PL PL10187987.2T patent/PL2292808T3/pl unknown
- 2008-04-30 HU HUE08749904A patent/HUE028450T2/en unknown
- 2008-04-30 EP EP08749904.2A patent/EP2145031B1/fr active Active
- 2008-04-30 BR BRPI0811537-0A2A patent/BRPI0811537A2/pt not_active Application Discontinuation
- 2008-04-30 MX MX2009011876A patent/MX2009011876A/es active IP Right Grant
- 2008-04-30 JP JP2010504740A patent/JP5917802B2/ja not_active Expired - Fee Related
- 2008-04-30 KR KR1020097025157A patent/KR20100028542A/ko not_active Application Discontinuation
- 2008-04-30 CN CN2008800147916A patent/CN101675181B/zh active Active
- 2008-04-30 CA CA2686380A patent/CA2686380C/fr not_active Expired - Fee Related
- 2008-04-30 PT PT08749904T patent/PT2145031E/pt unknown
- 2008-04-30 PT PT101879872T patent/PT2292808T/pt unknown
- 2008-04-30 ES ES08749904.2T patent/ES2575993T3/es active Active
- 2008-04-30 PL PL08749904.2T patent/PL2145031T3/pl unknown
- 2008-04-30 AU AU2008248694A patent/AU2008248694B2/en not_active Ceased
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- 2009-11-03 ZA ZA2009/07724A patent/ZA200907724B/en unknown
- 2009-11-18 US US12/621,206 patent/US8293334B2/en active Active
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Also Published As
Publication number | Publication date |
---|---|
MX2009011876A (es) | 2010-02-24 |
RU2482220C2 (ru) | 2013-05-20 |
EP2145031A2 (fr) | 2010-01-20 |
WO2008135478A3 (fr) | 2009-01-08 |
CN101675181B (zh) | 2012-10-24 |
AU2008248694A1 (en) | 2008-11-13 |
ZA200907724B (en) | 2011-04-28 |
RU2009144881A (ru) | 2011-06-10 |
ES2589380T3 (es) | 2016-11-14 |
HUE028450T2 (en) | 2016-12-28 |
DE102007021364A1 (de) | 2008-11-06 |
CA2686380C (fr) | 2016-04-05 |
PL2145031T3 (pl) | 2016-09-30 |
JP2010526206A (ja) | 2010-07-29 |
JP2016074985A (ja) | 2016-05-12 |
US8293334B2 (en) | 2012-10-23 |
KR20100028542A (ko) | 2010-03-12 |
PT2145031E (pt) | 2016-06-16 |
ES2575993T3 (es) | 2016-07-04 |
AU2008248694B2 (en) | 2012-10-04 |
PT2292808T (pt) | 2016-09-08 |
CA2686380A1 (fr) | 2008-11-13 |
US20100209732A1 (en) | 2010-08-19 |
WO2008135478A2 (fr) | 2008-11-13 |
JP5917802B2 (ja) | 2016-05-18 |
EP2292808B1 (fr) | 2016-06-08 |
BRPI0811537A2 (pt) | 2014-11-18 |
PL2292808T3 (pl) | 2016-12-30 |
EP2292808A1 (fr) | 2011-03-09 |
HUE030515T2 (en) | 2017-05-29 |
CN101675181A (zh) | 2010-03-17 |
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Inventor name: SANCHIS OTERO, GUADALUPE Inventor name: KUHM, PETER Inventor name: WOLPERS, MICHAEL Inventor name: ROTH, MARCEL Inventor name: HACKBARTH, KARSTEN Inventor name: LORENZ, WOLFGANG Inventor name: MEAGHER, KEVIN Inventor name: WARK, REINER Inventor name: WILKE, EVA Inventor name: ROSENKRANZ, CHRISTIAN |
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