EP2376674B1 - Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation - Google Patents
Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation Download PDFInfo
- Publication number
- EP2376674B1 EP2376674B1 EP09771552.8A EP09771552A EP2376674B1 EP 2376674 B1 EP2376674 B1 EP 2376674B1 EP 09771552 A EP09771552 A EP 09771552A EP 2376674 B1 EP2376674 B1 EP 2376674B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- activating agent
- phosphate
- aqueous
- aqueous colloidal
- water
- 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.)
- Active
Links
- 230000003213 activating effect Effects 0.000 title claims description 286
- 239000003795 chemical substances by application Substances 0.000 title claims description 278
- 238000000034 method Methods 0.000 title claims description 64
- 238000000576 coating method Methods 0.000 title claims description 43
- 239000011248 coating agent Substances 0.000 title claims description 36
- 229910052751 metal Inorganic materials 0.000 title description 5
- 239000002184 metal Substances 0.000 title description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 43
- 229910019142 PO4 Inorganic materials 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000010452 phosphate Substances 0.000 claims description 39
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 34
- 239000003381 stabilizer Substances 0.000 claims description 34
- 229910000077 silane Inorganic materials 0.000 claims description 28
- 230000004913 activation Effects 0.000 claims description 21
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 19
- 239000000084 colloidal system Substances 0.000 claims description 18
- -1 softener Substances 0.000 claims description 18
- 150000003377 silicon compounds Chemical class 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 125000000962 organic group Chemical group 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 230000003115 biocidal effect Effects 0.000 claims description 8
- 239000003139 biocide Substances 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000010979 pH adjustment Methods 0.000 claims description 5
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000003550 marker Substances 0.000 claims description 4
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- 239000003752 hydrotrope Substances 0.000 claims description 3
- 229920000867 polyelectrolyte Polymers 0.000 claims description 3
- 239000003352 sequestering agent Substances 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001246 colloidal dispersion Methods 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 238000007865 diluting Methods 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 description 36
- 239000010960 cold rolled steel Substances 0.000 description 35
- 230000008569 process Effects 0.000 description 25
- 239000013078 crystal Substances 0.000 description 23
- 238000001994 activation Methods 0.000 description 18
- 239000012190 activator Substances 0.000 description 18
- 239000012141 concentrate Substances 0.000 description 17
- 229910052725 zinc Inorganic materials 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 15
- 239000003973 paint Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 9
- 229910000165 zinc phosphate Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229940048084 pyrophosphate Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- PXOYQTCIULSVDQ-UHFFFAOYSA-H [Mn++].[Ni++].[Zn++].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical class [Mn++].[Ni++].[Zn++].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O PXOYQTCIULSVDQ-UHFFFAOYSA-H 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 2
- 150000003008 phosphonic acid esters Chemical class 0.000 description 2
- 150000004819 silanols Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910052718 tin 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010049040 Weight fluctuation Diseases 0.000 description 1
- XBPCOKJWYAVUIE-UHFFFAOYSA-N [SiH4].C(CCC(=O)O)(=O)O Chemical compound [SiH4].C(CCC(=O)O)(=O)O XBPCOKJWYAVUIE-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
-
- 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
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
- Y10T428/2958—Metal or metal compound in coating
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
Definitions
- the invention relates to a process for phosphating metallic surfaces, in which the metallic surfaces are treated before phosphating with an aqueous colloidal activator based on titanium phosphate before phosphating, and corresponding activating agents.
- phosphating has been a pretreatment process used for metallic surfaces for temporary or prolonged corrosion protection and often also for improving the adhesion of a subsequent primer or lacquer layer.
- the zinc-containing phosphating processes which are referred to as so-called layer-forming (i.e., highly visible crystalline layers) phosphating processes, are of excellent quality and to date are only to a limited extent replaced by pretreatment processes with equivalent layer properties.
- layer-forming (i.e., highly visible crystalline layers) phosphating processes are of excellent quality and to date are only to a limited extent replaced by pretreatment processes with equivalent layer properties.
- zinc-nickel or zinc manganese-nickel phosphates are of outstanding quality and usually on aluminum, iron or zinc-rich metallic surfaces under an organic coating for reasons of corrosion protection and paint adhesion mandatory.
- the zinc-containing phosphating require a prior activation for the formation of a high-quality coating, in which the clean or cleaned metallic surface with nuclei on the basis of phosphate colloid and / or phosphate particles and optionally with other substances is occupied.
- the layer of the crystalline zinc-containing phosphate can be formed largely to completely closed.
- a coating of zinc manganese nickel phosphate usually has a coating weight in the range of 1.0 to 3.5 g / m 2 and phosphate crystals of often less than 12 ⁇ m mean Crystal size looks up under the scanning electron microscope.
- the resulting phosphate layer will typically have a coating weight in the range of 5 to 8 g / m 2 and phosphate crystals of often more than 30 ⁇ m mean crystal size under the scanning electron microscope.
- the coat weight for the paint adhesion to the subsequent primer or lacquer layer is much too high, since if the phosphate layers are too thick, too little paint adhesion is to be expected.
- the consequence of the too large phosphate crystals are a lower paint adhesion, a lower corrosion resistance, a lower mechanical strength of the phosphate layer, uneven paint surfaces and a significantly higher chemical consumption. The quality of these properties is often strictly proportional.
- activating agents often have in series production only a period of use of about one day until they need to be enriched to a greater extent with a supplementary solution in order to remain well able to work or or until they are replaced by a new approach solution become.
- activating agents on the market that have a working life of up to about four or five days by the addition of organic polymer in mass production, but which is then limited to working within five working days.
- the limited duration of use manifests itself primarily in the fact that the formed during zinc phosphating phosphate layers due to the changing activator over the working week in their coating weight, for example, from about 1.3 g / m 2 to a coating weight of, for example, 4.5 g / m 2 and thus increase in their layer thickness. This is also associated with a deterioration in corrosion resistance and paint adhesion.
- coating weights of about 1.0 to about 3.5 g / m 2 are permissible in most automotive plants. With an even higher coating weight, however, a decrease in paint adhesion and a higher consumption of chemicals are also associated.
- bath here stands for the treatment bath.
- values of the changes and fluctuations in the layer weight in the range from ⁇ 0.3 to a maximum of ⁇ 1.0 g / m 2 were determined over a week, depending on the laboratory test series or plant, the layer weights always being in the range between 1 , 0 and 3.5 g / m 2 remained. It is advantageous if an activating agent causes only slight property fluctuations and changes in the properties of the phosphate layer produced during the phosphating over the duration of use.
- an activating agent can also be used for a longer time at a higher temperature, that is to say has a higher thermal stability. ie at temperatures in the range of 30 to 60 or possibly even in the range of 30 to 80 ° C can be used permanently. Due to such higher temperature stability, the entire process is less sensitive. Temperature fluctuations, especially in the higher temperature ranges, are then compensated and ensure a constant quality of the phosphate layer. Because if a less temperature-stable activating agent is used for a long time above its temperature stability limit, the agglomeration of the colloids is accelerated and thus degrades the activation effect much faster.
- US 2008/041498 A1 describes compositions and methods for activating metallic surfaces prior to zinc phosphating with activations based on colloidal titanium phosphate and amine compound.
- EP 0 454 211 B1 teaches methods of applying phosphate coatings to metal surfaces by activating with a titanium phosphate activating agent followed by zinc phosphating activating the metal surfaces with an activating bath containing 0.001 to 0.060 g / L Ti, 0.02 to 1.2 g / L orthophosphate calculated as P 2 O 5 , containing 0.001 to 0.1 g / L of Cu and alkali compounds.
- EP 1 930 475 A1 refers to particulate divalent or trivalent phosphate based activators having a mean particle diameter of not more than 3 microns, metal alkoxide and stabilizer, and to methods of activating metallic surfaces prior to zinc phosphating.
- the object is achieved with a method for phosphating metallic surfaces, wherein the metallic surfaces are treated prior to phosphating with an aqueous colloidal activating agent based on phosphate and titanium, wherein the activating agent selected from at least one water-soluble silicon compound having at least one organic group Bis (3-trimethoxysilylpropyl) amine and bis (3-triethoxysilylpropyl) amine, in particular, as hydrolyzed or / and condensed silane / silanol / siloxane / polysiloxane, the total content of the water-soluble silicon compounds having at least one organic group in the activating agent being in the range of 0, 0001 to 0.2 g / L, calculated respectively as silane and / or as a corresponding predominantly silicon-containing starting compound, and wherein the aqueous colloidal activating agent is selected from an aqueous colloidal activating agent (precursor A) via a powder Miges activating agent (precursor B) is prepared and then dissolved and
- the aqueous colloidal activating agent according to the invention preferably comprises titanium phosphate, orthophosphate, alkali metal and optionally at least one stabilizing agent and / or at least one further additive. It preferably contains at least one hydrolyzed or / and condensed silane / silanol / siloxane / polysiloxane.
- the activating agent may preferably be a colloidal solution or colloidal dispersion or a powdery activating agent, the latter being dissolved and dispersed for use in a coating process.
- a powdered activating agent may in particular have a residual water content, optionally including water of crystallization, of between 0 and about 15% by weight.
- at least one water-soluble silicon compound can already be present in a pulverulent activating agent and / or can only be added in water upon dissolution and dispersion of the pulverulent activating agent.
- An aqueous and often colloidal activating agent such as the activating agent A may initially preferably contain a water content in the range from 5 to 90% by weight of water.
- a powdery activating agent such as the activating agent B
- an initial water content of 5 to 30% by weight is preferred
- an aqueous activating agent such as the activating agent D e.g. From an activating agent A
- an initial water content of 20 to 90% by weight is preferred.
- the aqueous and usually colloidal activating agent A is an aqueous mixture which is prepared and / or prepared, for example, by mixing the respective components and optionally also by kneading and optionally with partial drying. Therefore, the aqueous colloidal activating agent A may optionally be present as a powder at the end of the preparation.
- At least one further substance also in the dissolved and / or pulverulent state, may be added to an aqueous or pulverulent activating agent, in particular to the activating agent A, e.g. Dipotassium phosphate, disodium phosphate, potassium pyrophosphate, sodium pyrophosphate, potassium tripolyphosphate, sodium tripolyphosphate, at least one other stabilizer or / and at least one agent e.g. for pH adjustment, e.g. at least one carbonate or / and at least one borate.
- Dipotassium phosphate e.g. Dipotassium phosphate, disodium phosphate, potassium pyrophosphate, sodium pyrophosphate, potassium tripolyphosphate, sodium tripolyphosphate, at least one other stabilizer or / and at least one agent e.g. for pH adjustment, e.g. at least one carbonate or / and at least one borate.
- the powdery activating agent B usually contains colloidal titanium phosphate in a dried state.
- at least one substance e.g. in each case at least one biocide, surfactant, stabilizer or / and additive for pH adjustment, in particular during dissolution and dispersion, are added.
- an aqueous colloidal activating agent according to the invention for example the activating agent D
- an aqueous activating agent such as the activating agent A
- a particularly storable aqueous colloidal activating agent such as the activating agent D
- the dilution is preferably carried out with stirring.
- at least one substance such as in each case at least one biocide, surfactant, stabilizer or / and additive for pH adjustment, in particular during dilution, may be added.
- the aqueous colloidal activating agent according to the invention can be prepared from an aqueous colloidal activating agent (precursor A) via a powdered activating agent (precursor B) and then dissolved and dispersed in water before application to the metallic surfaces (activating agent C) or from an aqueous colloidal activating agent (precursor A) via an aqueous colloidal activating agent (precursor D) are prepared and then diluted before use on the metallic surfaces in water (activating agent E).
- the activating agents may preferably contain at least one stabilizing agent.
- a stabilizer stabilizes in particular the titanium phosphate colloids.
- the titanium phosphate colloids may agglomerate more readily and / or more rapidly in some aqueous colloidal activating agents and / or in some situations of the activating bath, and in particular may impair the activation quality after a short time. The stability and duration of use are then limited. In some aqueous colloidal activators or / and in some situations of the activator bath, the addition or content of stabilizer is advantageous or even necessary for longer stability of the activator bath.
- Table 1 Overview of the various activating agents, their precursors, their contents and their state: activating agent made of Si compound Titanium phosphate colloids stabilizer usual concentration Status A - optional Yes* optional higher concentrated watery or moist B A optional dried up yes * optional higher concentrated powder C A over B Yes Yes optional Treatment bath + aqueous D A optional Yes Yes higher concentrated aqueous e A over D Yes Yes Yes Treatment bath + aqueous * Usually instead of the usual bath concentration, it can also be a concentrate
- the aqueous colloidal activating agents of the invention such as the activating agents C and E contain at least one water-soluble silicon compound having at least one organic group, while an activating agent such as e.g. the activating agents A, B and D in some process variants contain at least one water-soluble silicon compound having at least one organic group.
- the terms “colloid (s)” and “colloidal” designate only titanium phosphate colloids or corresponding contents, since only these colloids have a significant activating effect for a subsequent phosphating.
- An aqueous activating agent such as the activating agent A, C, D or / and E typically contains dissolved and often colloidal components. Its particles are typically partially or completely in the particle sizes of the otherwise conventionally used term “colloidal” (eg finely divided particles with particle sizes approximately between 1 and 100 nm or between 1 and eg 300 nm). You can However, sometimes also have a small proportion of particle sizes up to just over 1 micron size.
- the particle sizes of the activating agent were measured using a Zetasizer Nano ZS from Malvern Instruments Ltd. certainly. In this case, the pH values and conditions of the activator to be measured were chosen so that 0.1 g / L of solids and active ingredients were used without further additives in the state of a bath solution.
- the particle size distribution of an activating agent is polydispersed, ie in a bimodal or multimodal particle size distribution.
- the ready-for-use colloidal activating agents according to the invention are usually present in the concentration of the treatment bath of an activating agent bath, occasionally occasionally also in a slightly elevated concentration, before the concentration of the activator bath is adjusted by dilution with water.
- the activating agents C are commonly referred to in the art as “powder activation”, while the activating agents E are commonly referred to as "liquid activating”.
- An activating agent in a preliminary stage of the production process of an activating agent such as the activating agent A, B and D is usually in a higher concentration than that of the treating bath of an activating agent bath. Preferably, they are highly concentrated. They are usually precursors of the aqueous colloidal activating agents according to the invention, which are used in the concentration of the treatment bath of an activating agent bath.
- a powdered activating agent according to the invention is present as a powder, optionally as a granulated powder. In principle, it can also be produced by spray drying. It is largely or completely dry.
- a pulverulent activating agent preferably has a powder particle size distribution essentially in the range from 1 to 1000 ⁇ m, particularly preferably in the range from 10 to 500 ⁇ m, in substantially dry state determined by sieve analysis with sieves in the range of about 500 to about 25 ⁇ m mesh size. It preferably has an average powder particle size in the range from 25 to 150 ⁇ m, particularly preferably in the range from 40 to 80 ⁇ m.
- the powdered activating agent is preferably present in a readily free-flowing form.
- the colloids are preferably dried up.
- the colloids are in high quality and usually in sufficient quantity.
- aqueous colloidal activating agents of the invention e.g. the activating agents C or / and E are typically present in a colloidal solution and / or colloidal suspension.
- Their titanium phosphate particles are typically partially or completely colloidal.
- An aqueous colloidal activating agent A differs from an aqueous colloidal activating agent C in the concentration or / and in the phase inventory and optionally also in the overall chemical composition.
- the aqueous colloidal activating agent A often also does not contain any substantial content of stabilizing agent, but often substantially or even only at least one orthophosphate and titanium phosphate among the phosphates. It is often highly concentrated.
- an aqueous colloidal activating agent according to the invention in particular an activating agent C or / and E, is unstable, then it is advantageous or even necessary to add stabilizing agents.
- the stability is based on the low or high tendency of the colloids to agglomerate or to lack colloids. Agglomerated or missing colloids have a poor or no activation effect.
- An aqueous colloidal activating agent of the present invention preferably differs from an activating agent of a precursor such as the activating agent A due to the dilution and is usually in a somewhat more stable state because the agglomeration of the colloids is lower.
- An inventive aqueous colloidal activating agent such as the activating agent C with at least one stabilizing agent differs from an activating agent of a precursor such as the activating agent A in particular by a significantly increased stability and thus by overall significantly improved properties of the coating process and the phosphate coating.
- the aqueous colloidal activator D is often a concentrate. It contains colloids in the aqueous phase. Its stability is usually ensured by at least one stabilizing agent.
- an aqueous colloidal activating agent according to the invention e.g. the activating agent E may be prepared from an aqueous more highly concentrated colloidal activating agent of a precursor such as the activating agent D by dilution with water and optionally by adding at least one substance, e.g. in each case at least one biocide, surfactant, stabilizer or / and additive for pH adjustment are produced.
- the concentrates and baths of an aqueous colloidal activating agent according to the invention often have quite similar or identical properties to one another.
- the properties of the phosphate layers upon previous activation with an aqueous colloidal activating agent of the invention such as the aqueous activating agent C or E are often quite similar or the same among themselves.
- the suitability and quality of the activating agent bath can be determined in particular by means of coating weight, visually discernible uniformity of the zinc phosphate layer, degree of coverage with zinc phosphate layer, corrosion test results or / and paint adhesion test results.
- an activating agent such as the activating agent A, B, C, D or / and E as the main ingredient or as an essential ingredient contains at least one phosphate such as e.g. in each case at least one sodium, potassium or / and titanium-containing phosphate, in particular as main constituents, sodium and / or potassium orthophosphate (e) and at least one titanium-containing phosphate.
- phosphate such as e.g. in each case at least one sodium, potassium or / and titanium-containing phosphate, in particular as main constituents, sodium and / or potassium orthophosphate (e) and at least one titanium-containing phosphate.
- the phosphates are in an aqueous colloidal activating agent such as the activating agent A, C, D or / and E in the form of titanium phosphate, titanyl phosphate, disodium phosphate and / or dipotassium phosphate.
- an aqueous colloidal activating agent such as in particular the activating agent A, C, D or / and E may optionally also have a content of at least one stabilizing agent such as pyrophosphate and / or tripolyphosphate.
- the content of an aqueous activating agent such as the activating agent A, C, D or / and E of phosphate may be calculated as phosphate compounds preferably in the range of 0.05 to 400 g / L and more preferably in the range of 0.10 to 280 or from 0.20 to 200 g / L or in the case of a pulverulent activating agent such as activating agent B in the range from 0.5 to 98% by weight and in particular in the range from 3 to 90 or from 10 to 80% by weight ( each for concentrates and baths).
- the content of an aqueous activating agent such as the activating agent A, C, D or / and E of phosphate may be calculated as PO 4 preferably in the range of 0.005 to 300 g / L and more preferably in the range of 0.010 to 200 or 0.020 to 100 g / L or in the case of a pulverulent activating agent such as the activating agent B in the range of 0.1 to 80 wt .-% and in particular in the range of 1 to 65 or from 10 to 50 wt .-% (in each case for concentrates and baths ).
- this silicate content and this silicate do not belong to the term "silicon compound" in the context of this application.
- the at least one silane / silanol / siloxane / polysiloxane is not included in an aqueous or powdered activating agent precursor such as the activating agent A, B or D and then becomes effective only in the preparation of an aqueous colloidal activating agent of the invention such as the activating agent C or E. added.
- the total content of the water-soluble silicon compounds having at least one organic group in an activator precursor such as activator A, B or D may be either about zero or in an aqueous activator such as activator A, C, D or / and E is preferably 0 , 0001 to 50 g / L and in particular 0.001 to 20 g / L, in particular for coating on the metallic surfaces 0.001 to 0.2 g / L, or in a powdered activating agent as in the activating agent B preferably about zero or 0.001 to 25 wt .-% and in particular 0.01 to 5 wt .-%, calculated in each case as silane and / or as a corresponding mainly present silicon-containing starting compound (respectively for concentrates and baths).
- silane or "silanes / silanols / siloxanes / polysiloxanes” in the context of this application is used here for silanes, silanols, siloxanes, polysiloxanes and their reaction products or derivatives, which are often "silane” mixtures. It is also possible to add a polysiloxane. Particularly preferred is the addition of at least one silane having at least one organic group, where it is common to speak of "silane”, since it often does not know whether the often purchased "silane” at least one silane, at least one silanol, at least a siloxane, at least one polysiloxane or any mixture of these substances.
- silanes Even with self-modified "silanes", it is often impossible or only possible with extremely great effort to determine which substances are present at a certain stage of production or after storage or after addition to a solution or suspension. Due to the often complex chemical reactions that occur in this case, and complex analyzes and work, the respective other silanes or other reaction products can usually not be specified.
- the silicon compound in an activating agent such as in the activating agent A, B, D or / and E, it is preferable to contain at least one hydrolyzable or / and at least one at least partially hydrolyzed silane.
- the activating agent contains as silicon compound preferably at least one partially or completely hydrolyzed silane / silanol / siloxane or / and optionally also condensed silane / silanol / siloxane / polysiloxane.
- the content of titanium in an aqueous activating agent such as the activating agent A, C, D or / and E may preferably be in the range of 0.0001 to 10 g / L, more preferably in the range of 0.001 to 5 or 0.005 to 1 g / L or in a powdered activating agent such as the activating agent B preferably be about zero or in the range of 0.001 to 10 wt .-% and in particular in the range of 0.005 to 2 or from 0.01 to 1 wt .-% (in each case for concentrates and baths).
- the total content of cobalt, copper or / and nickel in an aqueous activating agent such as the activating agent A, C, D or / and E may preferably be about zero or in the range of 0.00001 to 0.1 g / L and in particular in the range of 0.0005 to 0.05 or from 0.01 to 0.02 g / L or in a powdered activating agent such as the activating agent B preferably be about zero or in the range of 0.0001 to 2 wt. % and in particular in the range of 0.001 to 0.8 or from 0.01 to 0.4 wt .-% (in each case for concentrates and baths).
- a content of cobalt, copper or / and nickel can contribute to the refinement of the phosphate layer and has a bactericidal effect.
- a weight ratio of the contents of titanium to those of water-soluble silicon compounds having at least one organic group is in the range of (0.3-2.6): 1 as good, in the range of (0.2 - 3.0): 1 as at least sufficient.
- the total content of sodium and / or potassium in an aqueous activating agent such as the activating agent A, C, D or / and E preferably in the range of 0.005 to 300 g / L and in particular in the range of 0.01 to 200 or from 0.02 to 100 g / l or in a powdered activating agent such as the activating agent B, preferably in the range from 0.1 to 70% by weight and in particular in the range from 1 to 60 or from 10 to 50% by weight. (each for concentrates and baths).
- the activating agent may preferably also contain a content of at least one biocide, wetting agent, softening agent, complexing agent, sequestering agent, stabilizing agent or / and markers.
- the total content of at least one labeling ion and / or on at least one labeling compound such. based on lithium, lanthanide (s), yttrium or / and tungsten, as a dye marker and / or as a fluorescent marker in an aqueous activating agent such as the activating agent A, C, D or / and E preferably be about zero or in the range of 0.0001 to 100 g / L and in particular in the range of 0.001 to 10 or from 0.01 to 1 g / L or in a powdered activating agent such as the activating agent B preferably be about zero or in the range of 0.001 to 20 wt .-% and in particular in the range of 0.01 to 10 or from 0.1 to 1 wt .-% (in each case for concentrates and baths).
- an aqueous activating agent such as the activating agent A, C, D or / and E preferably be about zero or in the range of 0.0001 to 100 g / L and in
- at least one softening agent such as in each case at least one / a dicarboxylic acid, tricarboxylic acid, higher carboxylic acid, polycarboxylic acid, oxydicarboxylic acid , Oxytricarbonklare, higher oxycarboxylic acid, polyoxycarboxylic
- HEDP (1-hydroxyethylidene) diphosphonic acid
- Such compounds serve in particular as complexing agents and / or as sequestering agents.
- the content of softening agents in an aqueous activating agent such as the activating agent A, C, D or / and E may preferably be zero or in the range of 0.0001 to 50 g / L and in particular 0.001 to 20 g / L in a powdered activating agent such as the activating agent B preferably be about zero or in the range of 0.001 to 25 wt .-% and in particular 0.01 to 5 wt .-% (in each case for concentrates and baths).
- an activating agent such as the activating agent A, B, C, D or / and E may optionally also contain in each case at least one addition of at least one stabilizing agent.
- a stabilizer stabilizes the titanium phosphate colloids.
- the stabilizing agent may comprise at least one substance, e.g. at least one based on at least one organic polymer, organic Copolvmer, pyrophosphate, tripolyphosphate and / or phosphonate or be.
- the activating agent preferably contains as stabilizing agent in each case at least one / an anionically modified polysaccharide, water-soluble organic copolymer, such as e.g.
- stabilizing agents especially one based on acrylate, ethylene or / and polyelectrolyte, carboxylic acid, phosphonic acid, diphosphonic acid, triphosphonic acid, polyphosphonic acid, polyelectrolyte or / and derivatives thereof, such as e.g. Carboxylic acid esters, phosphonic acid esters or / and derivatives thereof.
- the stabilization takes place via electrostatic and / or steric stabilization.
- orthophosphates also often have a certain, but not a high stabilizing effect, they are not referred to as stabilizing agents for the purposes of this application.
- the content of stabilizing agents in an aqueous activating agent such as the activating agent A, C, D or / and E may preferably be about zero or in the range of 0.0001 to 300 g / L and more preferably 1 to 200 g / L or in a powdered activating agent such as the activating agent B preferably be about zero or in the range of 0.001 to 80 Wt .-% and in particular 1 to 60 wt .-% are (in each case for concentrates and baths).
- an aqueous activating agent such as an activating agent A, C, D or / and E may also have a content of a detergent mixture, of at least one surfactant or / and of at least one hydrotrope such as e.g. in each case at least one alkane sulfate, alkanesulfonate or / and glycol or added to the activating agent.
- Suitable surfactants are in principle all amphoteric, nonionic, anionic and cationic surfactants in question.
- the content of each of at least one detergent mixture, surfactant or / and hydrotrope in an activating agent such as the activating agent A, C, D or / and E may preferably be about zero or in the range of 0.001 to 100 g / L and in particular Range from 0.005 to 50 or from 0.01 to 10 g / L or in a powdered activating agent such as the activating agent B preferably be about zero or in the range of 0.01 to 99 wt .-% and in particular in the range of 0, 05 to 90 or from 0.1 to 80 wt .-% (each for concentrates, baths and activating detergents).
- a wide variety of substances can be used to adjust the pH and / or to buffer the chemical system, preferably at least one borate or / and at least one carbonate.
- Particularly preferred are alkali metal compounds such as e.g. at least one alkali borate or / and at least one alkali carbonate. The content of these compounds can vary within wide limits.
- Activating agent B is preferably about zero or is 0.01 to 95 wt .-% and in particular 0.1 to 90 or 1 to 80 wt .-% (respectively for concentrates, baths and for activating detergents).
- the activating agent may preferably also contain a content of at least one biocide.
- the content of biocide (s) in an activating agent such as the activating agent A, B, C, D or / and E preferably be about zero or in the range of 0.0001 to 2 g / L and in particular in the range of 0.005 to 0 , 3 or from 0.01 to 0.05 g / L or in an activating agent such as the activating agent B preferably be about zero or in the range of 0.01 to 10 wt .-% and in particular in the range of 0.05 to 2 or from 0.1 to 1.5 wt .-% (each for concentrates and baths).
- the pH in an aqueous activating agent such as the activating agent A, C, D and / or E is in the range of 7 to 13, more preferably in the range of 8 to 12 or 8.5 to 11.
- the pH may be Value also be less than 7, if it does not come to disturbing precipitations in Aktivianssstoffbad, or even be greater than 13, if this bath does not attack the system parts too much.
- an aqueous colloidal activating agent of the present invention such as the activating agent C and / or E may be preferably applied at a temperature in the range of 10 to 80 ° C on the metallic surfaces, more preferably in the range of 15 to 60 or 20 to 50 ° C.
- the activating agent according to the invention may preferably be applied to the metallic surfaces by flooding, swelling, spraying, dipping or / and rolling on and optionally squeezing. In most embodiments, the activating agent is applied by spraying or dipping.
- the metallic surfaces may preferably be cleaned, degreased or / and pickled prior to activation and subsequently and / or optionally rinsed with water in between. In many embodiments it is necessary to subsequently rinse with water after cleaning, degreasing or / and pickling.
- the metallic surfaces can preferably be rinsed with water after activation and before phosphating. In many embodiments, this rinse is optional.
- the metallic surfaces may preferably be phosphated after rinsing, rinsed and / or with at least one organic coating such as e.g. at least one primer, at least one lacquer, at least one adhesive carrier and / or at least one adhesive are provided. This can be dried, rinsed or rinsed if necessary after the application of a coating and then dried.
- at least one organic coating such as e.g. at least one primer, at least one lacquer, at least one adhesive carrier and / or at least one adhesive are provided.
- the layer weight of the produced zinc phosphate layer has been found to be satisfactory in the tests at values of 1.5-3 g / m 2 , at values of> 3 - ⁇ 4 g / m 2 and at values between about 1 and 1.5 and between 4 and 4.5 g / m 2 mostly proved to be satisfactory.
- the coating weight is not the only criterion for evaluating the quality of an activating agent bath. Rather, the visually recognizable uniformity of the zinc phosphate layer, the degree of coverage with zinc phosphate layer, the corrosion test results and / or the paint adhesion test results can also be used here.
- the activating agents according to the invention have usually proven to be good if their activating effect turned out to be good or very good over at least 120 h, which is measurable in particular on the coating weight. A good to satisfactory activating effect could even be achieved over more than 300 hours in the case of activating agent baths according to the invention. Because when the activating effect decreases, the increase in the coating weight of the zinc phosphate layer to values above 3.5 g / m 2 and at the macroscopically observable degree of coverage with a zinc phosphate layer or on metallically shiny parts or at points with a rust attack are particularly evident.
- metallic materials are basically all kinds of metallic materials are possible, in particular those of aluminum, iron, copper, titanium, zinc, tin or / and alloys containing aluminum, iron, steel, copper, magnesium, nickel, titanium, zinc or / and tin, wherein their use can also be adjacent or / and successively.
- the material surfaces can also be precoated or / and be, for example, with zinc or an alloy containing aluminum or / and zinc.
- an aqueous colloidal activating agent based on titanium phosphate and at least one other titanium-free phosphate for the treatment of metallic surfaces before phosphating in which the activating agent comprises at least one water-soluble silicon compound having at least one organic group selected from bis (3) trimethoxysilylpropyl) amine and bis (3-triethoxysilylpropyl) amine, in particular, as hydrolyzed or / and condensed silane / silanol / siloxane / polysiloxane, the total content of the water-soluble silicon compounds having at least one organic group in the activating agent being in the range from 0.0001 to 0, 2 g / L, calculated in each case as silane or / and as a corresponding mainly present silicon-containing starting compound.
- the activating agent comprises at least one water-soluble silicon compound having at least one organic group selected from bis (3) trimethoxysilylpropyl) amine and bis (3-triethoxysilylpropyl) amine, in particular,
- the aqueous colloidal activating agent according to the invention is preferably an aqueous colloidal activating agent C which has been prepared from an aqueous colloidal activating agent A via a powdered activating agent B and in which the pulverulent activating agent B has then been dissolved and dispersed in water for application, or an aqueous colloidal activating agent E prepared from an aqueous colloidal activating agent A via an aqueous colloidal activating agent D, wherein the aqueous activating agent E was prepared by dilution with water, the term "colloidal" being based only on titanium phosphate colloids.
- the activating agent may preferably have a composition according to one of the method claims, in particular at least one stabilizing agent.
- aqueous activating agent according to the invention, to the knowledge of the applicant, it is surprisingly possible for the first time to achieve bath life which can be used well without or without the addition of concentrates or / and of supplementing agents for more than 120 h. In this case, either no addition or at most the addition of concentrates and / or supplementation is added up to the amount of bath bath discharged low over the bath life and thereby achieves a nearly constant low coating weight in the range of, for example, 1.0 to 3.5 g / m 2 ,
- the activating agent according to the invention may also preferably be added to a cleaning agent and used in a cleaning agent. This makes it possible to clean and activate in one step and saves at least one bath. This is particularly advantageous for simple production runs without very high quality requirements.
- the metallic articles activated and phosphated by the process according to the invention and optionally also further coated may be used in particular in the automotive industry, the automotive supplier industry and the steel industry, as well as in the construction industry and in apparatus construction.
- the substrates coated by the process according to the invention can be used in particular as wire, wire mesh, tape, sheet metal, profile, cladding, part of a vehicle or missile, element for a household appliance, element in construction, frame, guard rail, radiator or fence element, Form part of complicated geometry or small part such as Screw, nut, flange or spring.
- the duration of use of the activating agent could be increased in part by about a factor of 5 to 10, even without supplementing the activating agent, owing to the addition of a very small amount of at least one silicon compound.
- the quality of the deposited phosphate layer did not deteriorate as a result of the introduction of the measures according to the invention, but could be maintained in consistent quality over the long term.
- the layer weight of the phosphate layer remained largely constant over the entire production period, because the coating weight fluctuations could even be in a laboratory experiment over 5 working days from originally +/- 0.1 to +/- 3.0 g / m 2 in a conventional Aktivtechnischsstoffbad on + / 0.1 to +/- 1.0 g / m 2 are lowered in an activating agent bath according to the invention.
- the average crystal size was roughly estimated when viewed under the Scanning Electron Microscope (SEM) or appropriately magnified SEM images.
- the inventive examples B 1 to B 9 and B 16 to B 27 and the comparative examples VB 10 to VB 15 relate to so-called powder activations and B 28 to B 31 so-called liquid activations.
- phosphating solutions I to V were used in diving.
- they mainly contained nitrite, nitroguanidine or hydrogen peroxide as accelerators.
- cations in addition to alkali metal ions, iron ions, and cations leached from metallic surfaces, they essentially contained only zinc, manganese, and nickel as in typical low-zinc phosphating solutions.
- As anions they partially contained silicon hexafluoride and small amounts of free fluoride.
- the application of the phosphating I to V was carried out by dipping.
- Their free acid FS values ranged from 1.4 to 1.7
- their total acid GS values ranged from 22 to 28
- their total acid Fischer GSF values ranged from 15 to 20, and their S Values as the ratio of FS to GSF were approximately in the range of 0.07 to 0.10.
- Layer weight was determined gravimetrically by weighing before and after peeling the phosphate layer, peeling on aluminum alloys with nitric acid, on steel and zinc rich surfaces with ammonium dichromate solution.
- the various phosphating agents all looked similar and similarly good, but the crystal forms and crystal sizes of the phosphate crystals varied significantly. There were always good or even very good phosphate coatings.
- Table 3 Coatings and test results on coatings using the phosphating solutions on activating and phosphating for 5 days each B 1 B 2 B 3 B 4 B 5 B 6 B 7 B 8 B 9 Type of sheets CRS CRS CRS CRS CRS CRS CRS CRS CRS Activation type C C C C C C C Activating agent no. 17 1 2 3 4 8th 11 12 13 Coating weight g / m 2 beginning 1.7 1.7 1.5 1.5 1.5 1.5 1.8 1.6 1.3 1.7 Coating weight g / m 2 end 2.0 2.0 1.8 1.5 1.6 2 1.5 1.7 1.7 Degree of coverage visually in% 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
- the zinc phosphate crystal sizes were in the inventive examples partially slightly smaller or even significantly smaller than in the comparative examples.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Claims (19)
- Procédé de phosphatation de surfaces métalliques, selon lequel les surfaces métalliques sont traitées avant la phosphatation avec un agent activation aqueux colloïdal à base de phosphate et de titane, caractérisé en ce que l'agent d'activation contient au moins un composé de silicium soluble dans l'eau contenant au moins un groupe organique choisi parmi la bis(3-triméthoxysilylpropyl)amine et la bis(3-triéthoxysilylpropyl)amine notamment sous la forme d'un silane/silanol/siloxane/polysiloxane hydrolysé et/ou condensé, la teneur totale des composés de silicium solubles dans l'eau contenant au moins un groupe organique dans l'agent d'activation se situant dans la plage allant de 0,0001 à 0,2 g/l, calculée à chaque fois en tant que silane et/ou en tant que composé de départ contenant du silicium principalement présent correspondant, et l'agent d'activation aqueux colloïdal étant fabriqué à partir d'un agent d'activation aqueux colloïdal (précurseur A) par le biais d'un agent d'activation pulvérulent (précurseur B), puis dissous et dispersé dans de l'eau avant l'application sur les surfaces métalliques (agent d'activation C), ou à partir d'un agent d'activation aqueux colloïdal (précurseur A) par le biais d'un agent d'activation aqueux colloïdal (précurseur D), puis dilué dans de l'eau avant l'application sur les surfaces métalliques (agent d'activation E).
- Procédé selon la revendication 1, caractérisé en ce qu'au moins une substance telle que p. ex. à chaque fois au moins un biocide, un tensioactif, un stabilisateur et/ou un additif pour l'ajustement du pH est ajoutée, notamment lors de la dissolution et de la dispersion ou lors de la dilution.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent d'activation aqueux colloïdal contient du phosphate de titane, de l'orthophosphate, un métal alcalin, et éventuellement au moins un stabilisateur et/ou un autre additif.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la teneur de l'agent d'activation aqueux en titane se situe dans la plage allant de 0,0001 à 10 g/l.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la teneur de l'agent d'activation aqueux en phosphate calculée en tant que PO4 se situe dans la plage allant de 0,005 à 300 g/l.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le phosphate se présente dans l'agent d'activation aqueux colloïdal sous la forme de phosphate de titane, de phosphate de titanyle, de phosphate de disodium et/ou de phosphate de dipotassium.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la teneur totale de l'agent d'activation aqueux en cobalt, cuivre et/ou nickel se situe dans la plage allant de 0,00001 à 0,1 g/l.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent d'activation contient à chaque fois au moins un polysaccharide modifié anioniquement, un copolymère organique soluble dans l'eau, un acide carboxylique, un acide phosphonique, un acide diphosphonique, un acide triphosphonique, un acide polyphosphonique, un polyélectrolyte et/ou leurs dérivés.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent d'activation présente également une teneur en un mélange de détergents, en au moins un tensioactif et/ou en au moins un hydrotrope.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent d'activation présente également une teneur en à chaque fois au moins un biocide, un agent mouillant, un agent de ramollissement, un complexant, un séquestrant et/ou un marqueur.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent d'activation est une solution colloïdale ou une dispersion colloïdale ou un agent d'activation pulvérulent, ce dernier étant dissous et dispersé pour l'utilisation dans un procédé de revêtement.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent d'activation est appliqué sur les surfaces métalliques à une température dans la plage allant de 10 à 80 °C.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent d'activation est appliqué sur les surfaces métalliques par inondation, gonflement, pulvérisation, immersion et/ou cylindrage, et éventuellement essorage.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les surfaces métalliques sont nettoyées, dégraissées et/ou décapées avant l'activation et/ou rincées avec de l'eau après l'activation et avant la phosphatation.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'après l'activation, les surfaces métalliques sont phosphatées, rincées et/ou munies d'au moins un revêtement organique.
- Agent d'activation aqueux colloïdal à base de phosphate de titane et d'au moins un autre phosphate ne contenant pas de titane pour le traitement de surfaces métalliques avant une phosphatation, caractérisé en ce que l'agent d'activation contient au moins un composé de silicium soluble dans l'eau contenant au moins un groupe organique choisi parmi la bis(3-triméthoxysilylpropyl)amine et la bis(3-triéthoxysilylpropyl)amine notamment sous la forme d'un silane/silanol/siloxane/polysiloxane hydrolysé et/ou condensé, la teneur totale des composés de silicium solubles dans l'eau contenant au moins un groupe organique dans l'agent d'activation se situant dans la plage allant de 0,0001 à 0,2 g/l, calculée à chaque fois en tant que silane et/ou en tant que composé de départ contenant du silicium principalement présent correspondant.
- Agent d'activation aqueux colloïdal selon la revendication 16, qui est un agent d'activation aqueux colloïdal C, qui a été fabriqué à partir d'un agent d'activation aqueux colloïdal A par le biais d'un agent d'activation pulvérulent B, l'agent d'activation pulvérulent B ayant été dissous et dispersé dans de l'eau pour l'application, ou un agent d'activation aqueux colloïdal E, qui a été fabriqué à partir d'un agent d'activation aqueux colloïdal A par le biais d'un agent d'activation aqueux colloïdal D, l'agent d'activation aqueux E ayant été fabriqué par dilution avec de l'eau, le terme « colloïdal » se rapportant uniquement aux colloïdes de phosphate de titane.
- Utilisation d'un agent d'activation selon l'une quelconque des revendications 16 ou 17 dans un agent de nettoyage.
- Utilisation des substrats revêtus par le procédé selon l'une quelconque des revendications 1 à 15 en tant que fil, treillis métallique, bande, tôle, profilé, habillage, partie d'un véhicule ou d'un missile, élément pour un appareil ménager, élément dans le bâtiment, châssis, élément de glissière de sécurité, de corps de chauffe ou de clôture, pièce moulée de géométrie compliquée ou petite pièce.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008054407.8A DE102008054407B4 (de) | 2008-12-09 | 2008-12-09 | Verfahren zur Beschichtung von metallischen Oberflächen mit einem Aktivierungsmittel vor dem Phosphatieren, entsprechende Aktivierungsmittel sowie Verwendung der mit dem Verfahren beschichteten Substrate |
PCT/EP2009/066680 WO2010066765A1 (fr) | 2008-12-09 | 2009-12-09 | Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2376674A1 EP2376674A1 (fr) | 2011-10-19 |
EP2376674B1 true EP2376674B1 (fr) | 2018-03-14 |
Family
ID=41490397
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09771552.8A Active EP2376674B1 (fr) | 2008-12-09 | 2009-12-09 | Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation |
Country Status (10)
Country | Link |
---|---|
US (2) | US9364855B2 (fr) |
EP (1) | EP2376674B1 (fr) |
JP (1) | JP5595414B2 (fr) |
CN (2) | CN106947967B (fr) |
BR (1) | BRPI0922732B1 (fr) |
CA (1) | CA2746090C (fr) |
DE (1) | DE102008054407B4 (fr) |
ES (1) | ES2673644T3 (fr) |
MX (1) | MX2011006059A (fr) |
WO (1) | WO2010066765A1 (fr) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102013202286B3 (de) * | 2013-02-13 | 2014-01-30 | Chemetall Gmbh | Verwendung eines Silan-, Silanol- oder/und Siloxan-Zusatzes zur Vermeidung von Stippen auf Zink-haltigen Metalloberflächen und Verwendung der beschichteten Metallsubstrate |
WO2015124322A1 (fr) * | 2014-02-20 | 2015-08-27 | Tata Steel Ijmuiden B.V. | Traitement d'activation de substrats d'acier revêtus |
DE102014105226A1 (de) | 2014-04-11 | 2015-10-15 | Thyssenkrupp Ag | Verfahren zur Aktivierung von zu phosphatierenden Metalloberflächen, vorzugsweise verzinktem Stahlblech |
JP6660116B2 (ja) * | 2015-08-03 | 2020-03-04 | 東京応化工業株式会社 | シランカップリング剤水溶液、単分子膜製造方法及びめっき造形方法 |
CN105063577A (zh) * | 2015-08-25 | 2015-11-18 | 山东建筑大学 | 一种耐高温磷酸钙盐-磷灰石膜层的制备方法 |
CN105106022B (zh) * | 2015-08-25 | 2018-05-01 | 福建省诺希科技园发展有限公司 | 一种抗菌牙齿生长修复材料的制备方法 |
CN105887064B (zh) * | 2016-06-15 | 2018-01-23 | 武汉钢铁有限公司 | 一种汽车镀锌板磷化处理生产方法 |
CN107090206A (zh) * | 2017-05-04 | 2017-08-25 | 明光市飞洲新材料有限公司 | 一种铸造涂料专用悬浮触变剂的制造方法 |
GB2561260B (en) | 2017-06-21 | 2019-05-08 | C Ling Ltd | Pull-in head assembly |
KR101968836B1 (ko) * | 2017-09-26 | 2019-04-12 | 현대제철 주식회사 | 전기아연도금강판 및 이의 제조방법 |
CN111455366A (zh) * | 2020-04-03 | 2020-07-28 | 贵州水钢同鑫晟金属制品有限公司 | 一种改性无磷无硼镀膜剂及其制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58131177A (ja) * | 1982-01-29 | 1983-08-04 | Nisshin Steel Co Ltd | 耐熱性塗装アルミメツキ鋼板の製造方法 |
DE3731049A1 (de) * | 1987-09-16 | 1989-03-30 | Henkel Kgaa | Verfahren zur herstellung von aktivierenden titanphosphaten fuer die zinkphosphatierung |
DE4012795A1 (de) * | 1990-04-21 | 1991-10-24 | Metallgesellschaft Ag | Aktivierungsmittel fuer die phosphatierung |
EP1325089A2 (fr) * | 2000-09-25 | 2003-07-09 | Chemetall GmbH | Procede de pretraitement et d'enduction de surfaces metalliques, avant leur fa onnage, au moyen d'un revetement ressemblant a de la peinture, et utilisation de substrats ainsi enduits |
DE60324379D1 (de) * | 2002-12-24 | 2008-12-11 | Chemetall Gmbh | Chemisches Konversionsbeschichtungsmittel und beschichtete Metalloberflächen |
EP1930475A4 (fr) | 2005-08-19 | 2009-07-29 | Nippon Paint Co Ltd | Composition de conditionnement de surface, procédé de fabrication idoine, et procédé de conditionnement de surface |
JP2007204835A (ja) | 2006-02-03 | 2007-08-16 | Nippon Paint Co Ltd | 表面調整用組成物及び表面調整方法 |
US7947333B2 (en) | 2006-03-31 | 2011-05-24 | Chemetall Gmbh | Method for coating of metallic coil or sheets for producing hollow articles |
JP4671050B2 (ja) * | 2006-11-27 | 2011-04-13 | 信越化学工業株式会社 | 含ケイ素水溶性高分子化合物及びその製造方法、プライマー組成物、コーティング剤組成物、並びに該組成物が被覆・処理された物品 |
-
2008
- 2008-12-09 DE DE102008054407.8A patent/DE102008054407B4/de active Active
-
2009
- 2009-12-09 MX MX2011006059A patent/MX2011006059A/es active IP Right Grant
- 2009-12-09 CN CN201610883664.6A patent/CN106947967B/zh active Active
- 2009-12-09 WO PCT/EP2009/066680 patent/WO2010066765A1/fr active Application Filing
- 2009-12-09 US US13/131,106 patent/US9364855B2/en active Active
- 2009-12-09 JP JP2011540064A patent/JP5595414B2/ja active Active
- 2009-12-09 CA CA2746090A patent/CA2746090C/fr not_active Expired - Fee Related
- 2009-12-09 BR BRPI0922732 patent/BRPI0922732B1/pt active IP Right Grant
- 2009-12-09 EP EP09771552.8A patent/EP2376674B1/fr active Active
- 2009-12-09 CN CN2009801563256A patent/CN102308024A/zh active Pending
- 2009-12-09 ES ES09771552.8T patent/ES2673644T3/es active Active
-
2013
- 2013-10-25 US US14/063,209 patent/US9358574B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
DE102008054407A1 (de) | 2010-06-10 |
WO2010066765A1 (fr) | 2010-06-17 |
US9364855B2 (en) | 2016-06-14 |
CA2746090A1 (fr) | 2010-06-17 |
BRPI0922732B1 (pt) | 2019-12-10 |
BRPI0922732A2 (pt) | 2016-01-05 |
EP2376674A1 (fr) | 2011-10-19 |
DE102008054407B4 (de) | 2018-03-29 |
CN106947967A (zh) | 2017-07-14 |
US20110226159A1 (en) | 2011-09-22 |
JP5595414B2 (ja) | 2014-09-24 |
ES2673644T3 (es) | 2018-06-25 |
JP2012511631A (ja) | 2012-05-24 |
CA2746090C (fr) | 2018-04-17 |
US9358574B2 (en) | 2016-06-07 |
US20140051311A1 (en) | 2014-02-20 |
CN106947967B (zh) | 2020-07-03 |
CN102308024A (zh) | 2012-01-04 |
MX2011006059A (es) | 2011-08-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2376674B1 (fr) | Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation | |
EP2255025B2 (fr) | Procédé d enduction de surfaces métalliques avec un agent de passivation | |
DE102008014465B4 (de) | Mittel zur optimierten Passivierung auf Ti-/Zr-Basis für Metalloberflächen und Verfahren zur Konversionsbehandlung | |
EP0454211B1 (fr) | Procédé pour appliquer des couches de phosphates sur des surfaces métalliques | |
WO2014076105A2 (fr) | Procédé de revêtement de surfaces métalliques avec des couches d'oxyde de zinc nanocristallin, compositions aqueuses correspondantes et utilisation des surfaces ainsi revêtues | |
EP3802915A1 (fr) | Dispersion aqueuse pour l'activation d'une surface métallique et son procédé de phosphatation | |
EP3612663B1 (fr) | Procédé formant des couches de phosphatate de zinc sur des composants métalliques en série | |
WO2019158508A1 (fr) | Procédé de phosphatation sélective d'une construction métallique composite | |
WO2022048963A1 (fr) | Procédé en une étape pour la phosphatation du zinc | |
EP3676419B1 (fr) | Procédé amélioré de phosphatage sans nickel des surfaces métalliques | |
EP2255028B1 (fr) | Peinture électrophorétique par immersion optimisée d'éléments assemblés et partiellement préphosphatés | |
EP4065749B1 (fr) | Procédé économe en ressources permettant d'activer une surface métallique avant une phosphatation | |
WO2010031779A1 (fr) | Procédé de préparation de phosphate de titane iv | |
DE102013202286B3 (de) | Verwendung eines Silan-, Silanol- oder/und Siloxan-Zusatzes zur Vermeidung von Stippen auf Zink-haltigen Metalloberflächen und Verwendung der beschichteten Metallsubstrate | |
EP3918108B1 (fr) | Composition alternative et procédé alternatif de phosphatation effective de surfaces métalliques | |
EP4065748A1 (fr) | Procédé d'économie de ressources pour activer une surface métallique avant un processus de phosphatation | |
EP4196625A1 (fr) | Procédé de conservation de ressources pour la phosphatation au zinc d'une surface métallique | |
WO1993022474A1 (fr) | Procede de phosphatation sans nickel avec du cuivre | |
WO1999020696A1 (fr) | Procede pour recouvrir des metaux et metal muni d'un revetement selon ledit procede | |
WO2023078791A1 (fr) | Traitement en plusieurs étapes pour la phosphatation activée du zinc de composants métalliques avec surfaces de zinc | |
EP1509636A2 (fr) | Couche de conversion pour bases en zinc ou en alliages de zinc |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20110711 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20160226 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20171208 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 978965 Country of ref document: AT Kind code of ref document: T Effective date: 20180315 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502009014825 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2673644 Country of ref document: ES Kind code of ref document: T3 Effective date: 20180625 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20180314 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180614 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180614 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180615 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502009014825 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180716 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 |
|
26N | No opposition filed |
Effective date: 20181217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181209 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20181231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181231 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181231 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 978965 Country of ref document: AT Kind code of ref document: T Effective date: 20181209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180314 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180314 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20091209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180714 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20231219 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20231221 Year of fee payment: 15 Ref country code: FR Payment date: 20231226 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20240118 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20231227 Year of fee payment: 15 |