EP3350357A1 - Pre-treating aluminum surfaces with zirconium- and molybdenum-containing compositions - Google Patents
Pre-treating aluminum surfaces with zirconium- and molybdenum-containing compositionsInfo
- Publication number
- EP3350357A1 EP3350357A1 EP16770231.5A EP16770231A EP3350357A1 EP 3350357 A1 EP3350357 A1 EP 3350357A1 EP 16770231 A EP16770231 A EP 16770231A EP 3350357 A1 EP3350357 A1 EP 3350357A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- workpieces
- solution
- metal
- aqueous
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title description 4
- SWCGXFPZSCXOFO-UHFFFAOYSA-N [Zr].[Mo] Chemical compound [Zr].[Mo] SWCGXFPZSCXOFO-UHFFFAOYSA-N 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000011282 treatment Methods 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 19
- 238000005507 spraying Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 11
- 239000008397 galvanized steel Substances 0.000 claims abstract description 11
- 238000003466 welding Methods 0.000 claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 8
- 239000011707 mineral Substances 0.000 claims abstract description 8
- 238000010422 painting Methods 0.000 claims abstract description 5
- 239000011260 aqueous acid Substances 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 20
- 239000003929 acidic solution Substances 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000007598 dipping method Methods 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 238000004026 adhesive bonding Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000005304 joining Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 11
- 239000000956 alloy Substances 0.000 abstract description 11
- 238000007654 immersion Methods 0.000 abstract description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract 2
- 238000003754 machining Methods 0.000 abstract 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 15
- 238000005554 pickling Methods 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- -1 aluminum ions Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000007761 roller coating Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YGSCDVQTKKMYBS-UHFFFAOYSA-N 3-[2-aminoethyl(hydroxy)silyl]propan-1-amine Chemical compound NCC[SiH](O)CCCN YGSCDVQTKKMYBS-UHFFFAOYSA-N 0.000 description 1
- JVRHDWRSHRSHHS-UHFFFAOYSA-N 3-hydroxysilylpropan-1-amine Chemical compound NCCC[SiH2]O JVRHDWRSHRSHHS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JOUOJMIHRPQLAA-UHFFFAOYSA-N ethenylphosphonic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(=O)C=C JOUOJMIHRPQLAA-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—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 characterised by the process
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/76—Applying the liquid by spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
Definitions
- the invention relates to a method for the pretreatment of workpieces with a surface made of aluminum or aluminum alloys for non-cutting forming and / or joining by welding or gluing with similarly pretreated or otherwise otherwise precoated workpieces or with optionally pretreated parts made of steel and / or galvanized and / or alloy-galvanized steel, and for subsequent corrosion-protective treatment by phosphating, by chromium-free conversion treatment, by primer application or by painting.
- the method of EP-B-700 452 envisages contacting surfaces of aluminum or its alloys with an aqueous solution prior to a second permanent anticorrosion treatment for pretreatment, comprising complex fluorides of the elements boron, Contain silicon, titanium, zirconium or hafnium individually or in admixture with each other in concentrations of the fluoro-anions of 100 to 4000 mg / l and have a pH of 0.3 to 3.5.
- the parts made of aluminum or its alloys are subjected to a chipless and / or cutting deformation process, and / or connected to one another or to parts made of steel and / or galvanized and / or alloy-galvanized steel by gluing and / or welding.
- the application of the optionally polymers containing certain state of the art solution can be done by spraying, dipping or no-rinse method, wherein in the case of the no-rinse method, the wet film amount between 2 to 10, preferably between 4 and 6 ml / m 2 metal surface should. Regardless of the form of application of the solution, it is advantageous to dry at temperatures between 40 and 85 ° C.
- the parts made of aluminum or its alloys are acid or alkaline cleaned prior to the first conversion treatment, and cleaning steps and intermediate rinses with water and / or activating rinsing baths preferably take place before the permanent corrosion-protective treatment.
- the object of the invention is a method for the pretreatment of workpieces with a surface made of aluminum or aluminum alloys for non-cutting forming and / or joining by welding or gluing, in particular for bonding by gluing, with similarly pretreated or otherwise otherwise precoated workpieces or with Parts made of steel and / or galvanized and / or alloy galvanized steel, in particular with similarly pretreated workpieces, and to provide a permanent corrosion protection treatment by phosphating and / or by a chrome-free conversion treatment and by primer application and / or painting, in particular by phosphating and a Chrome-free conversion treatment as well as varnishing, which regularly leads to workpieces with a sufficiently low volume resistance and at the same time good phosphatability and adhesive adhesion.
- the method according to the invention should moreover lead to good temporary corrosion protection values and be largely insensitive to bath contamination by aluminum ions.
- the object is achieved, on the one hand, by configuring the method according to the invention in such a way that the workpieces a) are immersed in a dipping or spraying with a mineral acid-containing aqueous, acidic solution,
- aqueous, acidic solution which is chromium-free and contains Zr as complex fluoride and Mo as molybdate in a weight ratio (calculated as Zr / Mo metal) of Zr: Mo of 15: 1 to 3.5: 1, brought by dipping or spraying application in contact, so that after the subsequent drying a coating weight of 2 to 15 mg / m 2 of Zr and Mo results, the Solution contains 100 to 800 mg / l Zr and 30 to 100 mg / l Mo (calculated as Zr / Mo metal) and has a pH of 2.5 to 4.5.
- the aqueous, acidic solution in step c) preferably contains Zr and Mo in a weight ratio of 15: 1 to 5: 1, more preferably from 13: 1 to 7: 1 and very particularly preferably from 1: 1 by immersion or spraying : 1 to 9: 1.
- a coating weight of 2 to 12 mg / m 2 , particularly preferably 2 to 10 mg / m 2 and very particularly preferably 2 to 8 mg / m 2 of Zr and Mo preferably results in the case of immersion or spray application ,
- the aqueous solution contains 250 to 700 mg / l Zr and 30 to 80 mg / l Mo, more preferably 400 to 600 mg / l Zr and 40 to 60 mg / l Mo and most preferably 475 in the case of immersion or spray application to 525 mg / l Zr and 45 to 55 mg / l Mo.
- the aqueous solution in the case of immersion or spray application preferably has a pH of from 3.1 to 4.3 and more preferably from 3.6 to 4.0 and preferably a temperature of from 20 to 50 ° C. and more preferably from 20 to 30 ° C on.
- the object is achieved by the method of the type mentioned according to the invention is designed such that the workpieces a) with a mineral acid-containing aqueous, acidic solution in the dipping or spraying,
- roller coating method brings into contact, so that after the subsequent drying, a coating weight of 2 to 15 mg / m 2 of Zr and Mo results, the solution 0.4 to 7.5 g / l Zr and 0.4 to 7.5 contains g / l Mo (calc. as Zr / Mo metal) and has a pH of 1.0 to 3.0.
- the aqueous solution when applied by roller coating 1, 0 to 6.0 g / l Zr and 1, 0 to 6.0 g / l Mo, more preferably 2.0 to 4.0 g / l Zr and 2.0 to 4 , 0 g / l Mo and most preferably 2.8 to 3.2 g / l Zr and 2.8 to 3.2 g / l Mo.
- the aqueous solution preferably has a pH of from 1.4 to 2.7, and particularly preferably from 1.8 to 2.5, when applied by the roller application method on.
- the aqueous, acidic solution in step c) can by prior dilution of a corresponding concentrate, preferably by a factor of 1: 30 to 1: 100, more preferably by a factor of about 1:50, preferably with water and optionally adjusting the pH value can be provided.
- the workpieces are pickled with a mineral acid-containing aqueous, acidic solution by dipping or spraying.
- Alkaline cleaning results in the formation of zirconium / molybdenum layers with poor volume resistivity values.
- the compound of the invention pretreated workpieces can be pre-coated with similar pretreated or possibly otherwise, for.
- phosphated workpieces done with surfaces of aluminum or its alloys. If intended to be joined to steel and / or galvanized and / or alloy galvanized steel parts, these parts may have bare or precoated surfaces.
- a suitable pre-coating can, for. Example, a phosphate layer with a maximum coating weight of 2 g / m 2 or a layer of a conductive primer.
- the pickling process must be preceded by a cleaning / degreasing stage or the pickling process must be carried out in such a way that simultaneous cleaning / degreasing takes place.
- the latter can be done by adding surfactant to the pickling solution.
- Phosphatier alliance are those who work with solutions based on zinc phosphate, in particular according to the low-zinc technology, or with alkali metal phosphate in the foreground.
- the solutions may be modified by the addition of further small amounts of polyvalent cations, such as calcium, magnesium, nickel, copper or manganese.
- chromium-free conversion treatment in particular acid solutions of the fluoro complexes of titanium, zirconium, hafnium, but also silicon, optionally containing organic polymer, are used.
- These acidic solutions may additionally contain at least one organosilane and / or at least one hydrolysis product thereof and / or at least one condensation product thereof.
- the at least one organosilane preferably has at least one amino group. Particularly preferably it is one which can be hydrolyzed to an aminopropylsilanol and / or to 2-aminoethyl-3-amino-propyl-silanol and / or a bis (trimethoxysilylpropyl) amine.
- reaction primer so-called reaction primer or primer can be applied.
- the pre-treatment of the workpieces according to the invention ensures adequate, temporary corrosion protection for longer storage times. During this time, there is no negative influence on the weldability, in particular the electrical resistance welding, or the bondability. Also, with regard to the weldability, it is ensured that the volume resistance is practically the same on all surface areas of the workpiece.
- Workpieces in the context of the present invention are tape, sheet metal and individual parts, such as profiles.
- the application of the solution according to step c) can be done by spraying or dipping each with or without water rinse. When applied without water rinse, it is advantageous to remove excess treatment solution by squeezing rollers. In the treatment of sheet or strip, the application of the treatment solution by the roll coater method is particularly advantageous. It allows a defined setting of the desired wet film thickness in one operation.
- the workpiece is dried or the solution is dried.
- Object temperatures of 30 to 90 ° C are particularly advantageous.
- Concentrates which are diluted with low-salt water, preferably demineralized water, to the concentrations to be respectively adjusted are usually used to prepare the treatment liquids.
- low-salt water preferably demineralized water
- concentrations to be respectively adjusted are usually used to prepare the treatment liquids.
- the molybdate is advantageously introduced as ammonium heptamolybdate and / or sodium heptamolybdate, preferably as ammonium heptamolybdate and particularly preferably as ammonium heptamolybdate x 7 H 2 O.
- molybdate also includes protonated forms, in particular molybdic acid.
- the pickling of the workpieces is done with a mineral acid-containing aqueous, acidic solution. It can be carried out electrolytically or chemically. In the case of electrolytic pickling, phosphoric acid is particularly suitable as the mineral acid.
- the pickling by chemical means which is given preference because of the apparatus less laborious procedure in the rule, can be made with nitric acid or nitric acid / hydrofluoric acid.
- the workpieces are pickled with a solution by spraying or dipping containing surfactant, sulfuric acid and a compound selected from the group consisting of hydrofluoric acid, phosphoric acid and iron (III) sulfate, preferably hydrogen fluoride, wherein solutions, containing 3 to 8 g / l of sulfuric acid, 50 to 150 mg / l of non-complexed free fluoride and 1 to 3 g / l of nonionic surfactant have been found to be particularly suitable.
- Nonionic surfactants are ethylene oxide Adducts to fatty alcohols and, for example, abietic acid are particularly suitable.
- the measurement of the free fluoride was carried out with a fluoride-sensitive electrode, wherein the calibration of the electrode was carried out with solutions whose pH was identical to that of the solution to be tested.
- the pickling process should be carried out in such a way that a metal removal of about 0.1 to 0.6 g / m 2 workpiece surface is obtained.
- the subsequent to the pickling of the workpieces flushing - according to step b) - is preferably carried out in several rinsing stages, and it is particularly advantageous to perform the rinse water cascade-like the workpiece in the opposite direction.
- the last rinse step should be carried out with demineralized water.
- the subsequent to the pickling and rinsing step treatment according to step c) prevents the re-growth of an oxide layer occurs on the workpieces with a surface made of aluminum or aluminum alloy.
- the solution used in step c) additionally contains at least one polymer selected from the group consisting of poly (meth) acrylic acid, (meth) acrylic acid copolymers, polyvinylphosphonic acid, vinylphosphonic acid copolymers and maleic acid copolymers.
- the (meth) acrylic acid copolymers used are preferably (meth) acrylic acid / maleic acid copolymers and the vinylphosphonic acid copolymers vinylphosphonic acid / acrylic acid copolymers.
- polymers in particular polyacrylic acid and acrylic acid copolymers and in the latter especially acrylic acid-maleic acid copolymers are suitable.
- the poly (meth) acrylic acid used has a number average molecular weight (MW) in the range from 4,000 to 300,000 g / mol, more preferably from 50,000 to 250,000 g / mol and most preferably from 100,000 up to 250,000 g / mol.
- MW number average molecular weight
- the (meth) acrylic acid copolymer used has a number average molecular weight (MW) in the range from 4,000 to 100,000 g / mol and particularly preferably from 60,000 to 80,000 g / mol.
- MW number average molecular weight
- the polyvinylphosphonic acid or vinylphosphonic acid copolymer used preferably has a number average molecular weight (MW) in the range from 4,000 to 70,000 g / mol and particularly preferably in the range from 10,000 to 30,000 g / mol.
- MW number average molecular weight
- the concentration of the at least one polymer is between 100 and 600 mg / l, preferably between 100 and 400 mg / l, more preferably between 135 and 290 mg / l and most preferably between 170 and 180 mg / l.
- a coating weight of Zr and Mo which is more independent of the injection time and preferably largely independent of coating weight in the target range of 2 to 15 mg / m 2 can be achieved in spray application. This is particularly advantageous because even at different tape speeds similar coating weights can be achieved. Negative effects on the volume resistivity, however, are not observed by the polymer content.
- a further advantageous embodiment of the invention provides to apply a lubricant to the workpieces.
- a lubricant are in particular mineral oil-based forming oils, which may be fully synthetic or native, or dry lubricants based on polyethylene / polyacrylate.
- workpieces with layers are regularly obtained which permit perfect deformation and / or gluing or, as a result of the small electrical resistance which is uniform over the workpiece surface, a perfect and trouble-free welding.
- the workpieces are ideally suited for a subsequent permanent corrosion-protective treatment.
- the pickling process was carried out in such a way that the pickling rate for the alloy AA 5754 was 0.05 to 0.2 g / m 2 and for the alloy AA 61 1 1 0.05 to 0.4 g / m 2 . For this treatment times between 5 and 20 seconds were required.
- the volume resistances measured on the single sheet were about 60 ⁇ -ohms for the AA 5754 alloy and about 13 ⁇ -ohms for the AA 61 1 1 alloy.
- the polymers A to D in Table 1 were the following:
- A: polyacrylic acid, MW about 60,000 g / mol in colloidal solution,
- Adhesive adhesion was determined using a modified APGE (Arizona Proving Ground Equivalent) test. To this end, two test slides (each 56.25 x 25 x 0.25 mm) were coated with a dry lubricant customary in the industry and bonded using a suitable industrial adhesive. Six such test plate pairs were then bolted at their respective ends to a chain which was subjected to a tensile stress of 2400 N. The following climate program was used per test week:
- a sequence of steps 1. to 3. represents a cycle by definition. One cycle was passed if the adhesive bond between all of the test slides on the chain withstood. The test was passed as a whole, if at least 45 cycles were passed.
- the phosphatability was determined by scanning electron microscope images. Thus, a "+" - in Table 3, a closed, finely crystalline phosphate layer, an "o” a closed, coarsened phosphate layer (crystals with> 20 ⁇ edge length) and a "-" a non-closed to nonexistent phosphate layer.
- Comparative Example VB1 reveals that owing to an excessively high Zr support weight, the layer obtained in the treatment according to step c) (37 mg / m 2 at AA 5754 and 26 mg / m 2 at AA 61 1 1) has very high volume resistivities - in particular a storage of 30 days - be obtained (100 ⁇ -ohms for AA 5754 and 38 ⁇ -ohms for AA 61 1 1).
- examples B1 to B7 show that, in compliance with the conditions essential to the invention, with regard to the type of pickling treatment, the Zr / Mo ratio, the produced coating weight, the respective Concentration and pH ranges of the treatment solutions layers with extremely good volume resistances at the same time good adhesive properties are obtained.
- the pretreated test slides of Examples B6 and B7 and a non-pretreated bare test slide VB6 were further subjected to a multistage anticorrosive treatment consisting of the following steps: i) Alkaline purification (60 ° C., 180 s)
- the corrosion protection of B6 and B7 is similar to that of VB6.
- the pretreatment according to the invention therefore does not adversely affect the protection subsequently achieved by a corrosion-protective treatment.
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Abstract
Description
Claims
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DE102015217585 | 2015-09-15 | ||
PCT/EP2016/071657 WO2017046139A1 (en) | 2015-09-15 | 2016-09-14 | Pre-treating aluminum surfaces with zirconium- and molybdenum-containing compositions |
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EP3350357A1 true EP3350357A1 (en) | 2018-07-25 |
EP3350357B1 EP3350357B1 (en) | 2024-05-01 |
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US (2) | US20180237919A1 (en) |
EP (1) | EP3350357B1 (en) |
JP (1) | JP2018527467A (en) |
KR (1) | KR20180053306A (en) |
CN (1) | CN108350579A (en) |
CA (1) | CA2996465A1 (en) |
DE (1) | DE102016217507A1 (en) |
MX (1) | MX2018003246A (en) |
RU (1) | RU2750923C1 (en) |
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WO2018095684A1 (en) | 2016-11-23 | 2018-05-31 | Chemetall Gmbh | Composition and method for the chromium-free pretreatment of aluminium surfaces |
CN111601912B (en) * | 2017-09-14 | 2022-07-22 | 凯密特尔有限责任公司 | Method for pretreating aluminum material, in particular aluminum wheel hubs |
US11958989B2 (en) * | 2018-09-07 | 2024-04-16 | Rhodia Operations | Method for treating surfaces of aluminum containing substrates |
MX2021002641A (en) * | 2018-09-07 | 2021-05-12 | Chemetall Gmbh | Method for treating surfaces of aluminum containing substrates. |
JP6846558B1 (en) | 2019-09-27 | 2021-03-24 | 株式会社Uacj | Aluminum alloy material and its manufacturing method |
CN111020551B (en) * | 2019-12-30 | 2022-02-08 | 郑州大学 | Using ZrO2/MoO3Method for protecting irony cultural relics by composite nano film layer |
CN116457498A (en) | 2020-10-29 | 2023-07-18 | 凯密特尔有限责任公司 | Aqueous composition containing zirconium, molybdenum and acid functional polymers for treating metal surfaces |
EP4244404A1 (en) | 2020-11-10 | 2023-09-20 | Chemetall GmbH | Treatment of metallic surfaces by copolymer containing acidic aqueous compositions |
CA3197335A1 (en) | 2020-11-10 | 2022-05-19 | Nawel Souad Khelfallah | Treatment of metallic surfaces by oh-functional copolymer containing acidic aqueous compositions |
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US2312855A (en) | 1940-09-07 | 1943-03-02 | Parker Rust Proof Co | Method of coating aluminum |
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DE1769582C3 (en) | 1967-06-14 | 1979-12-13 | British Chrome & Chemicals Ltd., Stockton-On-Tees (Grossbritannien) | Surface treatment agents for metals, processes for their production and their use for producing corrosion-resistant and electrically resistant coatings |
US3562013A (en) * | 1967-10-23 | 1971-02-09 | Diversey Corp | Process of deoxidizing titanium and its alloys |
US4148670A (en) | 1976-04-05 | 1979-04-10 | Amchem Products, Inc. | Coating solution for metal surface |
DE3236247A1 (en) | 1982-09-30 | 1984-04-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR SURFACE TREATMENT OF ALUMINUM |
KR100292447B1 (en) | 1991-08-30 | 2001-06-01 | 웨인 씨. 제쉬크 | Method of forming protective modified coating on metal substrate surface |
DE69311802T2 (en) * | 1992-04-01 | 1998-02-12 | Henkel Corp | METHOD TREATMENT METHOD |
DE4317217A1 (en) | 1993-05-24 | 1994-12-01 | Henkel Kgaa | Chrome-free conversion treatment of aluminum |
US6020030A (en) | 1998-05-07 | 2000-02-01 | Aluminum Company Of America | Coating an aluminum alloy substrate |
DE19921842A1 (en) * | 1999-05-11 | 2000-11-16 | Metallgesellschaft Ag | Pretreatment of aluminum surfaces with chrome-free solutions |
US6736908B2 (en) * | 1999-12-27 | 2004-05-18 | Henkel Kommanditgesellschaft Auf Aktien | Composition and process for treating metal surfaces and resulting article |
DE10339165A1 (en) * | 2003-08-26 | 2005-03-24 | Henkel Kgaa | Colored conversion coatings on metal surfaces |
CN101332692A (en) * | 2007-06-25 | 2008-12-31 | 宝山钢铁股份有限公司 | Hot-dip aluminizing zinc chrome-free passivated steel-plate and technique thereof |
EP2532769A1 (en) * | 2011-06-10 | 2012-12-12 | Amcor Flexibles Kreuzlingen Ltd. | Method of producing a chromium-free conversion coating on a surface of an aluminium or aluminium alloy strip |
DE102012017438A1 (en) * | 2012-09-04 | 2014-03-06 | Carl Freudenberg Kg | Treatment solution and method for coating metal surfaces |
CN103866311B (en) * | 2014-03-06 | 2016-05-18 | 武汉材料保护研究所 | One is prepared chemical conversion film method based on molybdate in aluminum alloy surface |
CN104294258A (en) * | 2014-09-09 | 2015-01-21 | 北京聚龙伟业科技发展有限公司 | Metal environment-friendly silane ceramic film treatment agent and preparation method thereof |
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US20240209513A1 (en) | 2024-06-27 |
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CN108350579A (en) | 2018-07-31 |
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US20180237919A1 (en) | 2018-08-23 |
WO2017046139A1 (en) | 2017-03-23 |
KR20180053306A (en) | 2018-05-21 |
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EP3350357B1 (en) | 2024-05-01 |
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