EP0700452B1 - Chromium-free conversion-coating treatment of aluminium - Google Patents
Chromium-free conversion-coating treatment of aluminium Download PDFInfo
- Publication number
- EP0700452B1 EP0700452B1 EP94916970A EP94916970A EP0700452B1 EP 0700452 B1 EP0700452 B1 EP 0700452B1 EP 94916970 A EP94916970 A EP 94916970A EP 94916970 A EP94916970 A EP 94916970A EP 0700452 B1 EP0700452 B1 EP 0700452B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminium
- treatment
- aluminum
- concentrations
- pretreatment
- 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.)
- Expired - Lifetime
Links
- 238000011282 treatment Methods 0.000 title claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000004411 aluminium Substances 0.000 title claims abstract description 13
- 238000007739 conversion coating Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000003466 welding Methods 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 10
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- -1 fluoro anions Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 6
- 239000008397 galvanized steel Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000003754 machining Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 238000004026 adhesive bonding Methods 0.000 abstract description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910000838 Al alloy Inorganic materials 0.000 abstract 2
- 238000007493 shaping process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 13
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 8
- 238000004532 chromating Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229960002050 hydrofluoric acid Drugs 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000680 Aluminized steel Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 description 2
- 229910003708 H2TiF6 Inorganic materials 0.000 description 2
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 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 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 238000011022 operating instruction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C23C22/78—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
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—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
Definitions
- the invention is in the field of chemical surface treatment of aluminum for the purpose of corrosion protection, the so-called passivation. It describes chrome-free treatment processes for aluminum strips and molded aluminum parts to achieve temporary corrosion protection while maintaining weldability and bondability as well as the suitability of the material for a further conversion step, for example phosphating, chromating or chrome-free conversion treatment.
- aluminum means not only pure aluminum but also alloys whose main component is aluminum.
- frequently used alloy elements are silicon, magnesium, copper, manganese, chromium and nickel, the total weight fraction of these alloy elements in the alloy usually not exceeding 10%.
- Aluminum is increasingly used in vehicle construction for a variety of reasons, such as weight, rigidity or recyclability. While engine and transmission parts, wheels, seat frames etc. are already largely made of aluminum, use in body construction is currently limited to parts such as the radiator hood, trunk lid, interior door parts and various small parts, as well as truck cabins, side walls of vans or bodies of caravans . Overall, less than 5% of the metal surface of automobile bodies is made of aluminum worldwide. The increased use of aluminum in this area is being intensively examined by the aluminum and automotive industries.
- the material is pickled in order to remove the oxide layers formed during transport and storage and to reduce and even out the electrical surface resistance to the low values required for welding.
- This pickling for which acidic or alkaline aqueous solutions are used, has hitherto mainly occurred in parts plants at short notice before the welding process. The close coordination of time is intended to suppress the build-up of disruptive layers of corrosion and dirt.
- the aluminum is chemically pretreated in coil systems (coil systems), possibly with subsequent protective coating, currently only for parts that are no longer to be welded.
- the aluminum parts are often ground after forming to improve the fit.
- Toxic and carcinogenic chromium (VI) -containing compounds can occur in the grinding dust. Therefore, increased requirements must be placed on measures to maintain occupational safety on site.
- the aluminum parts pretreated with chromate are joined together with parts made of steel and / or galvanized steel to form a so-called multi-metal body and are passed through the body pre-treatment system.
- Soluble ones can be used in the usual alkaline cleaning step Chromium (VI) compounds are removed from the layer. On the one hand, this reduces the corrosion protection function of the layer and, on the other hand, the chromate-containing cleaning solution must be subjected to a special detoxification step during disposal.
- DE-C-19 33 013 discloses treatment baths with a pH above 3.5 which, in addition to complex fluorides of boron, titanium or zirconium, in amounts of 0.1 to 15 g / l, based on the metals, additionally 0.5 up to 30 g / l of oxidizing agents, especially sodium metanitrobenzenesulfonate.
- DE-C-24 33 704 describes treatment baths for increasing paint adhesion and permanent corrosion protection on, inter alia, aluminum, the 0.1 to 5 g / l polyacrylic acid or its salts or esters and 0.1 to 3.5 g / l ammonium fluorozirconate, calculated as ZrO 2 .
- the pH values of these baths can fluctuate over a wide range. The best results are generally obtained when the pH is 6-8.
- a molar ratio between the fluoric acid and phosphate of about 2.5: 1 to about 1:10 must be observed.
- DE-A-27 15 292 discloses treatment baths for the chromium-free pretreatment of aluminum cans which contain at least 10 ppm titanium and / or zirconium, between 10 and 1000 ppm phosphate and a sufficient amount of fluoride to form complex fluorides of the titanium and / or zirconium present however, contain 13 ppm and have pH values between 1.5 and 4.
- WO 92/07973 teaches a chromium- free treatment process for aluminum, the essential components in acidic aqueous solution being 0.01 to about 18% by weight of H 2 ZrF 6 and 0.01 to about 10% by weight of one 3- (NC 1-4 alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer used.
- Optional components are 0.05-10% by weight of dispersed SiO 2 , 0.06-0.6% by weight of a solubilizer for the polymer and surfactant.
- the polymer mentioned falls under the group of the "reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl group-containing amines" which can be used in the context of the present invention.
- DE-C-12 85 830 describes a process for the pretreatment of a surface of aluminum and its alloys before the application of chemically bound coatings by pickling in an aqueous acidic solution, characterized in that the surface with a cleaning solution which has a pH has from 1.8 to 3.2 and phosphate ions, fluoride ions and ions of one or more of the metals zinc, manganese, iron, sodium, potassium and ammonium are brought into contact.
- the invention is based on the object not previously made in the art of providing a chromium-free process for the pretreatment of surfaces made of aluminum or its alloys, in which the surfaces are provided with a temporary corrosion protection by a first chemical pretreatment process, then a non-cutting and / or cutting Subjected to the forming process and / or to one another or to parts made of steel and / or galvanized and / or alloy-galvanized steel by gluing and / or welding and in a subsequent second chemical treatment step being provided with a permanently corrosion-protective coating.
- Conversion methods to achieve permanent corrosion protection include, in particular, phosphating with acidic zinc-containing phosphating baths, chromating or chromium-free conversion treatment in accordance with the literature mentioned above, for example with reactive organic polymers and / or with compounds, in particular fluorocomplexes, the elements titanium, zirconium and / or hafnium into consideration.
- the pretreatment according to the task must ensure temporary protection against corrosion for a longer storage period, for example two to three months, without the material being bondable or weldable being adversely affected, for example by electrical resistance welding.
- the electrical surface resistance is as uniform as possible, does not exceed a value of approximately 400 mOhm and is preferably below approximately 100 mOhm. After alkaline pickling and subsequent storage for 4 weeks, on the other hand, sprinkle the electrical surface resistances locally very strong and cover a range of 100 to 1500 ⁇ Ohm.
- the surface resistance is measured in accordance with the DVS 2929 data sheet in the form of a single sheet measurement with iron electrodes with a diameter of 20 mm.
- a multi-metal body is a body that is made from at least two of the materials: aluminum, steel, galvanized, alloy-galvanized, aluminized or alloy-aluminized steel.
- Suitable multimetal phosphating processes are known to the person skilled in the field of conversion treatment, for example from DE-A-39 18 136 and EP-A-106 459 , and do not constitute an object of this invention.
- Conversion treatments in question which must not be hindered by the first conversion step according to the invention. Examples include chromating with treatment baths containing Cr (VI) and / or Cr (III) or the above-mentioned chromium-free conversion processes.
- a thin conversion coating which consists of (mixed) oxides, (mixed) fluorides and / or oxyfluorides of aluminum and at least one of the elements boron, silicon, titanium, zirconium or hafnium and which includes organic polymers of the polyacrylate type Acrylate-containing copolymers or reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines can be modified.
- the feature "thin” should be understood to mean that the concentration of the layer-forming elements boron, silicon, titanium, zirconium and / or hafnium on the aluminum surface together in the range 1-80 mg / m 2 , in particular is in the range 2 - 20 mg / m 2 .
- the polymer content of the conversion coating must not exceed 5 mg / m 2 and should preferably be in the range 0 to 3 mg / m 2 .
- the invention accordingly describes a Process for the pretreatment of surfaces made of aluminum or its alloys before a second, permanently corrosion-protective conversion treatment, preferably chromating, a chromium-free conversion treatment with reactive organic polymers and / or with compounds of the elements titanium, zirconium and / or hafnium, or phosphating with acidic zinc-containing Phosphating baths, characterized in that the surfaces are brought into contact with acidic aqueous treatment solutions, the complex fluorides of the elements boron, silicon, titanium, zirconium or hafnium individually or in a mixture with one another in concentrations of the fluoro anions of in total between 100 and 4000, preferably Contain 200 to 2000 mg / l and have a pH between 0.3 and 3.5, preferably between 1 and 3, and that between the pretreatment of the surfaces made of aluminum or its alloys and the permanent anti-corrosion conversion treatment Aluminum or its alloys are subjected to a non-cutting and / or metal-forming process and / or are connected
- the treatment solutions can additionally contain polymers of the type of the polyacrylates and / or the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines in concentrations below 500 mg / l, preferably below 200 mg / l. If the treatment solution contains Zr, the concentration of the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines should be less than 100 mg / l.
- the complex fluorides of the elements boron, silicon, titanium, zircon or hafnium, ie the anions BF 4 - , SiF 6 2- , TiF 6 2- , ZrF 6 2- or HfF 6 2- can be in the form of the free acids or as Salts are introduced.
- Counterions are in particular alkali metal and ammonium ions.
- This also applies to the optional components free fluoride and polyhydroxycarboxylic acids. If these components are not used or are not used exclusively in the form of the acids, the pH of the treatment baths may need to be adjusted to the range from 0.3 to 3.5 according to the invention. Phosphoric acid, nitric acid and sulfuric acid are particularly suitable for this.
- pH value of the treatment solution is preferred.
- Polymers of the acrylate type, including acrylate-containing copolymers, suitable as optional additives in concentrations below 500 mg / l are known as commercial products in the prior art.
- Water-soluble polyacrylic acids in the molecular weight range between 20,000 and 100,000 daltons are particularly suitable, in particular those with an average molecular weight of about 50,000 to 60,000 daltons, the 5% strength by weight aqueous solution of which has a pH of about 2.
- Suitable polymers of the type of the reaction products of polyvinylphenol with aldehydes and organic amines are known as agents for the surface treatment of metals and in particular for passivating rinsing of conversion-treated metal surfaces, for example from EP-A-319 016 and EP-A-319 017 . These are polymers with molecular weights up to 2,000,000 daltons with a preferred molecular weight range between 7,000 and 70,000 daltons.
- the optionally substituted phenol rings in the chains can be linked via one or two carbon atoms, it being possible for the chains to have been subjected to a post-crosslinking process. Characteristically, at least some of the phenol rings are bonded via a carbon atom to a nitrogen atom which bears a further alkyl substituent which has at least one hydroxyl function. This structure gives the polymer chelating properties against metal ions.
- the treatment solutions should have temperatures between 15 and 60 ° C and can be applied to the aluminum surfaces by spraying, dipping or using the no rinse process. In the case of spray or immersion applications, the required treatment times are between 5 and 90 seconds.
- the no-rinse process which can be carried out, for example, by roller application (so-called chemcoater)
- the setting of a specific wet film thickness by squeezing rolls is a process-relevant step.
- the wet film thickness should be between 2 and 10 ml / m 2 , preferably between 4 and 6 ml / m 2 .
- water rinsing with demineralized water can optionally take place after the immersion or spray treatment, the temperature of the rinsing water being between 10 and 40 ° C.
- Aluminum sheets of size 100 x 200 mm and thickness 1.1 mm of various alloys from the AA 6000 group from different manufacturers and of different ages (cf. Table 2) were coated with a 1% aqueous alkaline cleaning solution (Ridoline R C 72, from Henkel ) freed from corrosion protection greasing at 65 ° C for 10-12 s, rinsed in process water for 5 s at room temperature and then rinsed in demineralized (demineralized) water for 5 s at room temperature.
- This was followed by the conversion treatment with treatment solutions according to the invention and comparison solutions according to Table 1 and the process according to Table 2. This was carried out either by immersion, spraying or spin coating (simulation of the order in the chemcoater no rinse).
- the results obtained depend on the alloy selected and on the history of the material (storage time). The better results are generally obtained with the AC120 alloy. In all cases, conversion treatment according to the invention However, the findings regarding surface resistance and phosphatability are within the technically required framework.
- the test for bondability was carried out with tensile shear tests in accordance with DIN 53 283 using a commercially available two-component epoxy adhesive in accordance with the instructions for use (Terokal R 5045, Teroson, Heidelberg).
- the alloy AC 120 was used as the substrate, which was treated according to the method in Table 2 and then stored open for 30 days. There was no further pretreatment before the adhesive strength was determined. For comparison, the values for a degreased sample and for a green chromated sample were measured after the same storage period. The results are shown in Table 3.
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Abstract
Description
Die Erfindung liegt auf dem Gebiet der chemischen Oberflächenbehandlung von Aluminium zum Zwecke des Korrosionsschutzes, der sogenannten Passivierung. Sie beschreibt chromfreie Behandlungsverfahren für Aluminiumbänder und Aluminumformteile zur Erzielung eines temporären Korrosionschutzes unter Erhalt der Verschweiß- und Verklebbarkeit sowie der Eignung des Materials für einen weiteren Konversionsschritt, beispielsweise Phosphatierung, Chromatierung oder chromfreie Konversionsbehandlung.The invention is in the field of chemical surface treatment of aluminum for the purpose of corrosion protection, the so-called passivation. It describes chrome-free treatment processes for aluminum strips and molded aluminum parts to achieve temporary corrosion protection while maintaining weldability and bondability as well as the suitability of the material for a further conversion step, for example phosphating, chromating or chrome-free conversion treatment.
Unter "Aluminium" werden im Sinne der Erfindung nicht nur reines Aluminium, sondern auch Legierungen verstanden, deren Hauptkomponente Aluminium darstellt. Beispiele für häufig verwendete Legierungselemente sind Silicium, Magnesium, Kupfer, Mangan, Chrom und Nickel, wobei üblicherweise der gesamte Gewichtsanteil dieser Legierungselemente in der Legierung nicht über 10 % liegt.For the purposes of the invention, “aluminum” means not only pure aluminum but also alloys whose main component is aluminum. Examples of frequently used alloy elements are silicon, magnesium, copper, manganese, chromium and nickel, the total weight fraction of these alloy elements in the alloy usually not exceeding 10%.
Aus vielfältigen Gründen wie Gewicht, Steifigkeit oder Recyclingfähigkeit wird Aluminium verstärkt im Fahrzeugbau eingesetzt. Während Motor- und Getriebeteile, Räder, Sitzrahmen etc. schon zu großen Anteilen aus Aluminium hergestellt werden, ist der Einsatz im Karosseriebau derzeit noch auf Teile wie Kühlerhaube, Heckdeckel, Türinnenteile und diverse Kleinteile sowie auf Lastwagenkabinen, Bordwände von Transportern oder Aufbauten von Caravans beschränkt. Insgesamt wird weltweit weniger als 5 % der Metalloberfläche von Automobilkarossen aus Aluminium gefertigt. Der verstärkte Einsatz von Aluminium auf diesem Gebiet wird von der Aluminium- und der Automobilindustrie intensiv untersucht.Aluminum is increasingly used in vehicle construction for a variety of reasons, such as weight, rigidity or recyclability. While engine and transmission parts, wheels, seat frames etc. are already largely made of aluminum, use in body construction is currently limited to parts such as the radiator hood, trunk lid, interior door parts and various small parts, as well as truck cabins, side walls of vans or bodies of caravans . Overall, less than 5% of the metal surface of automobile bodies is made of aluminum worldwide. The increased use of aluminum in this area is being intensively examined by the aluminum and automotive industries.
Das Zusammenfügen einzelner Aluminiumteile für den Fahrzeugbau erfolgt üblicherweise durch elektrisches Widerstandsschweißen. Dies bringt gemäß Merkblatt DVS 2929 "Widerstandsschweißen. Messung des Übergangswiderstandes an Aluminiumwerkstoffen", Deutscher Verband für Sctmeißtechnik e.V., August 1985 folgende Problematik mit sich: "Die Affinität von Aluminium zu Sauerstoff führt immer zur Bildung einer Oxidschicht. Aufbau und Dicke dieser Oxidschicht beeinflussen in großem Maße die Widerstandsschweißung. Somit kommt der Oberflächenbehandlung und dem daraus resultierenden elektrischen Kontaktwiderstand der Blechteile für die Reproduzierbarkeit des Schweißergebnisses und für die Elektrodenstandmenge große Bedeutung zu. Beim Punktschweißen von unbehandelten Aluminiumblechen sind die ungleichmäßigen und relativ großen Kontaktwiderstände eine der Hauptursachen für Ungleichmäßigkeit der Schweißungen und für die geringen Elektrodenstandmengen. Durch Obeflächenbehandlungen wird der Kontaktwiderstand begrenzt und über die gesamte Fläche der zu fügenden Teile weitgehend gleichmäßig gestaltet."The joining of individual aluminum parts for vehicle construction is usually carried out by electrical resistance welding. According to leaflet DVS 2929 "Resistance welding. Measurement of contact resistance on aluminum materials", German Association for Welding Technology eV, August 1985, the following problems arise: "The affinity of aluminum to oxygen always leads to the formation of an oxide layer. The structure and thickness of this oxide layer influence in The surface treatment and the resulting electrical contact resistance of the sheet metal parts are of great importance for the reproducibility of the welding result and for the electrode life. In the spot welding of untreated aluminum sheets, the uneven and relatively large contact resistances are one of the main causes for uneven welding and For the low electrode life, surface contact treatment limits the contact resistance and makes it largely uniform over the entire surface of the parts to be joined t. "
Aus diesem Grunde wird der Werkstoff gebeizt, um die bei Transport und Lagerung gebildeten Oxidschichten zu entfernen und den elektrischen Oberflächenwiderstand auf die zur Verschweißung erforderlichen niedrigen Werte abzusenken und zu vergleichmäßigen. Dieses Beizen, für das man saure oder alkalische wäßrige Lösungen einsetzt, geschieht bisher überwiegend in Teileanlagen kurzfristig vor dem Verschweißungsprozeß. Durch die enge zeitliche Abstimmung soll der erneute Aufbau störender Korrosions- und Verschmutzungsschichten unterdrückt werden. Demgegenüber erfolgt eine chemische Vorbehandlung des Aluminiums in Bandanlagen (Coilanlagen), gegebenenfalls mit nachfolgender Schutzlackierung, derzeit nur für Teile, die nicht mehr geschweißt werden sollen.For this reason, the material is pickled in order to remove the oxide layers formed during transport and storage and to reduce and even out the electrical surface resistance to the low values required for welding. This pickling, for which acidic or alkaline aqueous solutions are used, has hitherto mainly occurred in parts plants at short notice before the welding process. The close coordination of time is intended to suppress the build-up of disruptive layers of corrosion and dirt. In contrast, the aluminum is chemically pretreated in coil systems (coil systems), possibly with subsequent protective coating, currently only for parts that are no longer to be welded.
Für einen verstärkten Einsatz von Aluminium in der Fahrzeug-Großserienfertigung ist es jedoch vorzuziehen, den Beizvorgang beim Hersteller bzw. Lieferanten des Aluminiumbandes durchzuführen. Dies ermöglicht es, die chemischen Arbeitsgänge Reinigen, Beizen, Spülen, Trocknen und Beölen sowie die damit verbundenen Vorgänge der Abwasserbehandlung und der Entsorgung rationeller, wirtschaftlicher und umweltverträglicher zu gestalten. Entsorgungstechnisch besonders günstig sind sogenannte "No-Rinse"-Verfahren, bei denen die Behandlungslösungen beispielsweise durch Walzenauftrag ("Chemcoater") aufgebracht und ohne Spülen aufgetrocknet werden. Diese Verfahren reduzieren den Chemikalienverbrauch und den Aufwand für die Aufarbeitung des Spülwassers erheblich. Sie sind allerdings nur für Substrate mit glatten Oberflächen, beispielsweise Metallbänder, geeignet.However, for an increased use of aluminum in the mass production of vehicles, it is preferable to carry out the pickling process at the manufacturer or supplier of the aluminum strip. This makes it possible to make the chemical cleaning, pickling, rinsing, drying and oiling processes and the associated processes of wastewater treatment and disposal more efficient, economical and environmentally compatible. So-called disposal technology is particularly cheap "No-rinse" processes in which the treatment solutions are applied, for example, by roller application ("chemcoater") and dried without rinsing. These processes significantly reduce the consumption of chemicals and the effort required to process the rinse water. However, they are only suitable for substrates with smooth surfaces, such as metal strips.
Eine solche lieferantenseitige chemische Vorbehandlung bringt jedoch das Problem mit sich, daß sich die gebeizten Aluminiumoberflächen je nach Lagerbedingungen (Temperatur, Feuchtigkeit, Luftverschmutzung, Zeit) wieder mit neuen wenig spezifischen, ungleichmäßigen und anorganisch oder organisch verunreinigten Oxid-/Hydroxidschichten überziehen. Durch diese unkontrollierte Veränderung des Oberflächenzustandes und des damit verbundenen elektrischen Oberflächenwiderstandes ist das Einhalten konstanter Arbeitsbedingungen bei den Verbindungstechniken Schweißen und Kleben nicht möglich.Such chemical pretreatment on the part of the supplier brings with it the problem that the pickled aluminum surfaces, depending on the storage conditions (temperature, humidity, air pollution, time), are covered again with new, less specific, uneven and inorganic or organic contaminated oxide / hydroxide layers. Due to this uncontrolled change in the surface condition and the associated electrical surface resistance, it is not possible to maintain constant working conditions when welding and gluing.
Nach dem Stand der Technik wäre dieses Problem dadurch lösbar, daß man direkt nach dem Beizvorgang Chromat-haltige Konversionsschichten aufbringt. in Verbindung mit einer Korrosionsschutzbeölung überstehen diese auch lange Lagerzeiten (bis zu 6 Monate) ohne Korrosion und ohne Einbuße an Klebefähigkeit. Chromat-haltige Konversionsschichten bringen jedoch hinsichtlich der betrachteten Einsatzgebiete folgende schwerwiegende Nachteile mit sich, die es erschweren, für das vorgesehene Einsatzgebiet solche Konversionsschichten zu verwenden:According to the prior art, this problem could be solved by applying chromate-containing conversion layers directly after the pickling process. in conjunction with anti-corrosion lubrication, they can withstand long storage times (up to 6 months) without corrosion and without loss of adhesive power. However, chromate-containing conversion layers have the following serious disadvantages with regard to the areas of use considered, which make it difficult to use such conversion layers for the intended area of use:
1. Die Aluminiumteile werden nach Umformung oft geschliffen, um die Paßform zu verbessern. Dabei können toxische und carzinogene Chrom(VI)-haltige Verbindungen im Schleifstaub auftreten. Deshalb müssen erhöhte Anforderungen an Maßnahmen zum Erhalt der Arbeitssicherheit vor Ort gestellt werden.1. The aluminum parts are often ground after forming to improve the fit. Toxic and carcinogenic chromium (VI) -containing compounds can occur in the grinding dust. Therefore, increased requirements must be placed on measures to maintain occupational safety on site.
2. Im Automobilbau werden die mit Chromat vorbehandelten Aluminiumteile mit Teilen aus Stahl und/oder verzinktem Stahl zu einer sogenannten Multimetallkarosse zusammengefügt und durch die Karossen-Vorbehandlungsanlage gefahren. In der üblichen alkalischen Reinigungsstufe können lösliche Chrom(VI)-Verbindungen aus der Schicht herausgelöst werden. Hierdurch nimmt zum einen die Korrosionsschutzfunktion der Schicht ab und zum anderen muß die Chromat-haltige Reinigerlösung bei der Entsorgung einem speziellen Entgiftungsschritt unterworfen werden.2. In automobile construction, the aluminum parts pretreated with chromate are joined together with parts made of steel and / or galvanized steel to form a so-called multi-metal body and are passed through the body pre-treatment system. Soluble ones can be used in the usual alkaline cleaning step Chromium (VI) compounds are removed from the layer. On the one hand, this reduces the corrosion protection function of the layer and, on the other hand, the chromate-containing cleaning solution must be subjected to a special detoxification step during disposal.
Die chromfreie Konversionsbehandlung von Aluminiumoberflächen mit Fluoriden von Bor, Silicium, Titan oder Zirkonium allein oder in Verbindung mit organischen Polymeren ist zur Erzielung eines permanenten Korrosionsschutzes und zur Erzeugung einer Grundlage für eine anschließende Lackierung prinzipiell bekannt:The chrome-free conversion treatment of aluminum surfaces with fluorides of boron, silicon, titanium or zirconium alone or in combination with organic polymers is known in principle to achieve permanent corrosion protection and to create a basis for subsequent painting:
Die US-A-5 129 967 offenbart Behandlungsbäder für eine No-Rinse-Behandlung (dort als "dried in place conversion coating" bezeichnet) von Aluminium, enthaltend
- a) 10 bis 16 g/l Polyacrylsäure oder deren Homopolymere,
- b) 12 bis 19 g/l Hexafluorozirkonsäure,
- c) 0,17 bis 0,3 g/l Fluorwasserstoffsäure und
- d) bis zu 0,6 g/l Hexafluorotitansäure.
- a) 10 to 16 g / l polyacrylic acid or its homopolymers,
- b) 12 to 19 g / l hexafluorozirconic acid,
- c) 0.17 to 0.3 g / l hydrofluoric acid and
- d) up to 0.6 g / l hexafluorotitanic acid.
EP-B-8 942 offenbart Behandlungslösungen, vorzugsweise für Aluminiumdosen, enthaltend
- a) 0,5 bis 10 g/l Polyacrylsäure oder eines Esters davon und
- b) 0,2 bis 8 g /1 an mindestens einer der Verbindungen H2ZrF6, H2TiF6 und H2SiF6, wobei der pH-Wert der Lösung unterhalb von 3,5 liegt,
- a) 25 bis 100 g/l Polyacrylsäure oder eines Esters davon,
- b) 25 bis 100 g/l von mindestens einer der Verbindungen H2ZrF6, H2TiF6 und H2SiF6, und
- c) einer Quelle freier Fluoridionen, die 17 bis 120 g/l freies Fluorid liefert.
- a) 0.5 to 10 g / l polyacrylic acid or an ester thereof and
- b) 0.2 to 8 g / l of at least one of the compounds H 2 ZrF 6 , H 2 TiF 6 and H 2 SiF 6 , the pH of the solution being below 3.5,
- a) 25 to 100 g / l polyacrylic acid or an ester thereof,
- b) 25 to 100 g / l of at least one of the compounds H 2 ZrF 6 , H 2 TiF 6 and H 2 SiF 6 , and
- c) a source of free fluoride ions which provides 17 to 120 g / l of free fluoride.
DE-C-19 33 013 offenbart Behandlungsbäder mit einem pH-Wert oberhalb 3,5, die neben komplexen Fluoriden des Bors, Titans oder Zirkoniums in Mengen von 0,1 bis 15 g/l, bezogen auf die Metalle, zusätzlich 0,5 bis 30 g/l Oxidationsmittel, insbesondere Natriummetanitrobenzolsulfonat enthalten. DE-C-19 33 013 discloses treatment baths with a pH above 3.5 which, in addition to complex fluorides of boron, titanium or zirconium, in amounts of 0.1 to 15 g / l, based on the metals, additionally 0.5 up to 30 g / l of oxidizing agents, especially sodium metanitrobenzenesulfonate.
DE-C-24 33 704 beschreibt Behandlungsbäder zur Erhöhung der Lackhaftung und des permanenten Korrosionsschutzes auf u.a. Aluminium, die 0,1 bis 5 g/l Polyacrylsäure oder deren Salze oder Ester sowie 0,1 bis 3,5 g/l Ammoniumfluorozirkonat, berechnet als ZrO2, enthalten können. Die pH-Werte dieser Bäder können über einen weiten Bereich schwanken. Die besten Ergebnisse werden im allgemeinen erhalten, wenn der pH bei 6 - 8 liegt. DE-C-24 33 704 describes treatment baths for increasing paint adhesion and permanent corrosion protection on, inter alia, aluminum, the 0.1 to 5 g / l polyacrylic acid or its salts or esters and 0.1 to 3.5 g / l ammonium fluorozirconate, calculated as ZrO 2 . The pH values of these baths can fluctuate over a wide range. The best results are generally obtained when the pH is 6-8.
US-A-4 992 116 beschreibt Behandlungsbäder für die Konversionsbehandlung von Aluminium mit pH-Werten zwischen etwa 2,5 und 5, die mindestens drei Komponenten enthalten:
- a) Phosphationen im Konzentrationsbereich zwischen 1,1x10-5 bis 5,3x10-3 mol/l entsprechend 1 bis 500 mg/l,
- b) 1,1x10-5 bis 1,3x10-3 mol/l einer Fluorosäure eines Elements der Gruppe Zr, Ti, Hf und Si (entsprechend je nach Element 1,6 bis 380 mg/l) und
- c) 0,26 bis 20 g/l einer Polyphenolverbindung, erhältlich durch Umsetzung von Poly(vinylphenol) mit Aldehyden und organischen Aminen.
- a) phosphate ions in the concentration range between 1.1x10 -5 to 5.3x10 -3 mol / l corresponding to 1 to 500 mg / l,
- b) 1.1x10 -5 to 1.3x10 -3 mol / l of a fluoric acid of an element from the group Zr, Ti, Hf and Si (corresponding to 1.6 to 380 mg / l depending on the element) and
- c) 0.26 to 20 g / l of a polyphenol compound, obtainable by reacting poly (vinylphenol) with aldehydes and organic amines.
Dabei ist ein Molverhältnis zwischen der Fluorosäure und Phosphat von etwa 2,5 : 1 bis etwa 1 : 10 einzuhalten.A molar ratio between the fluoric acid and phosphate of about 2.5: 1 to about 1:10 must be observed.
DE-A-27 15 292 offenbart Behandlungsbäder für die chromfreie Vorbehandlung von Aluminiumdosen, die mindestens 10 ppm Titan und/oder Zirkon, zwischen 10 und 1000 ppm Phosphat und eine zur Bildung komplexer Fluoride des vorhandenen Titans und/oder Zirkons ausreichenden Menge Flourid, mindestens jedoch 13 ppm, enthalten und pH-Werte zwischen 1,5 und 4 aufweisen. DE-A-27 15 292 discloses treatment baths for the chromium-free pretreatment of aluminum cans which contain at least 10 ppm titanium and / or zirconium, between 10 and 1000 ppm phosphate and a sufficient amount of fluoride to form complex fluorides of the titanium and / or zirconium present however, contain 13 ppm and have pH values between 1.5 and 4.
WO 92/07973 lehrt ein chromfreies Behandlungsverfahren für Aluminium, das als wesentliche Komponenten in saurer wäßriger Lösung 0,01 bis etwa 18 Gew.-% H2ZrF6 und 0,01 bis etwa 10 Gew.-% eines 3-(N-C1-4alkyl-N-2-hydroxyethylaminomethyl)-4-hydroxystyrol-Polymers verwendet. Fakultative Komponenten sind 0,05 - 10 Gew.-% dispergiertes SiO2, 0,06 bis 0,6 Gew.-% eines Lösevermittlers für das Polymer sowie Tensid. Das genannte Polymer fällt unter die Gruppe der unten beschriebenen und im Rahmen der vorliegenden Erfindung einsetzbaren "Umsetzungsprodukte von Poly(vinylphenol) mit Aldehyden und organischen Hydroxylgruppen-haltigen Aminen". WO 92/07973 teaches a chromium- free treatment process for aluminum, the essential components in acidic aqueous solution being 0.01 to about 18% by weight of H 2 ZrF 6 and 0.01 to about 10% by weight of one 3- (NC 1-4 alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer used. Optional components are 0.05-10% by weight of dispersed SiO 2 , 0.06-0.6% by weight of a solubilizer for the polymer and surfactant. The polymer mentioned falls under the group of the "reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl group-containing amines" which can be used in the context of the present invention.
Die DE-C-12 85 830 beschreibt ein Verfahren zur Vorbehandlung einer Oberfläche von Aluminium und dessen Legierungen vor dem Aufbringen von chemisch gebundenen Überzügen durch Anbeizen in einer wäßrigen sauren Lösung, dadurch gekennzeichnet, daß die Oberfläche mit einer Reinigungslösung, die einen pH-Wert von 1,8 bis 3,2 aufweist und Phosphationen, Fluoridionen sowie Ionen von einem oder mehreren der Metalle Zink, Mangan, Eisen, Natrium, Kalium und Ammonium enthält, in Berührung gebracht wird.DE-C-12 85 830 describes a process for the pretreatment of a surface of aluminum and its alloys before the application of chemically bound coatings by pickling in an aqueous acidic solution, characterized in that the surface with a cleaning solution which has a pH has from 1.8 to 3.2 and phosphate ions, fluoride ions and ions of one or more of the metals zinc, manganese, iron, sodium, potassium and ammonium are brought into contact.
Diese Behandlungsbäder nach dem Stand der Technik wurden zur Erzielung eines permanenten Korrosionsschutzes, ggf. in Verbindung mit guter Lackhaftung, entwickelt.These state-of-the-art treatment baths were developed to achieve permanent corrosion protection, possibly in conjunction with good paint adhesion.
Der Erfindung liegt demgegenüber die bisher in der Technik nicht gestellte Aufgabe zugrunde, ein chromfreies Verfahren zur Vorbehandlung von Oberflächen aus Aluminium oder seinen Legierungen bereitzustellen, bei dem die Oberflächen durch ein erstes chemisches Vorbehandlungsverfahren mit einem temporären Korrosionsschutz versehen, danach einem spanlosen und/oder spanabhebenden Umformungsprozeß unterzogen und/oder miteinander oder mit Teilen aus Stahl und/oder verzinktem und/oder legierungsverzinktem Stahl durch Kleben und/oder Schweißen verbunden und in einem nachfolgenden zweiten chemischen Behandlungsschritt mit einem permanent korrosionsschützenden Überzug versehen werden. Als Konversionsverfahren zur Erzielung eines permanenten Korrosionsschutzes kommen insbesondere eine Phosphatierung mit sauren zinkhaltigen Phosphatierbädern, eine Chromatierung oder eine chromfreie Konversionsbehandlung entsprechend der vorstehend genannten Literatur, beispielsweise mit reaktiven organischen Polymeren und/oder mit Verbindungen, insbesondere Flourokomplexen, der Elemente Titan, Zirkon und/oder Hafnium in Betracht. Die aufgabengemäße Vorbehandlung muß einen temporären Korrosionsschutz für eine längere Lagerzeit, beispielsweise zwei bis drei Monate, gewährleisten, ohne daß die Verklebbarkeit des Materials oder die Verschweißbarkeit beispielsweise durch elektrisches Widerstandsschweißen negativ beeinflußt werden. Für die Verschweißbarkeit mittels Widerstandsschweißen ist es insbesondere erforderlich, daß der elektrische Oberflächenwiderstand möglichst gleichmäßig ist, einen Wert von etwa 400 mOhm nicht überschreitet und vorzugsweise unterhalb von etwa 100 mOhm liegt. Nach alkalischer Beize und anschließender Lagerung von 4 Wochen streuen demgegenüber die elektrischen Oberflächenwiderstände örtlich sehr stark und überdecken einen Bereich von 100 bis 1500 µOhm. Die Messung des Oberflächenwiderstandes erfolgt dabei gemäß dem genannten Merkblatt DVS 2929 in Form einer Einzelblechmessung mit Eisenelektroden mit einem Durchmesser von 20 mm.In contrast, the invention is based on the object not previously made in the art of providing a chromium-free process for the pretreatment of surfaces made of aluminum or its alloys, in which the surfaces are provided with a temporary corrosion protection by a first chemical pretreatment process, then a non-cutting and / or cutting Subjected to the forming process and / or to one another or to parts made of steel and / or galvanized and / or alloy-galvanized steel by gluing and / or welding and in a subsequent second chemical treatment step being provided with a permanently corrosion-protective coating. As Conversion methods to achieve permanent corrosion protection include, in particular, phosphating with acidic zinc-containing phosphating baths, chromating or chromium-free conversion treatment in accordance with the literature mentioned above, for example with reactive organic polymers and / or with compounds, in particular fluorocomplexes, the elements titanium, zirconium and / or hafnium into consideration. The pretreatment according to the task must ensure temporary protection against corrosion for a longer storage period, for example two to three months, without the material being bondable or weldable being adversely affected, for example by electrical resistance welding. For weldability by means of resistance welding, it is particularly necessary that the electrical surface resistance is as uniform as possible, does not exceed a value of approximately 400 mOhm and is preferably below approximately 100 mOhm. After alkaline pickling and subsequent storage for 4 weeks, on the other hand, sprinkle the electrical surface resistances locally very strong and cover a range of 100 to 1500 µOhm. The surface resistance is measured in accordance with the DVS 2929 data sheet in the form of a single sheet measurement with iron electrodes with a diameter of 20 mm.
Weiterhin ist an die Beschichtung die Bedingung zu stellen, daß die damit überzogenen Teile nach dem Zusammenbau zu einer Multimetallkarosse bei der derzeit üblichen Multimetall-Vorbehandlung der fertigen Karosse im Automobilwerk, bestehend zumindest aus den Verfahrensschritten Reinigen, Spülen, Zinkphosphatieren, Spülen, VE-Wasser-Spülen, mit einer permanent korrosionsschützenden Zinkphosphatschicht bedeckt werden. Als Multimetallkarosse wird eine Karosse bezeichnet, die hergestellt ist aus mindestens zwei der Materialien: Aluminium, Stahl, verzinkter, legierungsverzinkter, aluminierter oder legierungsaluminierter Stahl. Geeignete Multimetall-Phosphatierverfahren sind dem Fachmann auf dem Gebiet der Konversionsbehandlung bekannt, beispielsweise aus DE-A-39 18 136 und EP-A-106 459, und stellen keinen Gegenstand dieser Erfindung dar. Alternativ kommen im Falle einer Ganzaluminium-Karosserie weitere permanent korrosionsschützende Konversionsbehandlungen in Frage, die durch den erfindungsgemäßen ersten Konversionsschritt nicht behindert werden dürfen. Beispielsweise genannt seien die Chromatierung mit Cr(VI)-und/oder Cr(III)-haltigen Behandlungsbädern oder die oben genannten chromfreien Konversionsverfahren.Furthermore, the coating must be subject to the condition that the parts coated with it after assembly to form a multimetal body in the currently customary multimetal pretreatment of the finished body in the automobile plant, consisting at least of the process steps of cleaning, rinsing, zinc phosphating, rinsing, demineralized water - Rinsing, covered with a permanently corrosion-protective zinc phosphate layer. A multi-metal body is a body that is made from at least two of the materials: aluminum, steel, galvanized, alloy-galvanized, aluminized or alloy-aluminized steel. Suitable multimetal phosphating processes are known to the person skilled in the field of conversion treatment, for example from DE-A-39 18 136 and EP-A-106 459 , and do not constitute an object of this invention. Alternatively, in the case of an all-aluminum body, there are further permanent corrosion-protecting bodies Conversion treatments in question, which must not be hindered by the first conversion step according to the invention. Examples include chromating with treatment baths containing Cr (VI) and / or Cr (III) or the above-mentioned chromium-free conversion processes.
Diese Aufgabe wird dadurch gelöst, daß man Oberflächen aus Aluminium oder seinen Legierungen zunächst nach dem Stand der Technik sauer oder alkalisch reinigt und spült. Erfindungsgemäß wird anschließend ein dünner Konversionsüberzug aufgebracht, der aus (Misch)Oxiden, (Misch)Fluoriden und/ oder Oxyfluoriden von Aluminium und mindestens einem der Elemente Bor, Silicium, Titan, Zirkon oder Hafnium besteht und der mit organischen Polymeren vom Typ der Polyacrylate einschließlich Acrylat-haltigen Copolymeren oder Umsetzungsprodukten von Poly(vinylphenol) mit Aldehyden und organischen Hydroxylgruppen-haltigen Aminen modifiziert sein kann. Das Merkmal "dünn" ist so zu verstehen, daß die Konzentration der schichtbildenden Elemente Bor, Silicium, Titan, Zirkon und/oder Hafnium auf der Aluminiumoberfläche zusammen im Bereich 1 - 80 mg/m2, insbesondere im Bereich 2 - 20 mg/m2 liegt. Der Polymergehalt des Konversionsüberzuges darf 5 mg/m2 nicht übersteigen und soll vorzugsweise im Bereich 0 bis 3 mg/m2 liegen.This object is achieved in that surfaces made of aluminum or its alloys are first cleaned and rinsed with acid or alkaline according to the prior art. According to the invention, a thin conversion coating is then applied, which consists of (mixed) oxides, (mixed) fluorides and / or oxyfluorides of aluminum and at least one of the elements boron, silicon, titanium, zirconium or hafnium and which includes organic polymers of the polyacrylate type Acrylate-containing copolymers or reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines can be modified. The feature "thin" should be understood to mean that the concentration of the layer-forming elements boron, silicon, titanium, zirconium and / or hafnium on the aluminum surface together in the range 1-80 mg / m 2 , in particular is in the range 2 - 20 mg / m 2 . The polymer content of the conversion coating must not exceed 5 mg / m 2 and should preferably be in the range 0 to 3 mg / m 2 .
Die Erfindung beschreibt demnach ein
Verfahren zur Vorbehandlung von Oberflächen aus Aluminium oder seinen Legierungen vor einer zweiten, permanent korrosionsschützenden Konversionsbehandlung, vorzugsweise einer Chromatierung, einer chromfreien Konversionsbehandlung mit reaktiven organischen Polymeren und/oder mit Verbindungen der Elemente Titan, Zirkon und/oder Hafnium, oder einer Phosphatierung mit sauren zinkhaltigen Phosphatierbädern, dadurch gekennzeichnet, daß man die Oberflächen mit sauren wäßrigen Behandlungslösungen in Kontakt bringt, die komplexe Fluoride der Elemente Bor, Silicium, Titan, Zirkon oder Hafnium einzeln oder im Gemisch miteinander in Konzentrationen der Fluoro-Anionen von insgesamt zwischen 100 und 4000, vorzugsweise 200 bis 2000, mg/l enthalten und einen pH-Wert zwischen 0,3 und 3,5, vorzugsweise zwischen 1 und 3, aufweisen und daß zwischen der Vorbehandlung der Oberflächen aus Aluminium oder seinen Legierungen und der permanent korrosionsschützenden Konversionsbehandlung die Teile aus Aluminium oder seinen Legierungen einem spanlosen und/oder spanabhebenden Umformungsprozeß unterzogen werden und/oder miteinander oder mit Teilen aus Stahl und/oder verzinktem und/oder legierungsverzinktem Stahl durch Kleben und/oder durch Schweißen, insbesondere durch elektrisches Widerstandsschweißen, verbunden werden.The invention accordingly describes a
Process for the pretreatment of surfaces made of aluminum or its alloys before a second, permanently corrosion-protective conversion treatment, preferably chromating, a chromium-free conversion treatment with reactive organic polymers and / or with compounds of the elements titanium, zirconium and / or hafnium, or phosphating with acidic zinc-containing Phosphating baths, characterized in that the surfaces are brought into contact with acidic aqueous treatment solutions, the complex fluorides of the elements boron, silicon, titanium, zirconium or hafnium individually or in a mixture with one another in concentrations of the fluoro anions of in total between 100 and 4000, preferably Contain 200 to 2000 mg / l and have a pH between 0.3 and 3.5, preferably between 1 and 3, and that between the pretreatment of the surfaces made of aluminum or its alloys and the permanent anti-corrosion conversion treatment Aluminum or its alloys are subjected to a non-cutting and / or metal-forming process and / or are connected to one another or to parts made of steel and / or galvanized and / or galvanized steel by gluing and / or by welding, in particular by electrical resistance welding.
Dabei können die Behandlungslösungen zusätzlich Polymere vom Typ der Polyacrylate und/oder der Umsetzungsprodukte von Poly(vinylphenol) mit Aldehyden und organischen Hydroxylgruppen-haltigen Aminen in Konzentrationen unter 500 mg/l, vorzugsweise unter 200 mg/l enthalten. Enthält die Behandlungslösung Zr, soll die Konzentration der Umsetzungsprodukte von Poly(vinylphenol) mit Aldehyden und organischen Hydroxylgruppen-haltigen Aminen kleiner als 100 mg/l sein.The treatment solutions can additionally contain polymers of the type of the polyacrylates and / or the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines in concentrations below 500 mg / l, preferably below 200 mg / l. If the treatment solution contains Zr, the concentration of the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines should be less than 100 mg / l.
Weitere potentielle Komponenten der Behandlungsbäder sind: freie Fluoridionen in Konzentrationen bis zu 500 mg/l und Polyhydroxycarbonsäuren oder ihre Anionen, insbesondere Gluconationen, in Konzentrationen bis zu 500 mg/l.Other potential components of the treatment baths are: free fluoride ions in concentrations up to 500 mg / l and polyhydroxycarboxylic acids or their anions, especially gluconate ions, in concentrations up to 500 mg / l.
Die komplexen Fluoride der Elemente Bor, Silicium, Titan, Zirkon oder Hafnium, d.h. die Anionen BF4 -, SiF6 2-, TiF6 2-, ZrF6 2- oder HfF6 2-, können in Form der freien Säuren oder als Salze eingebracht werden. Als Gegenionen kommen insbesondere Alkalimetall- und Ammoniumionen in Betracht. Dies gilt ebenso für die fakultativen Komponenten freies Fluorid und Polyhydroxycarbonsäuren. Sofern diese Komponenten nicht oder nicht ausschließlich in Form der Säuren eingesetzt werden, kann eine Einstellung des pH-Werts der Behandlungsbäder auf den erfindungsgemäßen Bereich von 0,3 bis 3,5 erforderlich werden. Hierfür sind insbesondere Phosphorsäure, Salpetersäure und Schwefelsäure geeignet. Bevorzugt ist eine Einstellung des pH-Werts der Behandlungslösung auf den Bereich 1 bis 3. Je nach Substrat kann die Anwesenheit von Sulfationen im Behandlungsbad in Konzentrationen bis zu 5 Gew.-%, insbesondere zwischen 0,1 und 3 Gew.-%, vorteilhaft sein.The complex fluorides of the elements boron, silicon, titanium, zircon or hafnium, ie the anions BF 4 - , SiF 6 2- , TiF 6 2- , ZrF 6 2- or HfF 6 2- , can be in the form of the free acids or as Salts are introduced. As Counterions are in particular alkali metal and ammonium ions. This also applies to the optional components free fluoride and polyhydroxycarboxylic acids. If these components are not used or are not used exclusively in the form of the acids, the pH of the treatment baths may need to be adjusted to the range from 0.3 to 3.5 according to the invention. Phosphoric acid, nitric acid and sulfuric acid are particularly suitable for this. An adjustment of the pH value of the treatment solution to the range 1 to 3 is preferred. Depending on the substrate, the presence of sulfate ions in the treatment bath in concentrations of up to 5% by weight, in particular between 0.1 and 3% by weight, can be advantageous be.
Als fakultative Zusätze in Konzentrationen unter 500 mg/l geeignete Polymere vom Typ der Acrylate einschließlich Acrylat-haltigen Copolymeren sind als Handelsprodukte im Stand der Technik bekannt. Besonders geeignet sind wasserlösliche Polyacrylsäuren im Molmassenbereich zwischen 20 000 und 100 000 Dalton, insbesondere solche mit einer mittleren Molmasse von etwa 50 000 bis 60 000 Dalton, deren 5 gew.-%ige wäßrige Lösung einen pH-Wert von etwa 2 aufweisen.Polymers of the acrylate type, including acrylate-containing copolymers, suitable as optional additives in concentrations below 500 mg / l are known as commercial products in the prior art. Water-soluble polyacrylic acids in the molecular weight range between 20,000 and 100,000 daltons are particularly suitable, in particular those with an average molecular weight of about 50,000 to 60,000 daltons, the 5% strength by weight aqueous solution of which has a pH of about 2.
Geeignete Polymere vom Typ der Umsetzungsprodukte von Polyvinylphenol mit Aldehyden und organischen Aminen sind als Mittel zur Oberflächenbehandlung von Metallen und insbesondere zu einer passivierenden Nachspülung konversionsbehandelter Metalloberflächen bekannt, beispielsweise aus der EP-A-319 016 und der EP-A-319 017. Dabei handelt es sich um Polymere mit Molmassen bis zu 2 000 000 Dalton bei einem bevorzugten Molmassenbereich zwischen 7000 und 70 000 Dalton. In den Ketten können die gegebenenfalls substituierten Phenolringe über ein oder zwei Kohlenstoffatome verknüpft sein, wobei gegebenenfalls die Ketten einem Nachvernetzungsprozeß unterworfen worden sein können. Charakteristischerweise ist zumindest an einen Teil der Phenolringe über ein Kohlenstoffatom ein Stickstoffatom gebunden, das einen weiteren Alkylsubstituenten trägt, der mindestens über eine Hydroxy-Funktion verfügt. Dieser Aufbau verleiht dem Polymer chelatisierende Eigenschaften gegenüber Metallionen.Suitable polymers of the type of the reaction products of polyvinylphenol with aldehydes and organic amines are known as agents for the surface treatment of metals and in particular for passivating rinsing of conversion-treated metal surfaces, for example from EP-A-319 016 and EP-A-319 017 . These are polymers with molecular weights up to 2,000,000 daltons with a preferred molecular weight range between 7,000 and 70,000 daltons. The optionally substituted phenol rings in the chains can be linked via one or two carbon atoms, it being possible for the chains to have been subjected to a post-crosslinking process. Characteristically, at least some of the phenol rings are bonded via a carbon atom to a nitrogen atom which bears a further alkyl substituent which has at least one hydroxyl function. This structure gives the polymer chelating properties against metal ions.
In der Technik der Konversionsbehandlung ist es üblich, die Behandlungsbäder nicht durch Zusammenmischen der einzelnen Komponenten vor Ort in den erwünschten Konzentrationen herzustellen, sondern vorgefertigte Konzentrate zur Herstellung der Bäder durch Verdünnen mit Wasser einzusetzen.In the technique of conversion treatment, it is customary not to produce the treatment baths by mixing the individual components together on site in the desired concentrations, but to use pre-prepared concentrates for the preparation of the baths by dilution with water.
Die Behandlungslösungen sollen Temperaturen zwischen 15 und 60 °C aufweisen und können durch Spritzen, Tauchen oder im No Rinse-Verfahren auf die Aluminiumoberflächen aufgebracht werden. Bei Spritz- oder Tauchapplikation liegen die erforderlichen Behandlungszeiten zwischen 5 und 90 Sekunden. Beim No-Rinse-Verfahren, das beispielsweise durch Walzenauftrag (sog. Chemcoater) durchgeführt werden kann, ist die Einstellung einer bestimmten Naßfilmdicke durch Abquetschwalzen ein verfahrensrelevanter Schritt. Die Naßfilmdicke soll zwischen 2 und 10 ml/m2, vorzugsweise zwischen 4 und 6 ml/m2 liegen.The treatment solutions should have temperatures between 15 and 60 ° C and can be applied to the aluminum surfaces by spraying, dipping or using the no rinse process. In the case of spray or immersion applications, the required treatment times are between 5 and 90 seconds. In the no-rinse process, which can be carried out, for example, by roller application (so-called chemcoater), the setting of a specific wet film thickness by squeezing rolls is a process-relevant step. The wet film thickness should be between 2 and 10 ml / m 2 , preferably between 4 and 6 ml / m 2 .
Während sich an die Behandlung im No-Rinse-Verfahren definitionsgemäß kein Spülschritt anschließt, kann im Anschluß an die Tauch- oder Spritzbehandlung fakultativ eine Wasserspülung mit vollentsalztem Wasser erfolgen, wobei die Temperatur des Spülwassers zwischen 10 und 40 °C liegen soll.While by definition no rinsing step follows the treatment in the no-rinse process, water rinsing with demineralized water can optionally take place after the immersion or spray treatment, the temperature of the rinsing water being between 10 and 40 ° C.
Unabhängig vom Applikationsverfahren ist es vorteilhaft, die Aluminiumoberflächen nach der Behandlung bei Temperaturen zwischen 40 und 85 °C zu trocknen.Regardless of the application method, it is advantageous to dry the aluminum surfaces after the treatment at temperatures between 40 and 85 ° C.
Da das beschriebene erfindungsgemäße Vorbehandlungsverfahren am Beginn der Bearbeitungskette Vorbehandeln - gegebenenfalls Umformen - Fügen (= Kleben oder Schweißen) - Konversionsbehandlung - Lackieren steht, ist es im funktionalen Zusammenhang mit den nachfolgenden Schritten zu sehen. Demgemäß fällt es unter den Rahmen der Erfindung, daß
- a) zwischen der Vorbehandlung der Oberflächen aus Aluminium oder seinen Le gierungen und der permanent korrosionsschützenden Konversionsbe handlung - insbesondere einer Phosphatierung mit sauren zinkhaltigen Phosphatierbädern, einer Chromatierung oder einer chromfreien Konversionsbehandlung - die Teile aus Aluminium oder seinen Legierungen einem spanlosen und/oder spanabhebenden Umformungsprozeß unterzogen werden und/oder
- b) zwischen der Vorbehandlung der Oberflächen aus Aluminium oder seinen Legierungen und der permanent korrosionsschützenden Konversionsbehandlung - insbesondere einer Phosphatierung mit sauren zinkhaltigen Phosphatierbädern, einer Chromatierung oder einer chromfreien Konversionsbehandlung - die Teile aus Aluminium oder seinen Legierungen miteinander oder mit Teilen aus Stahl und/oder verzinktem und/oder legierungsverzinktem Stahl und/oder aluminiertem und/oder legierungsaluminiertem Stahl durch Kleben und/oder durch Schweißen, insbesondere durch elektrisches Widerstandsschweißen verbunden werden.
- a) between the pretreatment of the surfaces made of aluminum or its alloys and the permanent corrosion-protecting conversion treatment - in particular phosphating with acidic zinc-containing Phosphating baths, chromating or chromium-free conversion treatment - the parts made of aluminum or its alloys are subjected to a non-cutting and / or machining process and / or
- b) between the pretreatment of the surfaces made of aluminum or its alloys and the permanent corrosion-protecting conversion treatment - in particular phosphating with acidic zinc-containing phosphating baths, chromating or chrome-free conversion treatment - the parts made of aluminum or its alloys with each other or with parts made of steel and / or galvanized and / or alloy-galvanized steel and / or aluminized and / or alloy-aluminized steel can be connected by gluing and / or by welding, in particular by electrical resistance welding.
Aluminiumbleche der Größe 100 x 200 mm und Dicke 1,1 mm verschiedener Legierungen aus der Gruppe AA 6000 verschiedener Hersteller und verschiedenen Alters (vergl. Tab. 2) wurden mit einer 1 %igen wäßrigen alkalischen Reinigerlösung (RidolineR C 72, Fa. Henkel) bei 65 °C 10-12 s von der Korrosionsschutzbefettung befreit, 5 s bei Raumtemperatur in Betriebswasser und dann 5 s bei Raumtemperatur in vollentsalztem (VE-)Wasser gespült. Anschließend erfolgte die Konversionsbehandlung mit erfindungsgemäßen Behandlungslösungen und Vergleichs lösungen gemäß Tab. 1 und Verfahren nach Tab. 2. Diese wurde entweder im Tauch-, Spritz- oder im Schleuderverfahren (Simulation des Auftrages im Chemcoater = No Rinse) durchgeführt. Nach dem Schleudern in einer Lackschleuder mit 550 Umdrehungen pro Minute, was bei einer Schleuderdauer von 5 Sekunden einen NaBfilm von 5 bis 6 µm ergibt, wurden die Muster sofort bei 70 °C im Trockenschrank 10 min getrocknet. Die im Spritz- oder Tauchverfahren behandelten Mustertafeln wurden anschließend noch 5 s unter leichter Bewegung in VE-Wasser gespült und anschließend getrocknet. Die Leitfähigkeit des ablaufenden Wassers nach der VE-Schlußspülung sollte dabei 20 µS nicht übersteigen. Als Hinweis auf eine gute Punktschweißbarkeit gilt der Oberflächenwiderstand. Er wird gemäß DVS-Merkblatt 2929 (Deutscher Verband für Schweißtechnik, Stand August 85) ermittelt. Es wurde die im Merkblatt 2929 dargestellte Einblechmethode verwendet (Elektrodenkraft: 75 KN, Stromstärke: 20 A). Bei den in Tab. 2 angegebenen Widerstandswerten ist der Nullwert (Elektroden sitzen aufeinander) bereits abgezogen. Tab.2 enthält die Widerstandswerte nach unterschiedlichen Lagerzeiten (1 Tag, 30 Tage, 60 Tage).Aluminum sheets of size 100 x 200 mm and thickness 1.1 mm of various alloys from the AA 6000 group from different manufacturers and of different ages (cf. Table 2) were coated with a 1% aqueous alkaline cleaning solution (Ridoline R C 72, from Henkel ) freed from corrosion protection greasing at 65 ° C for 10-12 s, rinsed in process water for 5 s at room temperature and then rinsed in demineralized (demineralized) water for 5 s at room temperature. This was followed by the conversion treatment with treatment solutions according to the invention and comparison solutions according to Table 1 and the process according to Table 2. This was carried out either by immersion, spraying or spin coating (simulation of the order in the chemcoater = no rinse). After spinning in a paint spinner at 550 revolutions per minute, which results in a NaB film of 5 to 6 μm after a spin duration of 5 seconds, the samples were immediately dried at 70 ° C. in a drying cabinet for 10 minutes. The sample panels treated by spraying or dipping were then rinsed in demineralized water for a further 5 s and then dried. The conductivity of the water running off after the VE final rinse should not exceed 20 µS. The surface resistance is an indication of good spot weldability. It is determined in accordance with DVS leaflet 2929 (German Welding Association, status August 85). The single-sheet method shown in leaflet 2929 was used (electrode force: 75 KN, current: 20 A). The zero value (electrodes sit on top of each other) has already been subtracted from the resistance values given in Tab. 2. Tab. 2 contains the resistance values according to different storage times (1 day, 30 days, 60 days).
Als Beispiel für eine permanent korrosionsschützende Konversionsbehandlung wurde die Überphosphatierbarkeit der behandelten Muster wie folgt geprüft: Die mit dem erfindungsgemäßen Vorbehandlungsverfahren bez. mit Vergleichsverfahren temporär korrosionsgeschützten Bleche wurden mit dem folgenden Verfahrensgang behandelt:
1 % in VE-Wasser
RT, 45 s
1% in demineralized water
RT, 45 s
Die visuelle Beurteilung aller phophatierten Oberflächen nach erfindungsgemäßer Passivierung ergab eine hellgraue, gleichmäßige, feste Phosphatschicht. Diese wurde durch Aufnahme von Vergrößerungen im Röntgenelektronenmikroskop bestätigt.The visual assessment of all phosphated surfaces after passivation according to the invention showed a light gray, uniform, solid phosphate layer. This was confirmed by taking enlargements in the X-ray electron microscope.
Wie die Ausführungsbeispiele zeigen, sind die erhaltenen Ergebnisse von der gewählten Legierung und von der Vorgeschichte des Materials (Lagerzeit) abhängig. Mit der Legierung AC120 werden generell die besseren Ergebnisse erhalten. In allen Fällen erfindungsgemäßer Konversionsbehandlung liegen jedoch die Befunde hinsichtlich Oberflächenwiderstand und Phosphatierbarkeit im technisch erforderlichen Rahmen.As the exemplary embodiments show, the results obtained depend on the alloy selected and on the history of the material (storage time). The better results are generally obtained with the AC120 alloy. In all cases, conversion treatment according to the invention However, the findings regarding surface resistance and phosphatability are within the technically required framework.
Demgegenüber zeigen die mit Vergleichslösungen behandelten Muster deutliche Abweichungen: Eine Erhöhung der Polymerkonzentration (Vergl. 1) führt zu hohen Oberflächenwiderständen und zum Verlust der Phosphatierbarkeit. Verringert man die Konzentration der komplexen Fluoride unter die erfindungsgemäße Mindestkonzentration (Vergl. 2 und 3), bleibt die Phosphatierbarkeit zwar erhalten, die Oberflächenwiderstände nehmen jedoch mit der Lagerzeit stark zu und streuen beträchtlich. Eine Erhöhung der Konzentration der komplexen Fluoride über den erfindungsgemäßen Bereich hinaus (Vergl. 4) führt zu zwar mit der Lagerzeit nur gering ansteigenden, aber generell zu großen Oberflächenwiderständen. Weiterhin wird die Phosphatierbarkeit negativ beeinflußt. Vergleichsbeispiel 5 zeigt den negativen Einfluß einer zu hohen Phosphatkonzentration auf den Oberflächenwiderstand.In contrast, the samples treated with comparison solutions show clear deviations: An increase in the polymer concentration (cf. 1) leads to high surface resistances and a loss of phosphatability. If the concentration of the complex fluorides is reduced below the minimum concentration according to the invention (compare 2 and 3), the phosphatability is retained, but the surface resistances increase sharply with the storage time and scatter considerably. An increase in the concentration of the complex fluorides beyond the range according to the invention (see FIG. 4) leads to surface resistances which increase only slightly with the storage time, but generally lead to high surface resistances. Furthermore, the phosphatability is negatively influenced. Comparative Example 5 shows the negative influence of too high a phosphate concentration on the surface resistance.
Die Prüfung auf Verklebbarkeit erfolgte mit Zugscherversuchen gemäß DIN 53 283 unter Verwendung eines handelsüblichen 2-Komponenten-Epoxiklebstoffs nach Gebrauchsanleitung (TerokalR 5045, Firma Teroson, Heidelberg). Als Substrat wurde die Legierung AC 120 verwendet, die nach Verfahren gemäß Tabelle 2 behandelt und anschließend 30 Tage offen gelagert wurde. Eine weitere Vorbehandlung vor der Bestimmung der Klebefestigkeit erfolgte nicht. Zum Vergleich wurden die Werte für eine nur entfettete und für eine grünchromatierte Probe nach gleicher Lagerzeit gemessen. Die Ergebnisse sind in Tabelle 3 enthalten.
Claims (8)
- A process for the pretreatment of surfaces of aluminium or its alloys before a second, permanently corrosion-preventing conversion treatment, characterized in that the surfaces are contacted with acidic aqueous treatment solutions which contain complex fluorides of the elements boron, silicon, titanium, zirconium or hafnium individually or in admixture with one another in concentrations of the fluoro anions of, in all, 100 to 4000 mg/l and which have a pH value of 0.3 to 3.5 and in that the parts of aluminium or its alloys are subjected to machining and/or forming and/or are joined to one another or to parts of steel and/or galvanized steel and/or alloy-galvanized steel by bonding and/or by welding between the pretreatment of the surfaces of aluminium or its alloys and the permanently corrosion-preventing conversion treatment.
- A process as claimed in claim 1, characterized in that the treatment solutions additionally contain polymers from the class of polyacrylates and/or reaction products of poly(vinylphenol) with aldehydes and organic hydroxyfunctional amines in concentrations below 500 mg/l and in that, where zirconium is present in the treatment solution, the concentration of the reaction products of poly(vinylphenol) with aldehydes and organic hydroxyfunctional amines is less than 100 mg/l.
- A process as claimed in one or both of claims 1 and 2, characterized in that the treatment solutions additionally contain free fluoride ions in concentrations of up to 500 mg/l.
- A process as claimed in one or more of claims 1 to 3, characterized in that the treatment solutions additionally contain polyhydroxycarboxylic acids or anions thereof in concentrations of up to 500 mg/l.
- A process as claimed in one or more of claims 1 to 4, characterized in that the treatment solutions additionally contain sulfate ions in concentrations of up to 50 g/l.
- A process as claimed in one or more of claims 1 to 5, characterized in that the treatment solutions have temperatures of 15 to 60°C and are applied to the aluminium surfaces by spraying, immersion or by the no-rinse method.
- A process as claimed in claim 6, characterized in that the aluminium surfaces are dried at temperatures of 40 to 85°C after the treatment.
- A process as claimed in one or more of claims 1 to 7, characterized in that, in addition, cleaning steps and rinsing with water and/or with activating rinsing baths are carried out between the pretreatment of the surfaces of aluminium or its alloys and the permanently corrosion-preventing conversion treatment.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4317217 | 1993-05-24 | ||
| DE4317217A DE4317217A1 (en) | 1993-05-24 | 1993-05-24 | Chrome-free conversion treatment of aluminum |
| PCT/EP1994/001600 WO1994028193A1 (en) | 1993-05-24 | 1994-05-17 | Chromium-free conversion-coating treatment of aluminium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0700452A1 EP0700452A1 (en) | 1996-03-13 |
| EP0700452B1 true EP0700452B1 (en) | 1997-07-23 |
Family
ID=6488772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94916970A Expired - Lifetime EP0700452B1 (en) | 1993-05-24 | 1994-05-17 | Chromium-free conversion-coating treatment of aluminium |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5584946A (en) |
| EP (1) | EP0700452B1 (en) |
| JP (1) | JP3476824B2 (en) |
| KR (1) | KR100326612B1 (en) |
| AU (1) | AU675328B2 (en) |
| CA (1) | CA2163621C (en) |
| DE (2) | DE4317217A1 (en) |
| ES (1) | ES2104390T3 (en) |
| WO (1) | WO1994028193A1 (en) |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017334A (en) * | 1973-10-04 | 1977-04-12 | Oxy Metal Industries Corporation | Process for treating aluminum cans |
| WO1990012902A1 (en) * | 1989-04-21 | 1990-11-01 | Henkel Corporation | A method and composition for coating aluminum |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2705500A (en) * | 1953-11-04 | 1955-04-05 | Leon L Deer | Cleaning aluminum |
| US3331710A (en) * | 1963-08-23 | 1967-07-18 | Hooker Chemical Corp | Method for coating aluminum |
| DE2031358C3 (en) * | 1970-06-25 | 1981-10-15 | Gerhard Collardin GmbH, 5000 Köln | Process for the production of protective layers on aluminum, iron and zinc by means of acidic solutions containing complex fluorides |
| US4191596A (en) * | 1978-09-06 | 1980-03-04 | Union Carbide Corporation | Method and compositions for coating aluminum |
| NZ195810A (en) * | 1979-12-26 | 1983-07-15 | Amchem Prod | Acidic aqueous solution forming a corrosion-resistant coating on aluminium |
| US4391652A (en) * | 1982-01-29 | 1983-07-05 | Chemical Systems, Inc. | Surface treatment for aluminum and aluminum alloys |
| US4457790A (en) * | 1983-05-09 | 1984-07-03 | Parker Chemical Company | Treatment of metal with group IV B metal ion and derivative of polyalkenylphenol |
| US4921552A (en) * | 1988-05-03 | 1990-05-01 | Betz Laboratories, Inc. | Composition and method for non-chromate coating of aluminum |
| US5294266A (en) * | 1989-07-28 | 1994-03-15 | Metallgesellschaft Aktiengesellschaft | Process for a passivating postrinsing of conversion layers |
| DE4017187A1 (en) * | 1990-05-29 | 1991-12-05 | Metallgesellschaft Ag | METHOD FOR REFILLING CONVERSION LAYERS |
| US5122202A (en) * | 1990-07-05 | 1992-06-16 | Elf Atochem North America, Inc. | Method and compositions for coating non-ferrous metals |
| US5089064A (en) * | 1990-11-02 | 1992-02-18 | Henkel Corporation | Process for corrosion resisting treatments for aluminum surfaces |
| AU662758B2 (en) * | 1991-08-30 | 1995-09-14 | Henkel Corporation | Process for treating metal with aqueous acidic composition that is substantially free from chromium (VI) |
| US5242714A (en) * | 1991-12-20 | 1993-09-07 | Henkel Corporation | Process for forming protective base coatings on metals |
-
1993
- 1993-05-24 DE DE4317217A patent/DE4317217A1/en not_active Withdrawn
-
1994
- 1994-05-17 DE DE59403473T patent/DE59403473D1/en not_active Expired - Lifetime
- 1994-05-17 ES ES94916970T patent/ES2104390T3/en not_active Expired - Lifetime
- 1994-05-17 US US08/545,684 patent/US5584946A/en not_active Expired - Lifetime
- 1994-05-17 WO PCT/EP1994/001600 patent/WO1994028193A1/en active IP Right Grant
- 1994-05-17 KR KR1019950705193A patent/KR100326612B1/en not_active IP Right Cessation
- 1994-05-17 AU AU68442/94A patent/AU675328B2/en not_active Ceased
- 1994-05-17 EP EP94916970A patent/EP0700452B1/en not_active Expired - Lifetime
- 1994-05-17 JP JP50017895A patent/JP3476824B2/en not_active Expired - Fee Related
- 1994-05-17 CA CA002163621A patent/CA2163621C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017334A (en) * | 1973-10-04 | 1977-04-12 | Oxy Metal Industries Corporation | Process for treating aluminum cans |
| WO1990012902A1 (en) * | 1989-04-21 | 1990-11-01 | Henkel Corporation | A method and composition for coating aluminum |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000068458A1 (en) * | 1999-05-11 | 2000-11-16 | Chemetall Gmbh | Pretreatment of aluminum surfaces with chrome-free solutions |
| WO2006084491A1 (en) | 2005-02-08 | 2006-08-17 | Henkel Kommanditgesellschaft Auf Aktien | Method for coating sheet metal, especially zinc sheets |
| US7709058B2 (en) | 2005-02-08 | 2010-05-04 | Henkel Kgaa | Process for coating metal sheet, especially zinc sheet |
| US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| US10920324B2 (en) | 2012-08-29 | 2021-02-16 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| DE102014225237B3 (en) * | 2014-12-09 | 2016-04-28 | Henkel Ag & Co. Kgaa | Process for the wet-chemical pretreatment of a large number of iron and aluminum components in series |
| DE102016217507A1 (en) | 2015-09-15 | 2017-03-16 | Chemetall Gmbh | Pre-treatment of aluminum surfaces with zirconium and molybdenum-containing compositions |
| WO2017046139A1 (en) | 2015-09-15 | 2017-03-23 | Chemetall Gmbh | Pre-treating aluminum surfaces with zirconium- and molybdenum-containing compositions |
| EP4442858A1 (en) * | 2023-04-06 | 2024-10-09 | Henkel AG & Co. KGaA | Composition for the corrosion-protective pretreatment and cleaning of metal surfaces in one step of the process |
| WO2024208739A1 (en) * | 2023-04-06 | 2024-10-10 | Henkel Ag & Co. Kgaa | Composition for the anticorrosive pretreatment and cleaning of metal surfaces in one process step |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2104390T3 (en) | 1997-10-01 |
| JP3476824B2 (en) | 2003-12-10 |
| AU675328B2 (en) | 1997-01-30 |
| CA2163621C (en) | 2004-10-26 |
| DE4317217A1 (en) | 1994-12-01 |
| JPH08510505A (en) | 1996-11-05 |
| US5584946A (en) | 1996-12-17 |
| DE59403473D1 (en) | 1997-08-28 |
| WO1994028193A1 (en) | 1994-12-08 |
| AU6844294A (en) | 1994-12-20 |
| EP0700452A1 (en) | 1996-03-13 |
| CA2163621A1 (en) | 1994-12-08 |
| KR960702539A (en) | 1996-04-27 |
| KR100326612B1 (en) | 2002-11-30 |
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