EP3456864B1 - Two stage pre-treatment of aluminium, in particular aluminium casting alloys, comprising a pickle and a conversion treatment - Google Patents
Two stage pre-treatment of aluminium, in particular aluminium casting alloys, comprising a pickle and a conversion treatment Download PDFInfo
- Publication number
- EP3456864B1 EP3456864B1 EP17191578.8A EP17191578A EP3456864B1 EP 3456864 B1 EP3456864 B1 EP 3456864B1 EP 17191578 A EP17191578 A EP 17191578A EP 3456864 B1 EP3456864 B1 EP 3456864B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pickling solution
- brought
- contact
- solution
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910052782 aluminium Inorganic materials 0.000 title claims description 44
- 238000006243 chemical reaction Methods 0.000 title claims description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 39
- 235000021110 pickles Nutrition 0.000 title claims description 6
- 238000005266 casting Methods 0.000 title description 6
- 229910045601 alloy Inorganic materials 0.000 title description 5
- 239000000956 alloy Substances 0.000 title description 5
- 238000002203 pretreatment Methods 0.000 title description 4
- 239000004411 aluminium Substances 0.000 title 2
- 238000005554 pickling Methods 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 67
- 239000010936 titanium Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- -1 fluoride ions Chemical class 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 2
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 63
- 230000008569 process Effects 0.000 description 28
- 239000003973 paint Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 12
- 239000010802 sludge Substances 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 241001499740 Plantago alpina Species 0.000 description 4
- 125000005233 alkylalcohol group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 101100379225 Drosophila melanogaster cass gene Proteins 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 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 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229910003708 H2TiF6 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- DQTJHJVUOOYAMD-UHFFFAOYSA-N oxotitanium(2+) dinitrate Chemical compound [O-][N+](=O)O[Ti](=O)O[N+]([O-])=O DQTJHJVUOOYAMD-UHFFFAOYSA-N 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical class OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- UEUMIMKGIUYUGH-UHFFFAOYSA-H [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Zr+6] UEUMIMKGIUYUGH-UHFFFAOYSA-H 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012556 adjustment buffer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- VEGSIXIYQSUOQG-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;zirconium Chemical compound [NH4+].[Zr].CC(O)C([O-])=O VEGSIXIYQSUOQG-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- WZHCOOQXZCIUNC-UHFFFAOYSA-N cyclandelate Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C(O)C1=CC=CC=C1 WZHCOOQXZCIUNC-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DKEUYXJXQSBKBQ-UHFFFAOYSA-N oxygen(2-);zirconium(4+);dinitrate Chemical compound [O-2].[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O DKEUYXJXQSBKBQ-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000000306 recurrent effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- SOCDLWOJPVKBHF-UHFFFAOYSA-J titanium(4+) tetraperchlorate Chemical compound [Ti+4].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O SOCDLWOJPVKBHF-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- MQGNWZLWQBTZJR-UHFFFAOYSA-J zirconium(4+) tetraperchlorate Chemical compound [Zr+4].[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O.[O-][Cl](=O)(=O)=O MQGNWZLWQBTZJR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—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
- C23C22/78—Pretreatment of the material to be coated
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
-
- 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
- C23C24/00—Coating starting from inorganic powder
Definitions
- the present invention relates to a process for the corrosion-protective treatment of components made of aluminum, in particular castings such as automobile rims, comprising a pretreatment stage and a subsequent coating.
- the pretreatment step again includes a pickle based on sulfuric acid and phosphate-free aqueous solutions containing water-soluble compounds of the element Ti and at least one polybasic ⁇ -hydroxycarboxylic acid and a source of fluoride ions, the conversion treatment based on an acidic aqueous solution containing water-soluble compounds of the elements Zr and / or Ti is upstream.
- the prior art discloses a multiplicity of pretreatment methods of components made of aluminum, in particular of aluminum casting, for imparting corrosion protection and as a paint adhesion base, which are based on a plurality of successive wet-chemical process steps.
- the component is first subjected to a cleaning, which is a combination of surface-active and etching substances both for removing superficial contaminants originating from upstream fabrication stages, for example mold release agents, as well as for producing a reproducible component surface, which is necessary for the application of a homogeneous adhesion-promoting conversion layer , contains.
- a cleaning which is a combination of surface-active and etching substances both for removing superficial contaminants originating from upstream fabrication stages, for example mold release agents, as well as for producing a reproducible component surface, which is necessary for the application of a homogeneous adhesion-promoting conversion layer , contains.
- additional process steps may be required in order to obtain a substrate surface optimally conditioned for the conversion layer formation.
- WO 94/28193 A1 It is known that a preservation of the aluminum surface produced after the cleaning and acid pickling or dewetting can be achieved for a subsequent permanent corrosion-protective pretreatment if the pickling already has passivating active components selected from water-soluble compounds of the elements Zr and / or Ti.
- active components in the acidic pickling polyhydroxycarboxylic acids, such as gluconic acid, or polymers based on acrylates or derivatized vinylphenols are optional.
- the after the WO 94/28193 A1 obtained passivation is intended to protect the surface against partial oxidation until the application of the permanent corrosion-protecting pretreatment and to preserve the largely homogenous chemical nature of the aluminum surface.
- the semifinished product treated in this way can be subjected to further component production such as chipless machining, welding or forming without the occurrence of adverse effects on the immediately following applied permanent corrosion protection until the application of the permanent corrosion protection.
- the object of the present invention is now to provide the operators of coating equipment for components made of aluminum and its alloys, in particular castings, a pretreatment stage based on the established process sequence of an acid pickling followed by a chromium-free conversion treatment based on the elements Zr and / or Ti built in the continuous operation of such a system, the bath life and maintenance intervals are extended over the prior art and ideally no caused by sludge maintenance of the pretreatment stage of the coating plant is required.
- every measure suitable for avoiding sludge formation should be taken at the same time exerts no negative influence on the corrosion protection and the paint adhesion of the pre-treated in such a coating system components.
- This object is achieved in a method for corrosion-protective treatment of aluminum-made components comprising a pretreatment stage and a subsequent coating, wherein the component in the pretreatment stage first with an aqueous sulfuric acid and phosphate-free pickling solution, the pH of 1 to 2.5, has a free acidity in points of at least 5 and at least one water-soluble compound of the element Ti; a source of fluoride ions and at least one polybasic ⁇ -hydroxycarboxylic acid, and then contacted with an aqueous conversion treatment solution having a pH of 1 to 3.5 and at least one water-soluble compound of the elements Zr and / or Ti becomes.
- the pH denotes the negative decadic logarithm of the activity of the hydronium ions.
- the pH is determined potentiometrically at 20 ° C. directly in the solution by means of pH-sensitive electrodes after two-point calibration with buffer solutions for the pH values of 4.01 and 7.01.
- a compound is water soluble if its solubility in deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) and at a temperature of 20 ° C is at least 1g / kg. All quantities in "g / kg" refer to the proportion of the respective component per kilogram of the respectively indicated reference solution.
- an excellent paint adhesion is achieved which, surprisingly, also in the absence of phosphates and with high tolerance to aluminum ions in the stain, is based on the combination of the Ti and Zr coating applied in the multistage process.
- the absence of phosphates and high tolerance to aluminum ions in the stain enable the pretreatment stage to produce no precipitates and therefore no sludge in continuous operation. This requires the presence of the polybasic ⁇ -hydroxycarboxylic acid.
- Polybasic ⁇ -hydroxycarboxylic acids in the context of the present invention have at least two carboxylic acid groups and at least one hydroxyl group in ⁇ position to one of the carboxylic acid groups.
- the at least one polybasic ⁇ -hydroxycarboxylic acid is selected from those compounds in which each carboxyl group has a hydroxyl group in the ⁇ - or ⁇ -position, and which furthermore preferably has not more than 8 carbon atoms.
- Particularly preferred representatives of the polybasic ⁇ -hydroxycarboxylic acid are tartaric acid and / or citric acid, particularly preferably citric acid.
- the proportion of polybasic ⁇ -hydroxycarboxylic acids in the pickling solution at least 0.1 g / kg, especially preferably at least 0.5 g / kg, especially
- the proportion of polybasic ⁇ - Hydroxycarboxylic acids in the pickling solution therefore in a preferred process according to the invention not greater than 4 g / kg, more preferably not greater than 2 g / kg.
- the positive effect of the mordant-containing water-soluble compounds of the element titanium in the presence of the source of fluoride ions on the subordinate conversion treatment is usually already achieved with small amounts in the range of a few milligrams of Ti per kilogram of mordant.
- the proportion of water-soluble compounds of the element Ti in the pickling solution is preferably at least 0.04 g / kg, more preferably at least 0.1 g / kg. Above one gram of Ti per kilogram of pickling solution, no significant improvement in paint adhesion is obtained after the conversion treatment.
- the pickling solution is preferably not more than 0.6 g / kg, more preferably not more than 0.3 g / kg in each case based on the element Ti of water-soluble compounds of the element Ti.
- water-soluble compounds of the element Ti titanyl sulfate (TiO (SO 4 )), titanyl nitrate (TiO (NO 3 ) 2 ) and / or hexafluorotitanic (H 2 TiF 6 ) and their salts are well suited and therefore preferred in the pickling solution of the process according to the invention , particularly preferred is hexafluorotitanic acid and its salts.
- a source of fluoride ions according to the invention is required for a sufficient stain of the aluminum-made component without a reproducible largely oxide-free surface can not be adjusted and the positive effect of containing in the stain water-soluble compounds of the element titanium on the paint adhesion does not apply can.
- a source of fluoride ions in the context of the present invention is any water-soluble inorganic compound containing fluorine containing at least 100 mg / kg of fluoride ions as 0.1% by weight aqueous solution after TISAB buffering with an aliquot of the buffer. determined potentiometrically at 20 ° C by means of a fluoride ion-sensitive electrode according to DIN 38 405-D-4-1, released. An aliquot of the buffer results in a volume mixing ratio of buffer to aqueous solution containing the source of fluoride of 1: 1.
- the TISAB Buffer (Total Lonic Strength Adjustment Buffer) is manufactured with a resolution of 58 g NaCl, 1 g of sodium citrate and 50 ml of glacial acetic acid in 500 ml of deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) and setting a pH of 5.3 by means of 5 N NaOH and filling to a total volume of 1000 ml again with deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ).
- the total fluoride content in the pickling solution is at least 0.02 g / kg, particularly preferably at least 0.05 g / kg, very particularly preferably at least 0.1 g / kg calculated as F.
- the total fluoride content is determined in the context of the present invention by means of a fluoride ion-sensitive electrode according to DIN 38 405-D-4-1 as described above.
- the proportion of free fluoride in the pickling solution is to be kept low for a moderate pickling rate of the aluminum material.
- the proportion of free fluoride is therefore less than 10 mg / kg, more preferably less than 5 mg / kg each potentiostatically determined directly in the pickling solution at 20 ° C by means of calibrated fluoride-sensitive electrode.
- Suitable sources of fluoride ions are, for example, ammonium bifluoride, sodium fluoride and / or complex fluorides, in particular hexafluorotitanic acid and its salts.
- complex fluorides of the element Zr should not be included in the pickling solution since these are also likely to cause the surfaces of the aluminum-made component to adhere and therefore compete with the conditioning of the aluminum surfaces achieved by the water-soluble compounds of the element Ti.
- the pickling solution therefore contains a total of less than 0.02 g / kg, more preferably less than 0.01 g / kg, most preferably less than 0.004 g / kg of water-soluble compounds of the element Zr calculated as Zr ,
- the pickling solution preferably has a pH below 2.0 in a process according to the invention. This ensures on a regular basis that a sufficient stain can take place in the pretreatment stage.
- the pickling solution has a free acid content of at least 6 points, so that a pickling removal which is largely independent of the type of aluminum material to be treated and sufficiently adequate for the subsequent conversion treatment is ensured, for example in the series treatment of different aluminum materials manufactured individual components or in the series treatment of individual components produced from a mix of different aluminum materials.
- the free acid content in points should preferably not be greater than 10 in order to effect sufficient conditioning of the aluminum surfaces on the basis of the water-soluble compounds of Ti element contained in the pickling solution.
- the free acid content in points is determined in the context of the present invention by diluting 10 ml of the pickling solution to 50 ml and titrating with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption of milliliters of caustic soda indicates the score.
- the presence of a certain buffer capacity or a certain acidity has proven to be a stable process control in a series treatment.
- the total acid content of importance and this is in the pickling solution of the method according to the invention preferably at least 12 points, but preferably not more than 18 points.
- the total acid content is inventively determined analogously to the free acid with the difference that is titrated to a pH of 8.5.
- An aqueous pickling solution is sulfuric if it contains sulfuric acid to adjust the pH and the proportion of other acids with a pKS 1 value of less than 2.5 for the first deprotonation step is less than 1 g / kg, more preferably less than 0 5 g / kg, more preferably less than 0.1 g / kg.
- the pickling solution in the process according to the invention for preventing the precipitation of sparingly soluble salts and the film formation on the surfaces of the aluminum-made component is phosphate-free.
- An aqueous pickling solution is phosphate-free if it contains less than 0.5 g / kg, preferably less than 0.1 g / kg, more preferably less than 0.05 g / kg of phosphates dissolved in water, calculated as PO 4 .
- Particularly suitable nonionic surfactants are selected from alkoxylated alkyl alcohols, alkoxylated fatty amines and / or alkylpolyglycosides, particularly preferably from alkoxylated alkyl alcohols and / or alkoxylated fatty amines, particularly preferably from alkoxylated alkyl alcohols.
- Alkoxylated alkyl alcohols and / or alkoxylated fatty amines are preferably end-capped, more preferably having an alkyl group, which in turn preferably has not more than 8 carbon atoms, more preferably not more than 4 carbon atoms.
- the component in the process of the invention, it is advantageous for sufficient staining and conditioning of the aluminum surfaces, and therefore also preferred, for the component to be contacted with the pickling solution for a duration sufficient to contain at least 2 mg of aluminum per square meter of surface area contacted to pickle the component and particularly preferably also sufficient to produce a coating layer of at least 4 mg of titanium per square meter on the contacted surface of the component.
- the pickling solution is also preferably adjusted for the observance of pretreatment-typical treatment times such that for a alloy according to EN AW-6014 (AIMg0.6Si0.6V) at 40 ° C in an unstirred pickling solution of the method according to the invention, a pickling rate of at least 15 mgm -2 s -1 based on the element aluminum results.
- EN AW-6014 AIMg0.6Si0.6V
- a conversion layer based on the elements Zr and / or Ti is applied in the method according to the invention.
- a layer of at least 50 .mu.mol / m 2 preferably at least 100 .mu.mol / m 2 , more preferably at least 200 .mu.mol / m 2 , but preferably determined by not more than 500 .mu.mol / m 2 by X-ray fluorescence analysis (RFA) based on the sum of the elements Zr and Ti, and the components made of aluminum are therefore brought into contact with the conversion treatment solution for such a duration that a corresponding layer support is realized.
- RFA X-ray fluorescence analysis
- At least 0.1 mmol / kg more preferably at least 0.5 mmol / kg of water-soluble compounds of the elements Zr and / or Ti calculated as a corresponding amount of the elements Zr and / or Ti however, for economic reasons, preferably not more than 5 mmol / kg, more preferably not more than 3 mmol / kg.
- Suitable representatives of water-soluble compounds are ammonium zirconium carbonate ((NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 ), titanyl sulfate (TiO (SO 4 )), zirconium sulfate (Zr (SO 4 ) 2 ), titanium nitrate (Ti (NO 3 ) 4 Zirconium nitrate (Zr (NO 3 ) 4 ), zirconyl nitrate (ZrO (NO 3 ) 2 ), titanyl nitrate (TiO (NO 3 ) 2 ), ammonium zirconium lactate (NH 4 Zr (C 3 H 5 O 3 ) 5 ), zirconium perchlorate ( Zr (ClO 4 ) 4 ), titanium perchlorate (Ti (ClO 4 ) 4 ), and / or hexafluorotitanic acid (H 2 TiF 6 ) or hexafluorozirconic acid (H 2
- the molar ratio of the total content of water-soluble compounds of the elements Zr and Ti relative to the respective elements to the total fluoride content in the conversion treatment solution is at least zero , 1, more preferably at least 0.4. It has surprisingly been found that the use
- the pH of the conversion treatment solution in the pretreatment stage is at least 1.8, more preferably at least 2.0.
- the conversion treatment solution therefore contains a total of less than 0.1 g / kg of water-soluble compounds of the element chromium calculated as Cr.
- the addition of phosphate ions to the conversion treatment solution is not advantageous, so that selbige in the process according to the invention is analogous to the pickling solution phosphate-free and therefore less than 0.5 g / kg, preferably less than 0.1 g / kg, more preferably less than 0 , 05 g / kg of phosphates dissolved in water, calculated as PO 4 .
- Components made of aluminum which are treated in accordance with the present invention corrosion protection, are those whose metallic component consists of aluminum and / or aluminum alloys, in particular aluminum casting alloys, or is composed.
- An alloy is an aluminum alloy in that it consists of at least 50 at.% Of the element Al.
- Suitable components made of aluminum in the method according to the invention are for example selected from semi-finished products such as sheet metal, strip, coil or wire or from complex three-dimensional production objects such as rims for the automotive sector.
- the components may be formed from strip material or sheets and / or joined together or made by casting.
- the treatment of components made of cast aluminum alloys for example AA 6014, in particular rims for the automotive sector is preferred.
- a pretreatment step in the sense of the present invention is a process step which is separate from the application of the paint finish and which comprises the process steps of pickling and conversion treatment which are separated from one another with the aid of liquid compositions in the form of the pickling liquor and each independently stored in system tanks Conversion treatment solution.
- the components made of aluminum are pretreated in series in the pretreatment stage of the process according to the invention.
- pretreatment in series involves contacting a plurality of components made of aluminum with the pickling and conversion treatment solution respectively stored in a system tank, without a complete exchange with a new batch of the following in each of the pretreatment of a single component made of aluminum System tanks of pre-treatment stage stockpiled pickling and conversion treatment solutions takes place.
- the transition of the component from the stain into the conversion treatment takes place "directly".
- a "rinsing step" in the sense of the present invention denotes a process which is intended solely to remove as far as possible active components from an immediately preceding wet-chemical treatment step, which are dissolved in a wet film adhering to the component, by means of a rinsing solution from the surface of the component. without replacing the active components to be removed by others. Active components are dissolved in water compounds that consume already by the mere contacting of the metallic surfaces of the component with the rinsing liquid.
- the rinsing fluid can be city water.
- the components to be treated in the process according to the invention originate from an upstream production process whose surfaces should therefore first be freed from impurities, such as mold release aids, in order to ensure good pickling.
- the component is therefore supplied in the pretreatment stage before being brought into contact with the pickling solution to an alkaline degreasing, more preferably by contacting with an alkaline aqueous composition having a pH above 9, however, preferably below 12, and having a free alkalinity of at least 3 points, but preferably less than 6 points, and optionally containing surface active compounds, preferably selected from nonionic surfactants.
- a rinsing step but preferably no drying step takes place.
- the application of the cleaning, pickling and conversion treatment solution stored in the respective system tanks of the pre-treatment stage can be carried out by all methods known in the art, with immersion and spraying methods for bringing the aluminum made into contact
- the spray method is particularly preferred as the type of application.
- the coating following the pretreatment stage comprises the application of a composition comprising a chemically or physically hardening binder to form a cover layer on the pretreated and aluminum-made component, wherein the cover layer resulting from the coating in the dried or cured state has a layer thickness of preferably at least one micrometer , particularly preferably of at least 10 .mu.m, measured according to the wedge-cut method according to DIN 50986: 1979-03.
- Suitable lacquers are autophoretic lacquers, electrodeposition lacquers, powder lacquers and liquid lacquers which can be applied by conventional means.
- paints based on inorganic binders such as, for example, silicate or lime
- paints based on organic binders can be used according to the invention.
- the following application of lacquers based on organic binders, in particular those containing less than 10% by weight of organic solvent constituents, which have a boiling point below 150 ° C. at 1 bar, is particularly advantageous.
- powder coatings are preferred, in particular those with binders based on epoxy resins, carboxyl- and hydroxyl-containing polyester resins and / or acrylate resins, each having an excellent paint adhesion to the pretreated according to the invention made of aluminum components.
- the component made of aluminum can be subjected after the pretreatment and before the painting of a sink, which serves to remove an adhering to the surface wet film of the conversion solution before the paint is applied. Furthermore, it is usual and may therefore be preferred that the component is dried before the application of the paint. This is the case in particular when a powder coating is to be applied, for which a particularly good paint adhesion base is provided in the method according to the invention and therefore there is a preference.
- the sludge-inhibiting effect of the polybasic ⁇ -hydroxycarboxylic acids is illustrated in Table 2, which assesses the sludge formation in a pickling solution according to the above process step II, but added a total of 1 g / kg of aluminum ions in the form of aluminum sulfate. From this table shows that an inhibition of sludge formation, ie the precipitation of aluminum and titanium salts, succeed in the presence of citric acid or tartaric acid.
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Description
Die vorliegende Erfindung betrifft ein Verfahren zur korrosionsschützenden Behandlung von aus Aluminium gefertigten Bauteilen, insbesondere Gussteilen wie Automobilfelgen, umfassend eine Vorbehandlungsstufe und eine nachfolgende Lackierung. Die Vorbehandlungsstufe beinhaltet wiederum eine Beize auf Basis schwefelsaurer und phosphatfreier wässriger Lösungen enthaltend wasserlösliche Verbindungen des Elements Ti sowie mindestens eine mehrbasige α-Hydroxycarbonsäure und eine Quelle für Fluorid-Ionen, die einer Konversionsbehandlung auf Basis einer sauren wässrigen Lösung enthaltend wasserlösliche Verbindungen der Elemente Zr und/oder Ti vorgelagert ist.The present invention relates to a process for the corrosion-protective treatment of components made of aluminum, in particular castings such as automobile rims, comprising a pretreatment stage and a subsequent coating. The pretreatment step again includes a pickle based on sulfuric acid and phosphate-free aqueous solutions containing water-soluble compounds of the element Ti and at least one polybasic α-hydroxycarboxylic acid and a source of fluoride ions, the conversion treatment based on an acidic aqueous solution containing water-soluble compounds of the elements Zr and / or Ti is upstream.
Im Stand der Technik ist eine Vielzahl an Vorbehandlungsverfahren von aus Aluminium gefertigten Bauteilen, insbesondere von Aluminiumguss, zur Vermittlung eines Korrosionsschutzes und als Lackhaftgrund bekannt, die auf mehreren aufeinanderfolgenden nasschemischen Verfahrensschritten basieren. Üblicherweise wird das Bauteil dabei zunächst einer Reinigung unterzogen, die eine Kombination von oberflächenaktiven und beizenden Substanzen sowohl zur Entfernung von aus vorgelagerten Fabrikationsstufen stammenden oberflächlichen Verschmutzungen, beispielsweise Formtrennmitteln, als auch zur Erzeugung einer reproduzierbaren Bauteiloberfläche, die für die Aufbringung einer homogenen haftungsvermittelnden Konversionsschicht notwendig ist, enthält. Je nach Art der Reinigung können zwischengelagert weitere Verfahrensschritte erforderlich sein, um eine für die Konversionsschichtbildung optimal konditionierte Substratoberfläche zu erhalten. So wird in der die
Auch die internationale Offenlegungsschrift
Auch ist aus der
Das Beizen umfasst nicht lediglich die Entfernung der Oxidschicht, sondern schließt üblicherweise auch das Beizen des aus Aluminium gefertigten Bauteils selbst ein. Dies ist regelmäßig erwünscht und notwendig, um eine homogene reproduzierbare metallische Oberfläche für die nachfolgende korrosionsschützende Konversionsbeschichtung bereitzustellen. Hier ergibt sich jedoch das Problem der Anreicherung von Aluminium-Salzen in der sauren Beize. Die hohe Aluminiumfracht ist ursächlich für die Ausfällung schwerlöslicher Salze insbesondere in Anwesenheit von in der sauren Beize enthaltenden passivierenden Aktivkomponenten auf Basis der Elemente Zr und/oder Ti. Die Ausfällungen führen im kontinuierlichen Betrieb einer Vorbehandlungsstufe zu Schlammbildung und Verkrustungen, die an bewegten Teilen der Beschichtungsanlage wie Ventilen für den Sprühauftrag oder Transportgestellen häufiger entfernt werden müssen. Damit ist eine wiederkehrende Wartung der Anlage erforderlich, die nicht im laufenden Betrieb der Anlage durchgeführt werden kann und üblicherweise den Austausch des gesamten Badvolumens erfordert, so dass auch die Badstandzeit erheblich verkürzt ist.Pickling not only involves removal of the oxide layer, but usually also includes pickling of the aluminum-made component itself. This is regularly desirable and necessary to provide a homogeneous reproducible metallic surface for the subsequent anti-corrosive conversion coating. Here, however, there is the problem of accumulation of aluminum salts in the acidic stain. The high aluminum load is the cause of the precipitation of sparingly soluble salts, especially in the presence of acidic pickling containing passivating active components based on the elements Zr and / or Ti. The precipitates lead in the continuous operation of a pretreatment stage to sludge formation and incrustations on moving parts of the coating plant how valves for spray application or transport racks need to be removed more frequently. Thus, a recurrent maintenance of the system is required, which can not be performed during operation of the system and usually requires the replacement of the entire bath volume, so that the bath life is significantly reduced.
Die vorliegende Erfindung stellt sich nun die Aufgabe den Betreibern von Beschichtungsanlage für aus Aluminium und seinen Legierungen gefertigten Bauteilen, insbesondere Formgussteilen, eine Vorbehandlungsstufe bereitzustellen, die auf der etablierten Prozessfolge einer sauren Beize gefolgt von einer chromfreien Konversionsbehandlung auf Basis der Elemente Zr und/oder Ti aufbaut, wobei im kontinuierlichen Betrieb einer solchen Anlage die Badstandzeiten und Wartungsintervalle gegenüber dem Stand der Technik verlängert sind und idealerweise keine durch Schlammbildung verursachte Wartung der Vorbehandlungsstufe der Beschichtungsanlage erforderlich ist. Gleichzeitig ist jedoch unabdingbar, dass jede für die Vermeidung der Schlammbildung geeignete Maßnahme gleichzeitig keinen negativen Einfluss auf den Korrosionsschutz und die Lackhaftung der in einer solchen Beschichtungsanlage vorbehandelten Bauteile ausübt.The object of the present invention is now to provide the operators of coating equipment for components made of aluminum and its alloys, in particular castings, a pretreatment stage based on the established process sequence of an acid pickling followed by a chromium-free conversion treatment based on the elements Zr and / or Ti built in the continuous operation of such a system, the bath life and maintenance intervals are extended over the prior art and ideally no caused by sludge maintenance of the pretreatment stage of the coating plant is required. At the same time, however, it is indispensable that every measure suitable for avoiding sludge formation should be taken at the same time exerts no negative influence on the corrosion protection and the paint adhesion of the pre-treated in such a coating system components.
Diese Aufgabe wird in einem Verfahren zur korrosionsschützenden Behandlung von aus Aluminium gefertigten Bauteilen umfassend eine Vorbehandlungsstufe und eine nachfolgende Lackierung gelöst, wobei das Bauteil in der Vorbehandlungsstufe zunächst mit einer wässrigen schwefelsauren und phosphatfreien Beizlösung, die einen pH-Wert von 1 bis 2,5, einen freien Säuregehalt in Punkten von zumindest 5 aufweist und mindestens eine wasserlösliche Verbindung des Elements Ti; eine Quelle für Fluorid-Ionen sowie mindestens eine mehrbasige α-Hydroxycarbonsäure enthält, und anschließend mit einer wässrigen Konversionsbehandlungslösung, die einen pH-Wert von 1 bis 3,5 und mindestens eine wasserlösliche Verbindung der Elemente Zr und/oder Ti enthält, in Kontakt gebracht wird.This object is achieved in a method for corrosion-protective treatment of aluminum-made components comprising a pretreatment stage and a subsequent coating, wherein the component in the pretreatment stage first with an aqueous sulfuric acid and phosphate-free pickling solution, the pH of 1 to 2.5, has a free acidity in points of at least 5 and at least one water-soluble compound of the element Ti; a source of fluoride ions and at least one polybasic α-hydroxycarboxylic acid, and then contacted with an aqueous conversion treatment solution having a pH of 1 to 3.5 and at least one water-soluble compound of the elements Zr and / or Ti becomes.
Der pH-Wert bezeichnet den negativen dekadischen Logarithmus der Aktivität der Hydronium-Ionen. Der pH-Wert wird erfindungsgemäß bei 20 °C unmittelbar in der Lösung mittels pH-sensitiver Elektroden nach Zwei-Punkt-Kalibrierung mit Pufferlösungen für die pH-Werte 4,01 und 7,01 potentiometrisch bestimmt.The pH denotes the negative decadic logarithm of the activity of the hydronium ions. According to the invention, the pH is determined potentiometrically at 20 ° C. directly in the solution by means of pH-sensitive electrodes after two-point calibration with buffer solutions for the pH values of 4.01 and 7.01.
Eine Verbindung ist wasserlöslich, wenn ihre Löslichkeit in entionisiertem Wasser (κ<1µScm-1) und bei einer Temperatur von 20 °C mindestens 1 g/kg beträgt. Alle Mengenangaben in "g/kg" beziehen sich auf den Anteil der jeweiligen Komponente pro Kilogramm der jeweils angezeigten Referenzlösung.A compound is water soluble if its solubility in deionized water (κ <1μScm -1 ) and at a temperature of 20 ° C is at least 1g / kg. All quantities in "g / kg" refer to the proportion of the respective component per kilogram of the respectively indicated reference solution.
Im erfindungsgemäßen Verfahren wird eine hervorragende Lackhaftung erzielt, die überraschenderweise auch in Abwesenheit von Phosphaten und bei hoher Toleranz gegenüber Aluminium-Ionen in der Beize auf die Kombination der im mehrstufigen Verfahren aufgebrachten Ti- und Zr-Auflage beruht. Die Abwesenheit von Phosphaten und hohe Toleranz gegenüber Aluminium-Ionen in der Beize ermöglichen, dass die Vorbehandlungsstufe im kontinuierlichen Betrieb keine Ausfällungen und damit keinen Schlamm produziert. Hierfür erforderlich ist die Anwesenheit der mehrbasigen α-Hydroxycarbonsäure.In the process according to the invention, an excellent paint adhesion is achieved which, surprisingly, also in the absence of phosphates and with high tolerance to aluminum ions in the stain, is based on the combination of the Ti and Zr coating applied in the multistage process. The absence of phosphates and high tolerance to aluminum ions in the stain enable the pretreatment stage to produce no precipitates and therefore no sludge in continuous operation. This requires the presence of the polybasic α-hydroxycarboxylic acid.
Mehrbasige α-Hydroxycarbonsäuren im Sinne der vorliegenden Erfindung besitzen mindestens zwei Carbonsäuregruppen und zumindest eine Hydroxyl-Gruppe in α-Stellung zu einer der Carbonsäuregruppen. In einer bevorzugten Ausführung ist die zumindest eine mehrbasige α-Hydroxycarbonsäure ausgewählt aus solchen Verbindungen, in denen jede Carboxyl-Gruppe eine Hydroxyl-Gruppe in α- oder β-Stellung aufweist, und die weiterhin bevorzugt nicht mehr als 8 Kohlenstoffatome aufweisen. Besonders bevorzugte Vertreter der mehrbasigen α-Hydroxycarbonsäure sind Weinsäure und/oder Zitronensäure, insbesondere bevorzugt Zitronensäure.Polybasic α-hydroxycarboxylic acids in the context of the present invention have at least two carboxylic acid groups and at least one hydroxyl group in α position to one of the carboxylic acid groups. In a preferred embodiment, the at least one polybasic α-hydroxycarboxylic acid is selected from those compounds in which each carboxyl group has a hydroxyl group in the α- or β-position, and which furthermore preferably has not more than 8 carbon atoms. Particularly preferred representatives of the polybasic α-hydroxycarboxylic acid are tartaric acid and / or citric acid, particularly preferably citric acid.
Für eine ausreichend hohe Toleranz gegenüber Aluminium-Ionen und weiterhin gute Ergebnisse in der Konditionierung der Aluminiumoberfläche für die Lackapplikation in der Vorbehandlungsstufe ist im erfindungsgemäßen Verfahren bevorzugt, dass der Anteil an mehrbasigen α-Hydroxycarbonsäuren in der Beizlösung mindestens 0,1 g/kg, besonders bevorzugt mindestens 0,5 g/kg, ganz besondersFor a sufficiently high tolerance to aluminum ions and furthermore good results in the conditioning of the aluminum surface for the paint application in the pretreatment stage is preferred in the inventive method that the proportion of polybasic α-hydroxycarboxylic acids in the pickling solution at least 0.1 g / kg, especially preferably at least 0.5 g / kg, especially
bevorzugt mindestens 1 g/kg beträgt. Aus Gründen der Wirtschaftlichkeit sind Anteile oberhalb von zehn Gramm pro Kilogramm der Beizlösung nicht sinnvoll und in der Beizlösung üblicherweise weder erforderlich für die Konditionierung der Aluminiumoberfläche in der Vorbehandlungsstufe noch für die Stabilisierung der gelösten Verbindungen des Elements Ti. Konsequenterweise ist der Anteil an mehrbasigen α-Hydroxycarbonsäuren in der Beizlösung daher in einem bevorzugten erfindungsgemäßen Verfahren nicht größer als 4 g/kg, besonders bevorzugt nicht größer als 2 g/kg.preferably at least 1 g / kg. For reasons of economy, proportions above ten grams per kilogram of the pickling solution are not meaningful and in the pickling solution usually neither necessary for the conditioning of the aluminum surface in the pretreatment stage nor for the stabilization of the dissolved compounds of the element Ti. Consequently, the proportion of polybasic α- Hydroxycarboxylic acids in the pickling solution therefore in a preferred process according to the invention not greater than 4 g / kg, more preferably not greater than 2 g / kg.
Der positive Effekt der in der Beize enthaltenden wasserlöslichen Verbindungen des Elements Titan in Gegenwart der Quelle für Fluorid-Ionen auf die nachrangige Konversionsbehandlung wird üblicherweise bereits mit geringen Mengen im Bereich von wenigen Milligramm an Ti pro Kilogramm der Beize erzielt. Bevorzugt liegt der Anteil an wasserlöslichen Verbindungen des Elements Ti in der Beizlösung bei mindestens 0,04 g/kg, besonders bevorzugt bei mindestens 0,1 g/kg. Oberhalb von einen Gramm an Ti pro Kilogramm der Beizlösung wird keine signifikante Verbesserung der Lackhaftung nach der Konversionsbehandlung erzielt. Auch zur Vermeidung von Ausfällungen und zur Erhöhung der Toleranz gegenüber Aluminium-Ionen ist es daher bevorzugt, wenn die Beizlösung vorzugsweise nicht mehr als 0,6 g/kg, besonders bevorzugt nicht mehr als 0,3 g/kg jeweils bezogen auf das Element Ti an wasserlöslichen Verbindungen des Elements Ti enthält.The positive effect of the mordant-containing water-soluble compounds of the element titanium in the presence of the source of fluoride ions on the subordinate conversion treatment is usually already achieved with small amounts in the range of a few milligrams of Ti per kilogram of mordant. The proportion of water-soluble compounds of the element Ti in the pickling solution is preferably at least 0.04 g / kg, more preferably at least 0.1 g / kg. Above one gram of Ti per kilogram of pickling solution, no significant improvement in paint adhesion is obtained after the conversion treatment. Also, to avoid precipitation and to increase the tolerance to aluminum ions, it is therefore preferable if the pickling solution is preferably not more than 0.6 g / kg, more preferably not more than 0.3 g / kg in each case based on the element Ti of water-soluble compounds of the element Ti.
Als wasserlösliche Verbindungen des Elements Ti sind Titanylsulfat (TiO(SO4)), Titanylnitrat (TiO(NO3)2)und/oder Hexafluorotitansäure (H2TiF6) sowie ihre Salze gut geeignet und daher in der Beizlösung des erfindungsgemäßen Verfahrens bevorzugte Vertreter, insbesondere bevorzugt ist Hexafluorotitansäure und ihre Salze.As water-soluble compounds of the element Ti titanyl sulfate (TiO (SO 4 )), titanyl nitrate (TiO (NO 3 ) 2 ) and / or hexafluorotitanic (H 2 TiF 6 ) and their salts are well suited and therefore preferred in the pickling solution of the process according to the invention , particularly preferred is hexafluorotitanic acid and its salts.
Eine Quelle für Fluorid-Ionen ist erfindungsgemäß erforderlich für eine hinreichende Beize des aus Aluminium gefertigten Bauteils ohne die eine reproduzierbare weitestgehend oxidfreie Oberfläche nicht eingestellt werden kann und der positive Effekt der in der Beize enthaltenden wasserlöslichen Verbindungen des Elements Titan auf die Lackhaftung nicht zum Tragen kommen kann.A source of fluoride ions according to the invention is required for a sufficient stain of the aluminum-made component without a reproducible largely oxide-free surface can not be adjusted and the positive effect of containing in the stain water-soluble compounds of the element titanium on the paint adhesion does not apply can.
Eine Quelle für Fluorid-Ionen im Sinne der vorliegenden Erfindung ist jede wasserlösliche anorganische Verbindung enthaltend Fluor, die als 0,1 Gew.-%ige wässrige Lösung nach TISAB-Pufferung mit einer aliquoten Menge des Puffers mindestens 100 mg/kg Fluorid-Ionen, potentiometrisch bei 20 °C mittels einer Fluorid-Ionensensitiven Elektrode nach der DIN 38 405-D-4-1 bestimmt, freisetzt. Eine aliquote Menge des Puffers resultiert in einem volumenbezogenen Mischungsverhältnis von Puffer zur wässrigen Lösung enthaltend die Quelle an Fluorid von 1:1. Der TISAB Puffer ("Total lonic Strength Adjustment Buffer") wird hergestellt durch Auflösung von 58 g NaCl, 1 g Natriumcitrat und 50 ml Eisessig in 500 ml entionisiertem Wasser (κ < 1µScm-1) und Einstellen eines pH-Wertes von 5,3 mittels 5 N NaOH sowie Auffüllen auf ein Gesamtvolumen von 1000 ml wiederum mit entionisiertem Wasser (κ < 1µScm-1).A source of fluoride ions in the context of the present invention is any water-soluble inorganic compound containing fluorine containing at least 100 mg / kg of fluoride ions as 0.1% by weight aqueous solution after TISAB buffering with an aliquot of the buffer. determined potentiometrically at 20 ° C by means of a fluoride ion-sensitive electrode according to DIN 38 405-D-4-1, released. An aliquot of the buffer results in a volume mixing ratio of buffer to aqueous solution containing the source of fluoride of 1: 1. The TISAB Buffer (Total Lonic Strength Adjustment Buffer) is manufactured with a resolution of 58 g NaCl, 1 g of sodium citrate and 50 ml of glacial acetic acid in 500 ml of deionized water (κ <1 μScm -1 ) and setting a pH of 5.3 by means of 5 N NaOH and filling to a total volume of 1000 ml again with deionized water (κ < 1μScm -1 ).
Vorliegend ist es bevorzugt, wenn der Gesamtfluorid-Gehalt in der Beizlösung mindestens 0,02 g/kg, besonders bevorzugt mindestens 0,05 g/kg, ganz besonders bevorzugt mindestens bei 0,1 g/kg berechnet als F beträgt. Der Gesamtfluorid-Gehalt wird im Rahmen der vorliegenden Erfindung mittels einer Fluorid-Ionensensitiven Elektrode nach der DIN 38 405-D-4-1 wie zuvor beschrieben bestimmt.In the present case, it is preferred if the total fluoride content in the pickling solution is at least 0.02 g / kg, particularly preferably at least 0.05 g / kg, very particularly preferably at least 0.1 g / kg calculated as F. The total fluoride content is determined in the context of the present invention by means of a fluoride ion-sensitive electrode according to DIN 38 405-D-4-1 as described above.
Der Anteil an freiem Fluorid ist in der Beizlösung ist für eine moderate Beizrate des Aluminiumwerkstoffes gering zu halten. In einer bevorzugten Ausführungsform ist der Anteil an freiem Fluorid daher kleiner als 10 mg/kg, besonders bevorzugt kleiner als 5 mg/kg jeweils potentiostatisch unmittelbar in der Beizlösung bei 20 °C mittels kalibrierter Fluorid-sensitiver Elektrode bestimmt.The proportion of free fluoride in the pickling solution is to be kept low for a moderate pickling rate of the aluminum material. In a preferred embodiment, the proportion of free fluoride is therefore less than 10 mg / kg, more preferably less than 5 mg / kg each potentiostatically determined directly in the pickling solution at 20 ° C by means of calibrated fluoride-sensitive electrode.
Geeignete Quellen für Fluorid-Ionen sind beispielsweise Ammoniumbifluord, Natriumfluorid und/oder komplexe Fluoride, insbesondere Hexafluorotitansäure und ihre Salze. Jedoch sollten vorzugsweise keine komplexen Fluoride des Elements Zr in der Beizlösung enthalten sein, da diese ebenfalls geeignet sind eine Belegung der Oberflächen des aus Aluminium gefertigten Bauteils herbeizuführen und daher mit der durch die wasserlöslichen Verbindungen des Elements Ti erzielten Konditionierung der Aluminiumoberflächen konkurrieren.Suitable sources of fluoride ions are, for example, ammonium bifluoride, sodium fluoride and / or complex fluorides, in particular hexafluorotitanic acid and its salts. However, preferably, complex fluorides of the element Zr should not be included in the pickling solution since these are also likely to cause the surfaces of the aluminum-made component to adhere and therefore compete with the conditioning of the aluminum surfaces achieved by the water-soluble compounds of the element Ti.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens enthält die Beizlösung daher insgesamt weniger als 0,02 g/kg, besonders bevorzugt weniger als 0,01 g/kg, ganz besonders bevorzugt weniger als 0,004 g/kg an wasserlöslichen Verbindungen des Elements Zr berechnet als Zr.In a preferred embodiment of the method according to the invention, the pickling solution therefore contains a total of less than 0.02 g / kg, more preferably less than 0.01 g / kg, most preferably less than 0.004 g / kg of water-soluble compounds of the element Zr calculated as Zr ,
Die Beizlösung weist in einem erfindungsgemäßen Verfahren vorzugsweise einen pH-Wert unterhalb von 2,0 auf. Damit ist regelmäßig sichergestellt, dass eine hinreichende Beize in der Vorbehandlungsstufe erfolgen kann.The pickling solution preferably has a pH below 2.0 in a process according to the invention. This ensures on a regular basis that a sufficient stain can take place in the pretreatment stage.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens weist die Beizlösung einen freien Säuregehalt von zumindest 6 Punkten auf, so dass ein von der Art des zu behandelnden Aluminiummaterials weitestgehend unabhängiger und für die nachfolgende Konversionsbehandlung hinreichender Beizabtrag sichergestellt ist, beispielsweise in der Serienbehandlung von jeweils aus unterschiedlichen Aluminiummaterialien gefertigten Einzelbauteilen oder in der Serienbehandlung von aus einem Mix unterschiedlicher Aluminiummaterialien gefertigter Einzelbauteile. Umgekehrt sollte der freie Säuregehalt in Punkten vorzugsweise nicht größer als 10 sein, um eine ausreichende Konditionierung der Aluminiumoberflächen auf der Basis der in der Beizlösung enthaltenden wasserlöslichen Verbindungen des Elements Ti zu bewirken.In a preferred embodiment of the process according to the invention, the pickling solution has a free acid content of at least 6 points, so that a pickling removal which is largely independent of the type of aluminum material to be treated and sufficiently adequate for the subsequent conversion treatment is ensured, for example in the series treatment of different aluminum materials manufactured individual components or in the series treatment of individual components produced from a mix of different aluminum materials. Conversely, the free acid content in points should preferably not be greater than 10 in order to effect sufficient conditioning of the aluminum surfaces on the basis of the water-soluble compounds of Ti element contained in the pickling solution.
Der freie Säuregehalt in Punkten wird im Rahmen der vorliegenden Erfindung bestimmt, indem man 10 ml der Beizlösung auf 50 ml verdünnt und mit 0,1 N Natronlauge bis zu einem pH-Wert von 3,6 titriert. Der Verbrauch an Millilitern Natronlauge gibt die Punktzahl an.The free acid content in points is determined in the context of the present invention by diluting 10 ml of the pickling solution to 50 ml and titrating with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption of milliliters of caustic soda indicates the score.
Neben der Einstellung eines freien Säuregehalts in der Beizlösung als Regelungsparameter für die Bereitstellung von im erfindungsgemäßen Verfahren optimal gebeizten Oberflächen der aus Aluminium gefertigten Bauteile, hat sich das Vorliegen einer gewissen Pufferkapazität oder eines gewissen Säurevorrats für eine stabile Prozessführung bei einer Serienbehandlung herausgestellt. Hierfür ist der Gesamtsäuregehalt von Bedeutung und dieser liegt in der Beizlösung des erfindungsgemäßen Verfahrens vorzugsweise bei zumindest 12 Punkten, jedoch vorzugsweise bei nicht mehr als 18 Punkten. Der Gesamtsäuregehalt wird erfindungsgemäß analog zur freien Säure bestimmt mit dem Unterschied, dass bis zu einem pH-Wert von 8,5 titriert wird.In addition to the setting of a free acid content in the pickling solution as a control parameter for the provision of optimally pickled in the process according to the invention surfaces of aluminum-made components, the presence of a certain buffer capacity or a certain acidity has proven to be a stable process control in a series treatment. For this purpose, the total acid content of importance and this is in the pickling solution of the method according to the invention preferably at least 12 points, but preferably not more than 18 points. The total acid content is inventively determined analogously to the free acid with the difference that is titrated to a pH of 8.5.
Bezüglich der in der Beizlösung der Vorbehandlungsstufe des erfindungsgemäßen Verfahrens für die Einstellung des Säuregehaltes zu verwendenden Säure wurde festgestellt, dass diese schwefelsauer für eine gute Beizwirkung sein sollte. Eine wässrige Beizlösung ist schwefelsauer, wenn sie zur Einstellung des pH-Wertes Schwefelsäure enthält und der Anteil an anderen Säuren mit einem pKS1-Wert von weniger als 2,5 für den ersten Deprotonierungsschritt geringer als 1 g/kg, besonders bevorzugt geringer als 0,5 g/kg, insbesondere bevorzugt geringer als 0,1 g/kg ist.With regard to the acid to be used in the pickling solution of the pretreatment stage of the process according to the invention for the adjustment of the acid content, it was determined that this should be sulfur-acidic for a good pickling action. An aqueous pickling solution is sulfuric if it contains sulfuric acid to adjust the pH and the proportion of other acids with a pKS 1 value of less than 2.5 for the first deprotonation step is less than 1 g / kg, more preferably less than 0 5 g / kg, more preferably less than 0.1 g / kg.
Weiterhin ist die Beizlösung im erfindungsgemäßen Verfahren zur Vermeidung der Ausfällung schwerlöslicher Salze und der Schichtbildung auf den Oberflächen des aus Aluminium gefertigten Bauteils phosphatfrei. Eine wässrige Beizlösung ist phosphatfrei, wenn sie weniger als 0,5 g/kg, vorzugsweise weniger als 0,1 g/kg, besonders bevorzugt weniger als 0,05 g/kg an in Wasser gelösten Phosphaten berechnet als PO4 enthält.Furthermore, the pickling solution in the process according to the invention for preventing the precipitation of sparingly soluble salts and the film formation on the surfaces of the aluminum-made component is phosphate-free. An aqueous pickling solution is phosphate-free if it contains less than 0.5 g / kg, preferably less than 0.1 g / kg, more preferably less than 0.05 g / kg of phosphates dissolved in water, calculated as PO 4 .
In einem bevorzugten erfindungsgemäßen Verfahren enthält die Beizlösung zusätzlich eine oberflächenaktive organische Verbindung, besonders bevorzugt ein Niotensid, wobei der Anteil an oberflächenaktiven organischen Substanzen in der Beizlösung vorzugsweise zumindest 0,1 mmol/L beträgt. In diesem Zusammenhang sind allgemein solche Niotenside bevorzugt, deren HLB-Wert (Hydrophilic-Lipophilic-Balance) zumindest 8, besonders bevorzugt zumindest 10, insbesondere bevorzugt zumindest 12 ist, jedoch besonders bevorzugt nicht mehr als 18, insbesondere bevorzugt nicht mehr als 16 beträgt. Der HLB-Wert dient zur quantitativen Klassifizierung von Niotensiden entsprechend ihrer inneren molekularen Struktur, wobei eine Aufgliederung des Niotensids in eine lipophile und eine hydrophile Gruppe vorgenommen wird. Der HLB Wert kann auf der willkürlichen Skala Werte von Null bis 20 annehmen und berechnet sich gemäß vorliegender Erfindung wie folgt:
- ML:
- Molmasse der lypophilen Gruppe des Niotensids
- M:
- Molmasse des Niotensids
- M L :
- Molar mass of the hypophilic group of nonionic surfactant
- M:
- Molar mass of the nonionic surfactant
Insbesonders geeignete Niotenside sind ausgewählt aus alkoxylierten Alkylalkoholen, alkoxylierten Fettaminen und/oder Alkylpolyglycosiden, besonders bevorzugt aus alkoxylierten Alkylalkoholen und/oder alkoxylierten Fettaminen, insbesondere bevorzugt aus alkoxylierten Alkylalkoholen. DieParticularly suitable nonionic surfactants are selected from alkoxylated alkyl alcohols, alkoxylated fatty amines and / or alkylpolyglycosides, particularly preferably from alkoxylated alkyl alcohols and / or alkoxylated fatty amines, particularly preferably from alkoxylated alkyl alcohols. The
alkoxylierten Alkylalkohole und/oder alkoxylierten Fettamine sind dabei vorzugsweise endgruppenverschlossen, besonders bevorzugt mit einer Alkyl-Gruppe, die wiederum vorzugsweise nicht mehr als 8 Kohlenstoffatome, besonders bevorzugt nicht mehr als 4 Kohlenstoffatome aufweist.Alkoxylated alkyl alcohols and / or alkoxylated fatty amines are preferably end-capped, more preferably having an alkyl group, which in turn preferably has not more than 8 carbon atoms, more preferably not more than 4 carbon atoms.
Im erfindungsgemäßen Verfahren ist es von Vorteil für eine ausreichende Beize und Konditionierung der Aluminiumoberflächen und daher auch bevorzugt, dass das Bauteil für eine solche Dauer mit der Beizlösung in Kontakt gebracht wird, die ausreicht, um mindestens 2 mg Aluminium pro Quadratmeter der in Kontakt gebrachten Oberfläche des Bauteils zu beizen und besonders bevorzugt ebenso ausreicht um eine Schichtauflage von mindestens 4 mg Titan pro Quadratmeter auf der in Kontakt gebrachten Oberfläche des Bauteils zu erzeugen. In diesem Zusammenhang ist die Beizlösung auch für die Einhaltung vorbehandlungstypischer Behandlungszeiten vorzugsweise derart eingestellt, dass für eine für eine Legierung nach EN AW-6014 (AIMg0.6Si0.6V) bei 40 °C in einer ungerührten Beizlösung des erfindungsgemäßen Verfahrens eine Beizrate von zumindest 15 mgm-2s-1 bezogen auf das Element Aluminium resultiert.In the process of the invention, it is advantageous for sufficient staining and conditioning of the aluminum surfaces, and therefore also preferred, for the component to be contacted with the pickling solution for a duration sufficient to contain at least 2 mg of aluminum per square meter of surface area contacted to pickle the component and particularly preferably also sufficient to produce a coating layer of at least 4 mg of titanium per square meter on the contacted surface of the component. In this context, the pickling solution is also preferably adjusted for the observance of pretreatment-typical treatment times such that for a alloy according to EN AW-6014 (AIMg0.6Si0.6V) at 40 ° C in an unstirred pickling solution of the method according to the invention, a pickling rate of at least 15 mgm -2 s -1 based on the element aluminum results.
In der der Beize unmittelbar nachfolgenden Konversionsbehandlung wird im erfindungsgemäßen Verfahren eine Konversionsschicht auf Basis der Elemente Zr und/oder Ti aufgebracht. Für eine hinreichende Lackhaftung ist bevorzugt, wenn nach der Konversionsbehandlung eine Schichtauflage von zumindest 50 µmol/m2, vorzugsweise zumindest 100 µmol/m2, besonders bevorzugt zumindest 200 µmol/m2, jedoch vorzugsweise von nicht mehr als 500 µmol/m2 bestimmt mittels Röntgenfluoreszenzanalyse (RFA) bezogen auf die Summe der Elemente Zr und Ti resultiert, und die aus Aluminium gefertigten Bauteile daher für eine solche Dauer mit der Konversionsbehandlungslösung in Kontakt gebracht werden, dass eine entsprechende Schichtauflage realisiert ist. Hierfür ist weiterhin bevorzugt, dass in der Konversionsbehandlungslösung des erfindungsgemäßen Verfahrens mindestens 0,1 mmol/kg, besonders bevorzugt mindestens 0,5 mmol/kg an wasserlöslichen Verbindungen der Elemente Zr und/oder Ti berechnet als entsprechende Menge der Elemente Zr und/oder Ti enthalten sind, jedoch aus wirtschaftlichen Gründen vorzugsweise nicht mehr als 5 mmol/kg, besonders bevorzugt nicht mehr als 3 mmol/kg. Geeignete Vertreter wasserlöslicher Verbindungen sind Ammoniumzirconiumcarbonat ((NH4)2Zr(OH)2(CO3)2), Titanylsulfat (TiO(SO4)), Zirconiumsulfat (Zr(SO4)2), Titannitrat (Ti(NO3)4), Zirconiumnitrat (Zr(NO3)4), Zirconylnitrat (ZrO(NO3)2), Titanylnitrat (TiO(NO3)2), Ammoniumzirconiumlactat (NH4Zr(C3H5O3)5), Zirconiumperchlorat (Zr(ClO4)4), Titanperchlorat (Ti(ClO4)4), und/oder Hexafluorotitansäure (H2TiF6) bzw. Hexafluorozirkonsäure (H2ZrF6) sowie ihre jeweiligen Salze.In the treatment immediately following the pickle, a conversion layer based on the elements Zr and / or Ti is applied in the method according to the invention. For a sufficient paint adhesion is preferred if after the conversion treatment, a layer of at least 50 .mu.mol / m 2 , preferably at least 100 .mu.mol / m 2 , more preferably at least 200 .mu.mol / m 2 , but preferably determined by not more than 500 .mu.mol / m 2 by X-ray fluorescence analysis (RFA) based on the sum of the elements Zr and Ti, and the components made of aluminum are therefore brought into contact with the conversion treatment solution for such a duration that a corresponding layer support is realized. For this purpose, it is further preferred that in the conversion treatment solution of the process according to the invention at least 0.1 mmol / kg, more preferably at least 0.5 mmol / kg of water-soluble compounds of the elements Zr and / or Ti calculated as a corresponding amount of the elements Zr and / or Ti however, for economic reasons, preferably not more than 5 mmol / kg, more preferably not more than 3 mmol / kg. Suitable representatives of water-soluble compounds are ammonium zirconium carbonate ((NH 4 ) 2 Zr (OH) 2 (CO 3 ) 2 ), titanyl sulfate (TiO (SO 4 )), zirconium sulfate (Zr (SO 4 ) 2 ), titanium nitrate (Ti (NO 3 ) 4 Zirconium nitrate (Zr (NO 3 ) 4 ), zirconyl nitrate (ZrO (NO 3 ) 2 ), titanyl nitrate (TiO (NO 3 ) 2 ), ammonium zirconium lactate (NH 4 Zr (C 3 H 5 O 3 ) 5 ), zirconium perchlorate ( Zr (ClO 4 ) 4 ), titanium perchlorate (Ti (ClO 4 ) 4 ), and / or hexafluorotitanic acid (H 2 TiF 6 ) or hexafluorozirconic acid (H 2 ZrF 6 ) and their respective salts.
In diesem Zusammenhang ist für eine effektive Schichtbildung auf Basis der Elemente Zr und/oder Ti in der Konversionsbehandlung weiterhin bevorzugt, wenn das molare Verhältnis des Gesamtanteils wasserlöslicher Verbindungen der Elemente Zr und Ti bezogen auf die jeweiligen Elemente zum Gesamtfluorid-Gehalt in der Konversionsbehandlungslösung mindestens 0,1, besonders bevorzugt mindestens 0,4 beträgt. Es hat sich überraschenderweise herausgestellt, dass die VerwendungIn this connection, for effective film formation based on the elements Zr and / or Ti in the conversion treatment, it is further preferable that the molar ratio of the total content of water-soluble compounds of the elements Zr and Ti relative to the respective elements to the total fluoride content in the conversion treatment solution is at least zero , 1, more preferably at least 0.4. It has surprisingly been found that the use
wasserlöslicher Verbindungen des Elements Zr, insbesondere von Hexafluorozirkonsäure und ihren Salzen, in der Konversionsbehandlungslösung in Kombination mit der Ti-haltigen Beizlösung die besten Lackhaftungsergebnisse erzielt und daher im erfindungsgemäßen Verfahren bevorzugt ist.water-soluble compounds of the element Zr, in particular of hexafluorozirconium acid and their salts, achieved in the conversion treatment solution in combination with the Ti-containing pickling solution, the best paint adhesion results and is therefore preferred in the process according to the invention.
In einer bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens liegt der pH-Wert der Konversionsbehandlungslösung in der Vorbehandlungsstufe bei zumindest 1,8, besonders bevorzugt bei zumindest 2,0.In a preferred embodiment of the method according to the invention, the pH of the conversion treatment solution in the pretreatment stage is at least 1.8, more preferably at least 2.0.
Für eine hinreichende Konversionsbehandlung in der Vorbehandlungsstufe des erfindungsgemäßen Verfahrens bedarf es nicht der Anwesenheit von wasserlöslichen Verbindungen des Elements Chrom. In einer weiteren bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens enthält die Konversionsbehandlungslösung daher insgesamt weniger als 0,1 g/kg an wasserlöslichen Verbindungen des Elements Chroms berechnet als Cr. Auch ist der Zusatz von Phosphat-Ionen zur Konversionsbehandlungslösung nicht vorteilhaft, so dass selbige im erfindungsgemäßen Verfahren analog zur Beizlösung phosphatfrei ist und daher weniger als 0,5 g/kg, vorzugsweise weniger als 0,1 g/kg, besonders bevorzugt weniger als 0,05 g/kg an in Wasser gelösten Phosphaten berechnet als PO4 enthält.For a sufficient conversion treatment in the pretreatment stage of the process according to the invention, it is not necessary for the presence of water-soluble compounds of the element chromium. In a further preferred embodiment of the method according to the invention, the conversion treatment solution therefore contains a total of less than 0.1 g / kg of water-soluble compounds of the element chromium calculated as Cr. Also, the addition of phosphate ions to the conversion treatment solution is not advantageous, so that selbige in the process according to the invention is analogous to the pickling solution phosphate-free and therefore less than 0.5 g / kg, preferably less than 0.1 g / kg, more preferably less than 0 , 05 g / kg of phosphates dissolved in water, calculated as PO 4 .
Aus Aluminium gefertigte Bauteile, die gemäß der vorliegenden Erfindung korrosionsschützend behandelt werden, sind solche, deren metallischer Bestandteil aus Aluminium und/oder Aluminiumlegierungen, insbesondere Aluminiumgusslegierungen, bestehen oder zusammengesetzt ist. Eine Legierung ist eine Aluminiumlegierung, insofern sie zu mindestens 50 At.-% aus dem Element AI besteht. Im erfindungsgemäßen Verfahren geeignete aus Aluminium gefertigte Bauteile sind beispielsweise ausgewählt aus Halbzeugen wie Blech, Band, Coil oder Draht oder aus komplexen dreidimensionalen Fertigungsobjekten wie Felgen für den automobilen Bereich. Die Bauteile wiederum können aus Bandmaterial oder Blechen geformt und/oder zusammengefügt oder im Gussverfahren hergestellt worden sein. Im Rahmen der vorliegenden Erfindung bevorzugt ist die Behandlung von aus Aluminiumgusslegierungen, beispielsweise AA 6014, gefertigten Bauteilen, insbesondere Felgen für den automobilen Bereich.Components made of aluminum, which are treated in accordance with the present invention corrosion protection, are those whose metallic component consists of aluminum and / or aluminum alloys, in particular aluminum casting alloys, or is composed. An alloy is an aluminum alloy in that it consists of at least 50 at.% Of the element Al. Suitable components made of aluminum in the method according to the invention are for example selected from semi-finished products such as sheet metal, strip, coil or wire or from complex three-dimensional production objects such as rims for the automotive sector. In turn, the components may be formed from strip material or sheets and / or joined together or made by casting. In the context of the present invention, the treatment of components made of cast aluminum alloys, for example AA 6014, in particular rims for the automotive sector is preferred.
Eine Vorbehandlungsstufe im Sinne der vorliegenden Erfindung ist eine von der Aufbringung der Lackierung getrennte Verfahrensstufe umfassend die voneinander zeitlich getrennten Verfahrensschritte Beize und Konversionsbehandlung unter Zuhilfenahme von jeweils unabhängig voneinander in Systemtanks bevorrateten flüssigen Zusammensetzungen in Form der Beiz- bzw. der Konversionsbehandlungslösung. In einer bevorzugten Ausführungsform werden die aus Aluminium gefertigten Bauteile in der Vorbehandlungsstufe des erfindungsgemäßen Verfahrens in Serie vorbehandelt. Als Vorbehandlung in Serie gilt erfindungsgemäß das In-Kontakt-Bringen einer Vielzahl von aus Aluminium gefertigten Bauteilen mit der jeweils in einem Systemtank bevorrateten Beiz- und Konversionsbehandlungslösung, ohne dass nach jeder Vorbehandlung eines einzelnen aus Aluminium gefertigten Bauteils ein vollständiger Austausch mit Neuansatz der in den Systemtanks der Vorbehandlungsstufe bevorrateten Beiz- und Konversionsbehandlungslösungen erfolgt.A pretreatment step in the sense of the present invention is a process step which is separate from the application of the paint finish and which comprises the process steps of pickling and conversion treatment which are separated from one another with the aid of liquid compositions in the form of the pickling liquor and each independently stored in system tanks Conversion treatment solution. In a preferred embodiment, the components made of aluminum are pretreated in series in the pretreatment stage of the process according to the invention. According to the invention, pretreatment in series involves contacting a plurality of components made of aluminum with the pickling and conversion treatment solution respectively stored in a system tank, without a complete exchange with a new batch of the following in each of the pretreatment of a single component made of aluminum System tanks of pre-treatment stage stockpiled pickling and conversion treatment solutions takes place.
Der Übergang des Bauteils von der Beize in die Konversionsbehandlung erfolgt "unmittelbar". Erfindungsgemäß bedeutet dies, dass die Konversionsbehandlung der Beize nachfolgt, ohne dass eine Benetzung des Bauteils mit einer anderen flüssigen Zusammensetzung, die weder eine Spülnoch Konversionsbehandlungslösung im Sinne der vorliegenden Erfindung darstellt, zwischengeschaltet ist, vorzugsweise ist jedoch mindestens ein Spülschritt auf Basis einer oder mehrerer Spüllösungen zwischengeschaltet. Ein "Spülschritt" im Sinne der vorliegenden Erfindung bezeichnet einen Vorgang, der allein dazu bestimmt ist, Aktivkomponenten aus einem unmittelbar vorausgegangenem nasschemischen Behandlungsschritt, die in einem dem Bauteil anhaftenden Nassfilm gelöst vorliegen, mittels einer Spüllösung von der Oberfläche des Bauteils möglichst weitgehend zu entfernen, ohne dass die zu entfernenden Aktivkomponenten durch andere ersetzt werden. Aktivkomponenten sind dabei in Wasser gelöste Verbindungen, die sich bereits durch das bloße In-Kontakt-Bringen der metallischen Oberflächen des Bauteils mit der Spülflüssigkeit verbrauchen. So kann die Spülflüssigkeit beispielsweise Stadtwasser sein.The transition of the component from the stain into the conversion treatment takes place "directly". According to the invention, this means that the conversion treatment follows the pickling without intervening a wetting of the component with another liquid composition which is neither a flushing nor conversion treatment solution in the sense of the present invention, but preferably at least one flushing step is based on one or more flushing solutions interposed. A "rinsing step" in the sense of the present invention denotes a process which is intended solely to remove as far as possible active components from an immediately preceding wet-chemical treatment step, which are dissolved in a wet film adhering to the component, by means of a rinsing solution from the surface of the component. without replacing the active components to be removed by others. Active components are dissolved in water compounds that consume already by the mere contacting of the metallic surfaces of the component with the rinsing liquid. For example, the rinsing fluid can be city water.
Zudem findet in einem bevorzugten erfindungsgemäßen Verfahren in der Vorbehandlungsstufe zwischen Beize und Konversionsbehandlung kein solcher Verfahrensschritt statt, bei dem durch die Bereitstellung und Nutzung technischer Mittel eine Trocknung oder eine Entfernung des wässrigen, auf der Oberfläche des Bauteils anhaftenden Flüssigfilms beabsichtigt ist, insbesondere durch Zuführung thermischer Energie oder Aufprägen einer Luftströmung.Moreover, in a preferred process according to the invention in the pretreatment stage between pickling and conversion treatment, no such process step takes place in which drying and removal of the aqueous liquid film adhering to the surface of the component is intended by the provision and use of technical means, in particular by supplying thermal Energy or imprinting an airflow.
Die im erfindungsgemäßem Verfahren zu behandelnden Bauteile stammen aus einem vorgelagerten Fertigungsprozess deren Oberflächen daher zur Gewährleistung einer guten Beize zunächst von Verunreinigungen wie Formtrennhilfsmitteln befreit werden sollten. In einem bevorzugten erfindungsgemäßen Verfahren wird das Bauteil daher in der Vorbehandlungsstufe vor dem In-Kontakt-Bringen mit der Beizlösung einer alkalischen Entfettung zugeführt, besonders bevorzugt durch In-Kontakt-Bringen mit einer alkalischen wässrigen Zusammensetzung, die einen pH-Wert oberhalb von 9, jedoch vorzugsweise unterhalb von 12, und eine freie Alkalität von mindestens 3 Punkten, jedoch vorzugsweise weniger als 6 Punkten aufweist und optional oberflächenaktive Verbindungen, vorzugsweise ausgewählt aus nichtionischen Tensiden, enthält.The components to be treated in the process according to the invention originate from an upstream production process whose surfaces should therefore first be freed from impurities, such as mold release aids, in order to ensure good pickling. In a preferred method according to the invention, the component is therefore supplied in the pretreatment stage before being brought into contact with the pickling solution to an alkaline degreasing, more preferably by contacting with an alkaline aqueous composition having a pH above 9, however, preferably below 12, and having a free alkalinity of at least 3 points, but preferably less than 6 points, and optionally containing surface active compounds, preferably selected from nonionic surfactants.
In diesem Zusammenhang ist weiterhin bevorzugt, dass nach der alkalischen Entfettung und vor dem In-Kontakt-Bringen mit der Beizlösung ein Spülschritt, jedoch vorzugsweise kein Trocknungsschritt erfolgt.In this context, it is further preferred that after the alkaline degreasing and before bringing into contact with the pickling solution, a rinsing step, but preferably no drying step takes place.
Die Applikation der in den jeweiligen Systemtanks der Vorbehandlungsstufe bevorrateten Reinigungs-, Beiz- und Konversionsbehandlungslösung kann mit allen im Stand der Technik bekannten Verfahren erfolgen, wobei Tauch- und Sprühverfahren für das In-Kontakt-Bringen der aus Aluminium gefertigtenThe application of the cleaning, pickling and conversion treatment solution stored in the respective system tanks of the pre-treatment stage can be carried out by all methods known in the art, with immersion and spraying methods for bringing the aluminum made into contact
Bauteile mit diesen Lösungen bevorzugt sind, besonders bevorzugt ist das Sprühverfahren als Applikationsart.Components with these solutions are preferred, the spray method is particularly preferred as the type of application.
Die der Vorbehandlungsstufe nachfolgende Lackierung beinhaltet erfindungsgemäß die Aufbringung einer Zusammensetzung enthaltend ein chemisch oder physikalisch aushärtendes Bindemittel zur Ausbildung einer Deckschicht auf dem vorbehandeltem und aus Aluminium gefertigtem Bauteil, wobei die aus der Lackierung resultierende Deckschicht im getrockneten oder ausgehärteten Zustand eine Schichtdicke von vorzugsweise zumindest einem Mikrometer, besonders bevorzugt von zumindest 10 µm, gemessen gemäß Keilschnittverfahren nach der DIN 50986:1979-03 aufweist.According to the invention, the coating following the pretreatment stage comprises the application of a composition comprising a chemically or physically hardening binder to form a cover layer on the pretreated and aluminum-made component, wherein the cover layer resulting from the coating in the dried or cured state has a layer thickness of preferably at least one micrometer , particularly preferably of at least 10 .mu.m, measured according to the wedge-cut method according to DIN 50986: 1979-03.
Geeignete Lacke sind autophorethische Lacke, Elektrotauchlacke, Pulverlacke sowie mit konventionellen Mitteln applizierbare Flüssiglacke. Hinsichtlich der verwendeten Bindemittel können erfindungsgemäß sowohl Lacke, die auf anorganischen Bindemitteln wie beispielsweise Silkat oder Kalk basieren, als auch Lacke basierend auf organischen Bindemittel eingesetzt werden. Besonders vorteilhaft ist erfindungsgemäß die nachfolgende Auftragung von auf organischen Bindemitteln basierten Lacken, insbesondere solchen, die weniger als 10 Gew.-% an organischen Lösemittelbestandteilen enthalten, die einem Siedepunkt unterhalb von 150 °C bei 1 bar aufweisen. In diesem Zusammenhang sind daher Pulverlacke bevorzugt, insbesondere solche mit Bindemitteln auf Basis von Epoxidharzen, carboxy- und hydroxygruppenhaltige Polyesterharzen und/oder Acrylatharzen, die jeweils eine hervorragende Lackhaftung auf den entsprechend der Erfindung vorbehandelten aus Aluminium gefertigten Bauteilen aufweisen.Suitable lacquers are autophoretic lacquers, electrodeposition lacquers, powder lacquers and liquid lacquers which can be applied by conventional means. With regard to the binders used, both paints based on inorganic binders, such as, for example, silicate or lime, and paints based on organic binders can be used according to the invention. According to the invention, the following application of lacquers based on organic binders, in particular those containing less than 10% by weight of organic solvent constituents, which have a boiling point below 150 ° C. at 1 bar, is particularly advantageous. In this context, therefore, powder coatings are preferred, in particular those with binders based on epoxy resins, carboxyl- and hydroxyl-containing polyester resins and / or acrylate resins, each having an excellent paint adhesion to the pretreated according to the invention made of aluminum components.
Das aus Aluminium gefertigte Bauteil kann nach der Vorbehandlung und vor der Lackierung einer Spüle unterworfen werden, die dazu dient, einen auf der Oberfläche anhaftenden Nassfilm der Konversionslösung zu entfernen bevor der Lack aufgetragen wird. Ferner ist es üblich und kann daher bevorzugt sein, dass das Bauteil vor der Auftragung des Lackes getrocknet wird. Dies ist insbesondere dann der Fall, wenn ein Pulverlack aufzutragen ist, für die im erfindungsgemäßen Verfahren ein besonders guter Lackhaftgrund bereitgestellt wird und daher eine Präferenz besteht.The component made of aluminum can be subjected after the pretreatment and before the painting of a sink, which serves to remove an adhering to the surface wet film of the conversion solution before the paint is applied. Furthermore, it is usual and may therefore be preferred that the component is dried before the application of the paint. This is the case in particular when a powder coating is to be applied, for which a particularly good paint adhesion base is provided in the method according to the invention and therefore there is a preference.
Im Folgenden wird die Korrosionsschutzwirkung einer erfindungsgemäßen Verfahrensabfolge anhand der Vorbehandlung von Aluminiumblechen (EN AW-6014) dargelegt und zudem die Neigung zur Schlammbildung in schwefelsauren Beizlösungen der Vorbehandlungsstufe enthaltend Fluorokomplexe des Elements Titan und 1 g/kg an gelösten Aluminium untersucht.The corrosion protection effect of a process sequence according to the invention is described below on the basis of the pretreatment of aluminum sheets (EN AW-6014) and, in addition, the tendency for sludge formation in sulfuric acid pickling solutions of the pretreatment stage containing fluorocomplexes of the element titanium and 1 g / kg of dissolved aluminum is investigated.
Die Verfahrensabfolge zur Behandlung der Aluminiumbleche (EN AW-6014) beinhaltete die aufeinanderfolgenden Verfahrensschritte I bis IV, wobei jedem der Verfahrensschritte I-III ein Spülschritt mit entionisierten Wasser (κ<1 µScm-1) folgte und die Bleche nach dem Spülschritt nach Verfahrensschritt III im Luftstrom getrocknet wurden, ehe die Lackierung im Schritt IV vorgenommen wurde:
I. Reinigung:
- 30 g/LBONDERITE C-AK G 414 (Henkel AG & Co. KGaA) in Stadtwasser
- In-Kontakt-Bringen erfolgt durch Sprühen für 160 Sekunden bei 60 °C und 1 bar
II. Beize:
- Schwefelsaure wässrige Lösung mit einem pH-Wert von 1,6 enthaltend 4,4 g/kg Al2(SO4)3·14 H2O und zusätzlich
- a. 0,5 g/kg H2TiF6
- b. 0,5 g/kg H2TiF6 / 1,3 g/kg Zitronensäure
- In-Kontakt-Bringen erfolgt durch Sprühen für 160 Sekunden bei 50 °C und 1 bar
III. Konversionsbehandlung
30 g/L BONDERITE M-NT 4595 R5 MU (Henkel AG & Co. KGaA) in entionisiertem Wasser (κ<1 µScm-1) ergebend eine Behandlungslösung enthaltend 100 mg/kg H2ZrF6, wobei ein pH-Wert von 2,8 mittels NH4CO3-Lösung eingestellt wurde.
IV. Lackierung
Pulverlack Freiotherm PO1857B plus Klarlack Freiotherm KO1853KRA999 (beide Emil Frei GmbH & Co. KG):
- Auftragsmenge des Pulverlacks betrug ca. 90 g/m2 und nach dem Einbrennen für 10 Minuten bei 180 °C ergab sich eine Trockenfilmdicke von ca. 60 µm.
- Auftragsmenge des Klarlacks betrug ca. 50 g/m2 und Einbrennen für 10 Minuten bei 150 °C ergab eine Trockenfilmdicke von ca. 20 µm
I. Cleaning:
- 30 g / LBONDERITE C-AK G 414 (Henkel AG & Co. KGaA) in town water
- Contacting is done by spraying for 160 seconds at 60 ° C and 1 bar
II. Pickling:
- Sulfuric acid aqueous solution with a pH of 1.6 containing 4.4 g / kg Al 2 (SO 4 ) 3 · 14 H 2 O and in addition
- a. 0.5 g / kg H 2 TiF 6
- b. 0.5 g / kg H 2 TiF 6 / 1.3 g / kg citric acid
- Contacting is done by spraying for 160 seconds at 50 ° C and 1 bar
III. conversion treatment
30 g / L BONDERITE M-NT 4595 R5 MU (Henkel AG & Co. KGaA) in deionized water (κ <1 μScm -1 ) resulting in a treatment solution containing 100 mg / kg H 2 ZrF 6 , wherein a pH of 2 8 was adjusted by means of NH 4 CO 3 solution.
IV. Paint
Powder coating Freiotherm PO1857B plus Clearcoat Freiotherm KO1853KRA999 (both Emil Frei GmbH & Co. KG):
- Application amount of the powder coating was about 90 g / m 2 and after baking for 10 minutes at 180 ° C resulted in a dry film thickness of about 60 microns.
- Application amount of the clearcoat was about 50 g / m 2 and baking for 10 minutes at 150 ° C gave a dry film thickness of about 20 microns
Die Ergebnisse der Tabelle 1 belegen anhand der insgesamt niedrigen Unterwanderungswerte den Vorteil einer Verfahrensführung, bei der der Beizlösung Fluorokomplexe des Elements Ti hinzugesetzt sind. Zusätzlich zu den sehr guten Korrosionsschutzergebnissen im CASS-Test, insbesondere in Gegenwart der Zitronensäure, wird in derartigen Beizlösungen die Schlammbildung durch die Zugabe von Zitronensäure effektiv verhindert.
Die schlamminhibierende Wirkung der mehrbasigen α-Hydoxycarbonsäuren ist in der Tabelle 2 veranschaulicht, die die Schlammbildung in einer Beizlösung gemäß obigen Verfahrensschritt II, der jedoch insgesamt 1 g/kg Aluminium-Ionen in Form von Aluminiumsulfat hinzugesetzt sind, beurteilt. Aus dieser Tabelle geht hervor, dass eine Inhibierung der Schlammbildung, also der Ausfällung von Aluminium- und Titan-Salzen, in Gegenwart von Zitronensäure oder Weinsäure gelingt.The sludge-inhibiting effect of the polybasic α-hydroxycarboxylic acids is illustrated in Table 2, which assesses the sludge formation in a pickling solution according to the above process step II, but added a total of 1 g / kg of aluminum ions in the form of aluminum sulfate. From this table shows that an inhibition of sludge formation, ie the precipitation of aluminum and titanium salts, succeed in the presence of citric acid or tartaric acid.
Claims (15)
- A method for the anti-corrosion treatment of components made of aluminum, comprising a pretreatment stage and subsequent coating, in which method, in the pretreatment stage, the component is first brought into contact with an aqueous phosphate-free sulfuric acid pickling solution which has a pH of from 1 to 2.5, a free acid content of at least 5 points and contains at least one water-soluble compound of the element Ti, a source of fluoride ions and at least one polybasic α-hydroxycarboxylic acid, and is subsequently brought into contact with an aqueous conversion treatment solution which has a pH of from 1 to 3.5 and contains at least one water-soluble compound of the elements Zr and/or Ti.
- The method according to claim 1, characterized in that the proportion of α-hydroxycarboxylic acids in the pickling solution is at least 0.1 g/kg, preferably at least 0.5 g/kg, particularly preferably at least 1 g/kg, but preferably does not exceed 4 g/kg, particularly preferably does not exceed 2 g/kg.
- The method according to one or both of the preceding claims, characterized in that the α-hydroxycarboxylic acids in the pickling solution are selected from citric acid and/or tartaric acid, preferably from citric acid.
- The method according to one or more of the preceding claims, characterized in that the proportion of water-soluble compounds of the element Ti in the pickling solution is at least 0.04 g/kg, preferably at least 0.1 g/kg, but preferably does not exceed 0.6 g/kg, particularly preferably does not exceed 0.3 g/kg, in each case based on the element Ti.
- The method according to one or more of the preceding claims, characterized in that the pickling solution has a pH below 2.
- The method according to one or more of the preceding claims, characterized in that the pickling solution has a free acid content of at least 6 points, but preferably no more than 10 points.
- The method according to one or more of the preceding claims, characterized in that the pickling solution has a total acid content of at least 12 points, but preferably no more than 18 points.
- The method according to one or more of the preceding claims, characterized in that the proportion of water-soluble compounds of the elements Zr and/or Ti in the conversion treatment solution is at least 0.1 mmol/kg, preferably at least 0.5 mmol/kg, but preferably does not exceed 5 mmol/kg, particularly preferably does not exceed 3 mmol/kg, calculated in each case as corresponding amounts of the elements Zr and/or Ti.
- The method according to one or more of the preceding claims, characterized in that the water-soluble compounds of the elements Zr and/or Ti are selected from water-soluble compounds of the element Zr, which are in turn preferably selected from hexafluorozirconic acid and the salts thereof.
- The method according to one or more of the preceding claims, characterized in that the component is brought into contact with the pickling solution for long enough to pickle at least 2 mg of aluminum per square meter of the surface of the component that has been brought into contact, and to preferably also at least produce a coating layer of at least 4 mg of titanium per square meter of the surface of the component that has been brought into contact.
- The method according to one or more of the preceding claims, characterized in that, before being brought into contact with the pickling solution, the component undergoes alkaline degreasing, preferably by being brought into contact with an alkaline aqueous composition which has a pH of greater than 9, but preferably less than 12, and a free alkalinity of at least 3 points but preferably less than 6 points and which optionally contains surface-active compounds which are preferably selected from non-ionic surfactants.
- The method according to claim 11, characterized in that, after the alkaline degreasing and before being brought into contact with the pickling solution, a rinsing step, but preferably not a drying step, takes place.
- The method according to one or more of the preceding claims, characterized in that, after being brought into contact with the pickling solution and before being brought into contact with the conversion treatment solution, a rinsing step, but preferably not a drying step, takes place.
- The method according to one or more of the preceding claims, characterized in that, after being brought into contact with the conversion treatment solution and before being coated, a rinsing step takes place, and immediately before being coated, a drying step preferably also takes place.
- The method according to one or more of the preceding claims, characterized in that the component is coated in the subsequent coating with a powder coating.
Priority Applications (9)
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ES17191578T ES2767852T3 (en) | 2017-09-18 | 2017-09-18 | Two-stage aluminum pretreatment, in particular aluminum alloys, comprising pickling and conversion treatment |
PL17191578T PL3456864T3 (en) | 2017-09-18 | 2017-09-18 | Two stage pre-treatment of aluminium, in particular aluminium casting alloys, comprising a pickle and a conversion treatment |
EP17191578.8A EP3456864B1 (en) | 2017-09-18 | 2017-09-18 | Two stage pre-treatment of aluminium, in particular aluminium casting alloys, comprising a pickle and a conversion treatment |
HUE17191578A HUE048447T2 (en) | 2017-09-18 | 2017-09-18 | Two stage pre-treatment of aluminium, in particular aluminium casting alloys, comprising a pickle and a conversion treatment |
MX2020001673A MX2020001673A (en) | 2017-09-18 | 2018-06-26 | Two-stage pre-treatment of aluminum, in particular aluminum casting alloys, comprising pickle and conversion treatment. |
CN201880060188.5A CN111094624B (en) | 2017-09-18 | 2018-06-26 | Two-stage pretreatment of aluminum, particularly cast aluminum alloys, including pickling and conversion treatment |
KR1020207007534A KR102538202B1 (en) | 2017-09-18 | 2018-06-26 | Two-step pretreatment of aluminum, particularly aluminum casting alloys, including pickling and conversion treatment |
PCT/EP2018/067027 WO2019052701A1 (en) | 2017-09-18 | 2018-06-26 | Two-stage pre-treatment of aluminum, in particular aluminum casting alloys, comprising pickle and conversion treatment |
US16/817,044 US11499237B2 (en) | 2017-09-18 | 2020-03-12 | Two-stage pretreatment of aluminum, in particular aluminum casting alloys, comprising pickle and conversion treatment |
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EP17191578.8A EP3456864B1 (en) | 2017-09-18 | 2017-09-18 | Two stage pre-treatment of aluminium, in particular aluminium casting alloys, comprising a pickle and a conversion treatment |
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JPS5173938A (en) * | 1974-12-25 | 1976-06-26 | Nippon Packaging Kk | Aruminiumuoyobi sonogokinnohyomenshoriho |
DE4317217A1 (en) | 1993-05-24 | 1994-12-01 | Henkel Kgaa | Chrome-free conversion treatment of aluminum |
DE19921842A1 (en) | 1999-05-11 | 2000-11-16 | Metallgesellschaft Ag | Pretreatment of aluminum surfaces with chrome-free solutions |
US6821633B2 (en) | 2002-05-17 | 2004-11-23 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Non-chromate conversion coating compositions, process for conversion coating metals, and articles so coated |
GB0500071D0 (en) * | 2005-01-05 | 2005-02-09 | Houghton Australia Pty Ltd | Cleaning formulation |
CN101463475A (en) * | 2007-12-19 | 2009-06-24 | 鸿富锦精密工业(深圳)有限公司 | Magnesium alloy phosphating method and formation solution thereof |
DE102012215679A1 (en) * | 2012-09-04 | 2014-05-15 | Henkel Ag & Co. Kgaa | Process for the corrosion-protective surface treatment of metallic components in series |
WO2015052546A1 (en) * | 2013-10-09 | 2015-04-16 | ArcelorMittal Investigación y Desarrollo, S.L. | Sheet metal having a znaimg coating and improved flexibility and corresponding production method |
DE102014206407A1 (en) * | 2014-04-03 | 2015-10-08 | Henkel Ag & Co. Kgaa | Two-stage pre-treatment of aluminum including pickle and passivation |
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2017
- 2017-09-18 EP EP17191578.8A patent/EP3456864B1/en active Active
- 2017-09-18 ES ES17191578T patent/ES2767852T3/en active Active
- 2017-09-18 HU HUE17191578A patent/HUE048447T2/en unknown
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2018
- 2018-06-26 CN CN201880060188.5A patent/CN111094624B/en active Active
- 2018-06-26 KR KR1020207007534A patent/KR102538202B1/en active IP Right Grant
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2020
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Also Published As
Publication number | Publication date |
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EP3456864A1 (en) | 2019-03-20 |
HUE048447T2 (en) | 2020-08-28 |
US20200208273A1 (en) | 2020-07-02 |
MX2020001673A (en) | 2020-07-13 |
US11499237B2 (en) | 2022-11-15 |
WO2019052701A1 (en) | 2019-03-21 |
CN111094624B (en) | 2023-01-24 |
PL3456864T3 (en) | 2020-05-18 |
KR20200054974A (en) | 2020-05-20 |
KR102538202B1 (en) | 2023-05-30 |
CN111094624A (en) | 2020-05-01 |
ES2767852T3 (en) | 2020-06-18 |
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