EP2812462A1 - Procédé de traitement de surface de pièces en alliage d'aluminium ou de magnesium - Google Patents
Procédé de traitement de surface de pièces en alliage d'aluminium ou de magnesiumInfo
- Publication number
- EP2812462A1 EP2812462A1 EP13703431.0A EP13703431A EP2812462A1 EP 2812462 A1 EP2812462 A1 EP 2812462A1 EP 13703431 A EP13703431 A EP 13703431A EP 2812462 A1 EP2812462 A1 EP 2812462A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- salt
- corrosion
- parts
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 107
- 238000004381 surface treatment Methods 0.000 title claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910000838 Al alloy Inorganic materials 0.000 title description 17
- 229910000861 Mg alloy Inorganic materials 0.000 title description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 56
- 230000007797 corrosion Effects 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- -1 rare-earth salt Chemical class 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims description 56
- 238000007654 immersion Methods 0.000 claims description 34
- 238000011282 treatment Methods 0.000 claims description 20
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- 238000002048 anodisation reaction Methods 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001844 chromium Chemical class 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 150000002603 lanthanum Chemical class 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 150000004673 fluoride salts Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 34
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 238000007743 anodising Methods 0.000 abstract description 14
- 239000011651 chromium Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 24
- 229910052804 chromium Inorganic materials 0.000 description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000007921 spray Substances 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 239000003973 paint Substances 0.000 description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 229910052746 lanthanum Inorganic materials 0.000 description 8
- 229910000547 2024-T3 aluminium alloy Inorganic materials 0.000 description 7
- 238000005238 degreasing Methods 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 101100330295 Arabidopsis thaliana OASB gene Proteins 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000004532 chromating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 229910052766 Lawrencium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- CNQCVBJFEGMYDW-UHFFFAOYSA-N lawrencium atom Chemical compound [Lr] CNQCVBJFEGMYDW-UHFFFAOYSA-N 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 150000003325 scandium Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
-
- 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
- C23C22/05—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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/57—Treatment of magnesium or alloys based thereon
-
- 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
- C23C22/83—Chemical 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Definitions
- the present invention is in the field of surface treatment of light alloy parts made of aluminum, aluminum alloy, magnesium or magnesium alloy, in order to give them protection against corrosion. More particularly, it relates to a method of surface treatment of aluminum or magnesium parts or their respective alloys.
- parts made from aluminum alloy or magnesium alloy must undergo surface treatment operations, in order to increase their corrosion resistance. This is particularly the case for parts intended for use in the aeronautical industry, for which it is imposed stringent requirements, particularly in terms of performance test salt spray resistance.
- a first of these techniques is the chemical conversion treatment of the aluminum alloy.
- the most common of these processes known under the trade name "Alodine® 1200" from Henkel, carries out a chromating treatment. He uses a substance based on hexavalent chromium for this purpose. If this process makes it possible to confer on the aluminum alloy a good resistance to corrosion, while ensuring a capacitance of electrical conduction of the part, by the formation on the part of a complex surface layer composed mainly of hydroxides
- chromium oxyhydroxides and aluminum it raises an environmental problem. Hexavalent chromium substances are toxic to living organisms.
- Another technique conventionally used to significantly improve the corrosion resistance of aluminum alloy parts involves an anodizing step, followed by one or more clogging steps, that is to say closing or closing existing porosities in the porous anodic layer created on the surface of the room by the anodizing step.
- the most commonly used to achieve a significant increase in the resistance of parts to corrosion, especially to meet the requirements of the aerospace sector consists of chromic anodic oxidation, followed by hydrothermal clogging based on potassium dichromate. .
- this process uses a substance based on hexavalent chromium, which is dangerous for health.
- magnesium alloy parts there are also currently several surface treatment techniques to increase their corrosion resistance properties.
- etching performs a chromating treatment. He uses a substance based on hexavalent chromium for this purpose. If this process makes it possible to confer on the magnesium alloy a good resistance to corrosion, by forming a complex surface layer composed mainly of hydroxides, chromium oxyhydroxides and magnesium on the part, it nevertheless raises also, for the same reasons as expressed above, an environmental problem.
- the present invention aims to remedy the disadvantages of the processes surface treatment of aluminum alloy or magnesium alloy parts in order to increase their resistance to corrosion, as proposed by the prior art, in particular to those described above, by proposing a such a process which does not implement any substance that is toxic to living organisms, and in particular no hexavalent chromium, while at the same time having performances, in terms of protecting the parts against oxidation, that are at least equivalent to the processes of the art prior art using substances based on hexavalent chromium.
- corrosion inhibitor means an element which, present in a low concentration in a coating formed on a part, slows or stops the corrosion process of the part in contact with a corrosive medium.
- the metal salt present in the first bath is a salt of a transition metal corrosion inhibitor.
- a transition metal is here defined conventionally in itself. same, as a metal of the block d of Mendeleyev's painting, with the exception of lutetium and lawrencium.
- the corrosion inhibiting metal salt may be, for example, a salt of zinc, manganese, yttrium, zirconium, molybdenum, copper, iron, vanadium, titanium, palladium, silver, gold, nickel, cobalt, chromium, platinum, etc.
- This salt may especially be a sulphate, a chloride, a nitrate, a fluoride, an acetate, etc.
- Trivalent chromium salts are particularly preferred in the context of the invention. In the present description, conventional trivalent chromium is understood to mean chromium in the +3 oxidation state. Hexavalent chromium means chromium in the +6 oxidation state.
- the second bath comprises, in addition to an oxidizing compound, a rare earth salt corrosion inhibitor.
- Rare earths are here defined in a classical way in itself, and include the fifteen lanthanides, scandium and ytthum.
- the rare earth salt corrosion inhibitor may be for example a salt of lanthanides such as cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, d holmium, erbium, thulium, ytterbium, lutetium; a scandium salt; or yttrium salt.
- This salt may especially be a sulphate, a chloride, a nitrate, a fluoride, an acetate, etc.
- the cerium salts which may be in the +4 oxidation state, and preferably in the +3 oxidation state, in particular in the nitrate form, are particularly preferred in the context of the invention, as are lanthanum salts.
- the chromium-based substances in a +3 oxidation state, as well as the cerium salts and the lanthanum salts, are in particular advantageously not harmful to the environment or health.
- Such a process advantageously makes it possible to form on the surface of the part a layer of oxides / hydroxides containing metal derived from the metal salt present in the first bath, for example trivalent chromium, and the rare earth from the rare earth salt present in the second bath, for example cerium or lanthanum.
- This layer has excellent corrosion resistance properties and thus effectively protects the part against corrosion.
- the succession of the immersion steps in each of the first bath and the second bath, each inducing a chemical conversion of the material on the surface of the part makes it possible to obtain a synergistic effect, which leads, unexpectedly, to properties of resistance to corrosion of the room much greater than those obtained by immersion in one of these baths, or in two successive baths, the second containing only an oxidizing compound, or only a rare earth salt corrosion inhibitor.
- the conversion layer obtained on the surface of the part also advantageously makes it possible to provide electrical conduction, and it also constitutes a good hanging base for paint systems used in particular in the aeronautical sector.
- adhesion of conventional paint systems to the surface layer formed on the part by the process according to the invention is in particular as good as that obtained for the parts treated by the processes of the prior art using hexavalent chromium .
- one or more rinsing steps of the part for example with water, are carried out between immersion in the first bath and immersion in the second bath.
- the oxidizing compound in the one and the other of the first bath and the second bath, can be of any type known in itself for the chemical conversion baths of aluminum or magnesium or their respective alloys. Compounds having no adverse effect on the environment are particularly preferred in the context of the invention.
- oxidizing compounds are fluoride-based substances, such as ammonium fluoride or potassium fluoro-zirconate K 2 ZrF 6 , of permanganate, such as potassium permanganate, hydrogen peroxide H 2 O 2. etc.
- the concentration of oxidizing compound in the first bath may especially be between 0.1 and 50 g / l.
- the corrosion inhibiting metal salt and the oxidizing compound present in the first bath may be constituted by two different compounds, or by one and the same compound capable of ensuring on its own the two functions of corrosion inhibition and oxidation, for example, trivalent chromium fluoride CrF 3 .
- the oxidizing compound is chosen to be able to oxidize the surface of the part, thus causing its own simultaneous reduction, with, again, local increase in pH and precipitation of rare earth oxides / hydroxides / trivalent chromium / metal constituting the piece.
- oxidizing compounds are fluoride-based substances, such as potassium fluoride or zirconate K 2 ZrF 6 , of permanganate, such as potassium permanganate, hydrogen peroxide H2O2 etc.
- the invention also satisfies the following characteristics, implemented separately or in each of their technically operating combinations.
- the trivalent chromium salt can be brought in any conventional form in itself for chemical conversion treatments of metal substrate, especially in the form of fluoride, chloride, nitrate, acetate, acetate hydroxide, sulfate, potassium sulfate, etc., trivalent chromium, for example CrF 3 , xH 2 O, CrCl 3 , xH 2 O, Cr (NO 3 ) 3, xH 2 O, (CH 3 CO 2 ) 2 Cr, xH 2 O, (CH 3 CO 2 ) 7 Cr 3 (OH) 2 , xH 2 O, Cr 2 (SO 4 ) 3 , xH 2 O, CrK (SO 4 ) 2 , xH 2 O, etc.
- the trivalent chromium salt present in the first bath is selected from fluorides and sulphates. These are, for example, chromium trifluoride CrF 3 , potassium chromium sulphate CrK (SO 4 ) 2, or chromium sulphate Cr 2 (SO 4 ) 3.
- the immersion step in the first bath meets one or more of the following operating parameters:
- the temperature of the first bath is between 10 and 80 ° C, preferably between 20 and 50 ° C, for example equal to 40 ° C;
- the pH of the first bath is between 1 and 7, preferably between 2 and 5, for example equal to 3.5;
- the immersion time in the first bath is between 1 and 60 minutes, preferably between 5 and 30 minutes, and preferably between 10 and 20 minutes;
- the concentration of metal salt, for example trivalent chromium salt, in the first bath is preferably between 0.5 and 50 g / l, preferably between 1 and 20 g / l.
- compositions of the first bath use potassium fluorokirconate K 2 ZrF 6 as an oxidizing compound, and correspond to the following respective compositions:
- - CrF 3 , 4H 2 O at a concentration of between 0.5 and 50 g / l, preferably between 1 and 20 g / l, preferably equal to 6 g / l; and K 2 ZrF 6 at a concentration of between 0.1 and 30 g / l, preferably between 0.5 and 10 g / l, preferably equal to 1 g / l; - or CrK (SO 4 ) 2 , 6H 2 O at a concentration between 0.5 and
- K 2 ZrF 6 at a concentration of between 0.5 and 50 g / l, preferably between 1 and 20 g / l, preferably equal to 5 g / l;
- the cerium or lanthanum that may be present in the second bath preferably have a +3 oxidation state.
- the cerium or lanthanum salt can be brought in any form, especially chloride, fluoride, nitrate, sulfate, acetate, etc., of cerium, for example CeCl 3, xH 2 O, CeF 3 , xH 2 O, Ce (NO 3 ) 3, xH 2 O, Ce 2 (SO 4 ) 3 , xH 2 O, Ce (CH 3 CO 2 ) 3 , xH 2 O, etc. ; or lanthanum, e.g.
- the rare earth salt present in the second bath is cerium nitrate Ce (NO 3 ) 3 or lanthanum nitrate La (NO 3 ) 3 .
- the immersion step in the second bath meets one or more of the following operating parameters:
- the temperature of the second bath is between 10 and 80 ° C, preferably between 15 and 40 ° C, and preferably between 20 and 30 ° C;
- the pH of the second bath is between 1 and 7, preferably between 2 and 5, for example equal to 3 or 3.5;
- the duration of immersion in the second bath is between 1 and 60 minutes, preferably between 2 and 20 minutes, and preferably between 5 and 10 minutes;
- the concentration of rare earth salt, in particular of cerium or lanthanum salt, in the second bath is between 0 and 50 g / l, preferably between 1 and 10 g / l, for example equal to 5 g / l.
- a particularly preferred composition for the second bath uses dihydrogen peroxide H 2 O 2 as an oxidizing compound, and corresponds to one of the following compositions: Ce (NO 3 ) 3 , 6H 2 O or (NO3) 3.6H 2 O, at a concentration of between 0.1 and 50 g / l, preferably between 1 and 10 g / l, preferably equal to 5 g / l, and H2O2, 35% solution.
- / v at a concentration of between 5 and 500 mL / L, preferably between 5 and 200 mL / L, more preferably between 10 and 100 mL / L, preferably equal to 50 mL / L.
- the oxidizing compound chosen for the second bath is hydrogen peroxide H2O2
- the latter is incorporated in the form of an aqueous solution, for example at 35% v / v or 30% v / v, for obtain a concentration in the bath of between 5 and 500 ml / l, preferably between 5 and 200 ml / l, more preferably between 10 and 100 ml / l, and preferably equal to 50 ml / l.
- the piece is subjected to an anodization treatment step prior to immersion in the first bath and the second bath.
- the invention is then also expressed in terms of post-anodization clogging process.
- the prior stage of anodizing treatment can be implemented according to any known method in itself. Preferably, it does not use any substances based on hexavalent chromium.
- anodizations of the sulfuric anodization type diluted or not, such as standard Anodic Sulfuric Oxidation (so-called standard OAS), dilute Anodic Sulfuric Oxidation (so-called dilute OAS), oxidation Anodic Sulfo-Tartric (OAST), Anodic Sulpho-Boric Oxidation (OASB), etc.
- standard OAS Anodic Sulfuric Oxidation
- dilute OAS dilute Anodic Sulfuric Oxidation
- OAST oxidation Anodic Sulfo-Tartric
- OFB Anodic Sulpho-Boric Oxidation
- the part is subjected to a degreasing and / or stripping step prior to immersion of the first bath and the second bath, so as to eliminate grease, dirt and oxides present on its surface.
- this surface preparation step part degreasing and / or pickling is advantageously carried out before the anodization.
- the preliminary surface preparation step can include one or more of the following:
- - alkaline degreasing to dissolve fats present on the surface of the room.
- This operation may be carried out by dipping, spraying, or any other technique known in itself. It may for example be carried out by dipping in a mixture of TURCO 4215 NCLT at 40 to 60 g / L, and TURCO 4215 additive at 5 to 20 g / L, sold by HENKEL, at a temperature between 50 and 70 ° C, for a period of between 10 and 30 minutes; - alkaline pickling, to dissolve naturally formed oxides on the surface of the workpiece. This operation may be carried out by dipping, spraying, or any other technique known in itself.
- a sodium hydroxide solution at 30 to 70 g / l, at a temperature between 20 and 60 ° C, for a period of between 10 seconds and 2 minutes.
- the part is covered with a powdery layer formed of oxidation products of intermetallic compounds, which should be removed by an acid pickling step;
- This operation may be carried out by dipping, spraying, or any other technique known in itself. It may for example be carried out by dipping in a 15 to 25% v / v solution of SMUT-GO NC, marketed by HENKEL, at a temperature of between 10 and 50 ° C. for a period of between 1 and 10 hours. minutes ; or soaking in a solution of ARDROX 295GD at 15 to 30% v / v, marketed by CHEMETALL, at a temperature between 10 and 30 ° C, for a period of between 1 and 10 minutes.
- Interleaved rinses are preferably carried out between the successive steps above, and before immersion of the piece in the first bath.
- the invention is expressed in terms of the chemical conversion process of aluminum or one of its alloys, or magnesium or one of its alloys.
- the parts are then subjected to successive immersions in the next aqueous bath, and in respectively one of the following second aqueous baths.
- the first bath based on trivalent chromium, named Bath 1, corresponds to the composition: CrK (SO 4 ) 2 , 6H 2 O at 2 g / L + K 2 ZrF 6 at 5 g / L, in water.
- the immersion time in this first bath is equal to 10 min.
- the second aqueous bath corresponds to one of the compositions indicated in Table 1 below.
- Three of these baths, comprising an oxidizing compound and a rare earth salt, respectively of cerium (baths D1 and D2) or of lanthanum (bath D3) are in accordance with the present invention, and two of them, Comp.1 and Comp.2, are comparative examples.
- the temperature of each of these baths is the ambient temperature, ie a temperature of between 18 and 25 ° C.
- the immersion time in each of these second baths is equal to 5 min. Parts are also treated, after surface preparation, by immersion only in the bath 1 described above.
- identical pieces, having undergone identical surface preparation are processed by the following prior art commercial chemical conversion processes: Alodine® 1200 (Henkel) (using chromium) hexavalent), SurTec® 650 (SurTec) (using trivalent chromium), and Lanthane® VS 613.3 (Coventya) (using trivalent chromium).
- Table 4 Resistance to salt spray, in terms of the appearance of the first corrosion pitting and the generalization of corrosion, of rolled 2024 T3 aluminum alloy parts processed by a method according to a method of implementation of the invention and by methods of chemical conversion of the prior art
- An adhesion test of conventional paint systems on the conversion layer formed on the part, on the one hand by a process according to the invention above, comprising immersing the piece in the bath 1 and then in the Bath 2 designated D1 (cerium salt), and secondly by the method of the prior art Alodine® 1200, is carried out as follows.
- Two paint systems are tested: a water-based epoxy system (P60 + F70) and a solvent-based polyurethane system (PAC33 + PU66).
- the tests are carried out according to the ISO 2409 standard, for dry adhesion, after drying of the paint system, and for wet adhesion: after drying of the paint system, the samples are immersed in demineralized water for 14 hours. days and then dried before undergoing the adhesion test according to the standard.
- the parts treated by the process according to the invention comprising immersing the part in the bath 1 and then in the bath 2 designated D1 (cerium salt), are subjected to an electrical conductivity test in accordance with the standard MIL- DTL-81760B, which measures the resistivity of the layer / substrate / layer system.
- Alodine® 1200 layer As comparative examples, are also subjected to the same test parts treated by the commercial chemical conversion method proposed by the prior art Alodine® 1200, as described in Table 2 above ("Alodine® 1200 layer”). thick), as well as parts treated by the same Alodine® 1200 chemical conversion process, but including immersion in the treatment bath for only 30 seconds (“Alodine® 1200 thin layer”).
- the thick layer of Alodine® 1200 is recommended when good properties of corrosion resistance are sought, to the detriment of electrical conduction properties.
- the thin layer of Alodine® 1200 is recommended when good electrical conduction properties are sought, with, however, a reduction in the anti-corrosion performance of the treatment by half. The results obtained are shown in Table 6 below.
- the method according to the invention thus makes it possible to form on the part a layer advantageously combining corrosion protection performance superior to those obtained by the method of the prior art Alodine® 1200 thick layer, and good electrical conductivity.
- Example 1 Aluminum parts similar to those used for Example 1 are subjected to the prior surface preparation steps described in Example 1.
- the temperature is the temperature ambient, and the immersion time in Bath 2 is 5 min.
- the part is then subjected to successive immersions in the first and second aqueous baths.
- the first bath based on trivalent chromium, named Bain 1, corresponds to the composition:
- the immersion time in this first bath is equal to 10 min.
- the second bath based on cerium, named Bath 2
- Bath 2 has the following composition: Ce (NO 3 ) 3.6H 2 O at 5 g / L; H 2 O 2 , 35% v / v solution, 50 mL / L, in water. Its pH is set at 3, and its temperature is the ambient temperature, ie a temperature between 18 and 25 ° C approximately.
- the immersion time in this second bath is equal to 5 min.
- Parts 2024T3 laminated aluminum alloy 120x80x2 mm dimensions are treated by anodizing, then clogging, according to the methods below. Beforehand, they are subjected to surface preparation steps, by alkaline degreasing and acid pickling, as indicated in Example 1 above.
- anodizing step three different anodizing methods, namely the diluted OAS, the OAST and the OASB, are implemented, to obtain on the surface of the pieces an anodic layer with a thickness of 2 to 5 ⁇ .
- the parts obtained are subjected to a sealing step, either of the hydrothermal type, or of the hydrothermal type with nickel salts, or according to the process according to the invention implemented in the conditions indicated in Example 1 above, concerning the immersion in Bath 1 and Bath 2.
- a sealing step either of the hydrothermal type, or of the hydrothermal type with nickel salts, or according to the process according to the invention implemented in the conditions indicated in Example 1 above, concerning the immersion in Bath 1 and Bath 2.
- hydrothermal clogging immersion of the piece in deionized water at a temperature of 98 ° C. for 40 minutes;
- Table 13 Salt spray resistance of 2024 T3 aluminum alloy rolled parts treated by anodizing and clogging, the clogging being carried out by a method according to an embodiment of the invention or by clogging processes.
- the present invention achieves the objectives it has set for itself.
- it provides a method of surface treatment of aluminum or aluminum alloy parts, or magnesium or magnesium alloy, which, without using hexavalent chromium, provides performance in terms of protection of the piece against corrosion which are superior to those obtained by the processes of the prior art.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1251268A FR2986806B1 (fr) | 2012-02-10 | 2012-02-10 | Procede de traitement de surface de pieces en alliage d'aluminium ou de magnesium |
PCT/EP2013/052701 WO2013117767A1 (fr) | 2012-02-10 | 2013-02-11 | Procédé de traitement de surface de pièces en alliage d'aluminium ou de magnesium |
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EP2812462A1 true EP2812462A1 (fr) | 2014-12-17 |
EP2812462B1 EP2812462B1 (fr) | 2019-04-10 |
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EP13703431.0A Active EP2812462B1 (fr) | 2012-02-10 | 2013-02-11 | Procédé de traitement de surface de pièces en alliage d'aluminium ou de magnesium |
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US (1) | US9879347B2 (fr) |
EP (1) | EP2812462B1 (fr) |
BR (1) | BR112014019739B1 (fr) |
CA (1) | CA2864109C (fr) |
ES (1) | ES2729113T3 (fr) |
FR (1) | FR2986806B1 (fr) |
TR (1) | TR201908092T4 (fr) |
WO (1) | WO2013117767A1 (fr) |
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FR3106838B1 (fr) * | 2020-01-31 | 2022-01-14 | Safran Aircraft Engines | Procede de colmatage des alliages d’aluminium |
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US11926899B2 (en) * | 2020-12-04 | 2024-03-12 | Raytheon Company | Process for application of oxyhydroxides coating for aluminum containing material |
US20230136068A1 (en) * | 2021-11-03 | 2023-05-04 | United States Of America As Represented By The Secretary Of The Navy | Corrosion resistant chromium free conversion coatings |
FR3137393A1 (fr) * | 2022-06-30 | 2024-01-05 | Safran Landing Systems | Piece en alliage d’aluminium et procede de fabrication associe |
FR3140382A1 (fr) | 2022-10-04 | 2024-04-05 | Safran Landing Systems | Procede de colmatage post-anodisation de l’aluminium et des alliages d’aluminium sans utiliser de chrome |
DE102022126251A1 (de) | 2022-10-11 | 2024-04-11 | Liebherr-Aerospace Lindenberg Gmbh | Verfahren zur Oberflächenbehandlung |
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CA1014831A (en) * | 1973-06-06 | 1977-08-02 | Donald J. Melotik | Rare earth metal rinse for metal coatings |
US5304257A (en) * | 1993-09-27 | 1994-04-19 | The United States Of America As Represented By The Secretary Of The Navy | Trivalent chromium conversion coatings for aluminum |
US5374347A (en) * | 1993-09-27 | 1994-12-20 | The United States Of America As Represented By The Secretary Of The Navy | Trivalent chromium solutions for sealing anodized aluminum |
US6248184B1 (en) * | 1997-05-12 | 2001-06-19 | The Boeing Company | Use of rare earth metal salt solutions for sealing or anodized aluminum for corosion protection and paint adhesion |
US7452427B2 (en) * | 2004-12-01 | 2008-11-18 | Deft, Inc. | Corrosion resistant conversion coatings |
EP1848841B1 (fr) * | 2005-02-15 | 2013-03-20 | The United States of America as represented by The Secretary of The Navy | Composition et procede permettant de preparer des revetements de chrome-zirconium sur des substrats metalliques |
PL1984536T3 (pl) * | 2006-02-14 | 2012-09-28 | Henkel Ag & Co Kgaa | Kompozycje i sposoby odpornej na korozję powłoki trójwartościowego chromu do suszenia na miejscu do stosowania na powierzchniach metalicznych |
US20110159315A1 (en) * | 2008-05-27 | 2011-06-30 | Yuken Industry Co., Ltd. | Finishing Agent and Member Having an Overcoat Formed from the Finishing Agent |
KR20110054009A (ko) * | 2008-09-17 | 2011-05-24 | 호덴 세이미츠 카코 켄쿄쇼 컴퍼니 리미티드 | 아연 또는 아연 합금 표면의 흑색화 화성 처리용 수용액과 그 처리용 수용액을 이용하는 흑색화 방청 피막 형성 방법 |
US9347134B2 (en) * | 2010-06-04 | 2016-05-24 | Prc-Desoto International, Inc. | Corrosion resistant metallate compositions |
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2012
- 2012-02-10 FR FR1251268A patent/FR2986806B1/fr active Active
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2013
- 2013-02-11 TR TR2019/08092T patent/TR201908092T4/tr unknown
- 2013-02-11 ES ES13703431T patent/ES2729113T3/es active Active
- 2013-02-11 CA CA2864109A patent/CA2864109C/fr active Active
- 2013-02-11 EP EP13703431.0A patent/EP2812462B1/fr active Active
- 2013-02-11 WO PCT/EP2013/052701 patent/WO2013117767A1/fr active Application Filing
- 2013-02-11 BR BR112014019739-3A patent/BR112014019739B1/pt active IP Right Grant
- 2013-02-11 US US14/377,849 patent/US9879347B2/en active Active
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Also Published As
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FR2986806B1 (fr) | 2015-03-20 |
WO2013117767A1 (fr) | 2013-08-15 |
BR112014019739A2 (fr) | 2017-06-20 |
EP2812462B1 (fr) | 2019-04-10 |
BR112014019739B1 (pt) | 2020-11-24 |
BR112014019739A8 (pt) | 2017-07-11 |
TR201908092T4 (tr) | 2019-06-21 |
US9879347B2 (en) | 2018-01-30 |
CA2864109A1 (fr) | 2013-08-15 |
CA2864109C (fr) | 2020-02-04 |
US20150020925A1 (en) | 2015-01-22 |
FR2986806A1 (fr) | 2013-08-16 |
ES2729113T3 (es) | 2019-10-30 |
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