EP2507408A1 - Multi-stage pre-treatment method for metal components having zinc and iron surfaces - Google Patents
Multi-stage pre-treatment method for metal components having zinc and iron surfacesInfo
- Publication number
- EP2507408A1 EP2507408A1 EP10776723A EP10776723A EP2507408A1 EP 2507408 A1 EP2507408 A1 EP 2507408A1 EP 10776723 A EP10776723 A EP 10776723A EP 10776723 A EP10776723 A EP 10776723A EP 2507408 A1 EP2507408 A1 EP 2507408A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- ppm
- composition
- nickel
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 28
- 239000011701 zinc Substances 0.000 title claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 20
- 238000002203 pretreatment Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 78
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 75
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 34
- 239000010959 steel Substances 0.000 claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 26
- 239000008397 galvanized steel Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 17
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011135 tin Substances 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 36
- 229910052726 zirconium Inorganic materials 0.000 claims description 33
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 31
- 230000007797 corrosion Effects 0.000 claims description 26
- 238000005260 corrosion Methods 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 18
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- -1 silver ions Chemical class 0.000 claims description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910001453 nickel ion Inorganic materials 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 235000021317 phosphate Nutrition 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical class SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000004715 keto acids Chemical class 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052845 zircon Inorganic materials 0.000 abstract 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 19
- 238000000151 deposition Methods 0.000 description 19
- 230000008021 deposition Effects 0.000 description 19
- 239000003973 paint Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 238000003618 dip coating Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000004532 chromating Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 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
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 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
- 239000002966 varnish Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001928 zirconium oxide 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
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—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
Definitions
- the present invention relates to an acidic, aqueous, chromium-free composition (A) for the anticorrosive treatment of steel and / or galvanized steel surfaces, comprising metal ions (M) selected from ions of at least one of the elements nickel, cobalt, molybdenum, iron or tin, and a multi-stage process using the composition (A) for the anticorrosive pretreatment of metallic components having surfaces of steel and / or galvanized steel.
- metal ions selected from ions of at least one of the elements nickel, cobalt, molybdenum, iron or tin
- the invention relates to metallic surfaces of zinc or iron, which have a passive layer system containing at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium and sulfur, wherein nickel is at least 30 at .-% in metallic form, obtainable in a method according to the invention.
- Corrosion inhibitors which are an acidic aqueous solution of fluoro complexes, have long been known and substitute those long used in the art
- WO 07/065645 describes aqueous compositions containing fluorocomplexes of, inter alia, titanium and / or zirconium, wherein in addition a further component is present, which is selected from: nitrate ions, copper ions, silver ions, vanadium or vanadate ions, bismuth ions, magnesium ions, zinc ions, manganese ions, cobalt ions, nickel ions, tin ions, buffer systems for the pH range from 2.5 to 5.5, aromatic carboxylic acids with at least two groups containing donor atoms, or derivatives of such carboxylic acids, silica particles having a mean particle size below 1 ⁇ .
- Pretreatment before a zirconium-based conversion treatment of metal surfaces, in particular of steel and galvanized steel known.
- a pretreatment with an acidic aqueous composition containing water-soluble salts of electropositive metals selected from nickel, copper, silver and / or gold is carried out before the conversion treatment.
- Such a composition for metallization may additionally contain defoamers and wetting agents.
- sparingly soluble copper salts it is proposed to use complexing agents in WO 2009045845 in order to increase the concentration of copper ions in the metallizing composition. It turns out that in the WO
- Chromium (VI) -free electrolyte containing at least 50 g / l of zinc ions and at least 50-300 g / l of metal cations selected from cations of the elements iron, cobalt and / or nickel.
- the aqueous composition may contain electropositive metal cations of the elements copper, silver, tin and / or bismuth.
- Further constituents of the electrolytic layer formation compositions disclosed in US Pat. No. 5,032,236 are ionogenic compounds which improve the formation of layers, including inorganic and organic sulfur compounds. According to the teaching of US Pat. No.
- alkaline aqueous composition containing metal cations selected from ions of the elements cobalt, nickel, iron and / or tin in an amount of 0.01-1 g / l, a complexing agent selected from pyrophosphate and / or Nitrilotriacetic acid for preventing the precipitation of sparingly soluble heavy metal salts and optionally a reducing agent, preferably sulfite.
- metal cations selected from ions of the elements cobalt, nickel, iron and / or tin in an amount of 0.01-1 g / l
- a complexing agent selected from pyrophosphate and / or Nitrilotriacetic acid for preventing the precipitation of sparingly soluble heavy metal salts
- a reducing agent preferably sulfite.
- Zinc surfaces wherein such a coated zinc surface after chromating and application of a paint system high corrosion resistance at good paint adhesion values having. Due to the low ionic concentrations and the presence of the complexing agent, a high bath stability is ensured. However, that allows in the
- Corrosion protection and paint adhesion properties of a trication zinc phosphating is at least equivalent and can be operated in a resource-saving manner.
- the object of the present invention is therefore to provide a method for
- Pretreatment of metallic components having surfaces of steel and / or galvanized steel comprising the method steps i-iii), each of which involve contacting the metallic component with an aqueous treatment solution, wherein the respective method steps i-iii) follows are characterized:
- An acidic aqueous, chromium-free composition (A) according to the invention which, when brought into contact with steel and / or galvanized steel, in a process according to the invention effective corrosion protection already effected by deposition of small amounts of active components contains
- metallic components comprising steel and galvanized steel are treated with a composition (A) according to the invention, the surface of the metallic component consisting of at least 10% galvanized steel surfaces, the pH is preferably in the range from 4.0 to 7.0, more preferably in a range of 5.0 to 7.0, especially in the range of 6.0 to 6.8.
- the composition (A) is chromium-free, if less than 10 ppm,
- chromium preferably less than 1 ppm of chromium, in particular no chromium (VI) are contained.
- Composition (A) causes deposition of the metal ions (M) (active component) on the metal surfaces.
- the layer formation takes place at least partially in the form of metallic phases of the elements nickel, cobalt, molybdenum, iron or tin.
- the composition (A) may additionally contain chelating organic compounds which have at least two functional groups with oxygen and / or nitrogen atoms selected from carboxyl, hydroxyl, amine, phosphoric acid or phosphonic acid groups. Particularly preferred are chelating organic compounds containing phosphoric acid, phosphonic acid and / or hydroxyl groups, for example, 1-hydroxyethane (1, 1 -diphosphonic acid). It has been found that such chelating agents in the composition (A) according to the invention mainly complex zinc ions and therefore weaken the inhibition of the deposition of the metal ions (M) on the metal surfaces.
- the chelating organic compounds are preferably contained in such an amount that the molar excess of zinc ions relative to the chelating organic Compounds not greater than 2 g / l, preferably not greater than 1 g / l, more preferably not greater than 0.5 g / l of zinc ions.
- compositions (A) are preferred whose content of zinc ions is not greater than 2 g / l, preferably not greater than 1 g / l, more preferably not greater than 0.5 g / l of zinc ions.
- the amount of phosphate ions is limited in the compositions (A) according to the invention, since higher proportions can cause the formation of a thin phosphate passivation, which is disadvantageous for the deposition of the metal ions (M) on the metal surfaces. This is surprising as the passivating treatment of the metal surface with a
- compositions based on zirconium, titanium and / or hafnium analogously to the treatment step iii) according to the invention, is not detrimental to the layer-forming deposition of the metal ions (M). Therefore, such compositions (A) according to the invention are preferred in which the proportion of dissolved phosphate is not more than 500 ppm, more preferably not more than
- compositions (A) according to the invention can inhibit the deposition of the metal ions (M) on the steel surfaces.
- such compositions (A) do not result in precipitation of zirconium, titanium and / or hafnium so that the use of these compounds provides no advantage and is uneconomical.
- the at least one water-soluble compound containing sulfur in an oxidation state of less than +6 is preferably selected from inorganic compounds, more preferably from oxo acids of sulfur such as sulphurous acid, thiosulphuric acid, dithionic acid, polythionic acid, sulphurous acid, dibasic acid and / or dithionic acid and their salts, especially preferably from sulphurous acid.
- the water-soluble compound containing sulfur may also be selected from salts of the organic acids thiocyanic acid and / or thiourea, with the aforementioned water-soluble inorganic compounds containing sulfur being preferred over organic acids and salts.
- the oxidation state in the context of the present invention, is defined according to IUPL Rule I-5.5.2.1 ("Nomenclature of Inorganic Chemistry - Recommendations 1990", Blackwell: Oxford, 1990) and designates the hypothetical charge assigned to an element in a molecule would be if this element were to be assigned all the electrons shared with other elements of the molecule for which the element has a higher electronegativity than that of the element with which it shares the electrons.
- the preferred concentration of water-soluble compounds containing sulfur in an oxidation state less than +6 is at least 1 mM, preferably at least 5 mM, but not more than 100 mM, preferably not more than 50 mM. Below 1 mM is one
- Layer-forming deposition of metal ions (M) in typical treatment times of a few minutes is not given or does not occur. Above 100 mM, on the one hand, no further acceleration of the layer formation on contacting a cleaned steel surface with such a composition (A) is found, and on the other hand, higher amounts of sulfur-containing compounds are rejected for economic and occupational hygiene reasons.
- reducing agents based on water-soluble compounds containing phosphorus and / or nitrogen in an oxidation state of less than +5 are surprisingly unsuitable for the deposition of the metal ions (M), in particular for the deposition of nickel and / or cobalt ions that these reducing agents in the composition (A) for economic reasons, preferably not or only in very small amounts below 50 ppm are included.
- compositions (A) are preferably at least 0.2 g / l, but not more than 5 g / l, preferably not more than 2 g / l of metal ions (M) selected from ions of at least one of the elements nickel, cobalt , Molybdenum, iron or tin. If this value is undershot, the activity of the metal ions (M) in the composition (A) is usually too low for adequate deposition. Above 5 g / l there is no additional benefit, whereas the increased precipitation of insoluble salts of the metal ions (M) increases, so that such high concentrations of metal ions (M) in treatment baths according to step ii) of the process according to the invention are uneconomical and also require increased processing costs.
- M metal ions
- metal ions (M) which are deposited on the metal surfaces in process step ii) from the acidic aqueous composition (A) in a preferred embodiment, in particular nickel and / or cobalt, more preferably nickel.
- Metal surfaces of steel and / or galvanized steel which are brought into contact with an aqueous composition (A) containing nickel and / or cobalt ions, particularly preferably nickel ions, independently of the sequence of process steps ii) and iii) are provided within a short treatment time with a thin layer containing the elements nickel and / or Kolbalt, which gives an excellent paint adhesion to subsequently applied organic paint systems and thereby meets the highest standards of corrosion protection.
- A aqueous composition containing nickel and / or cobalt ions, particularly preferably nickel ions, independently of the sequence of process steps ii) and iii) are provided within a short treatment time with a thin layer containing the elements nickel and / or Kolbalt, which gives an excellent paint adhesion to subsequently applied organic paint systems and thereby meets the highest standards of corrosion protection.
- Preferred water-soluble compounds which release metal ions (M) are all water-soluble salts which do not contain chloride ions. Particular preference is given to sulfates, nitrates and acetates.
- a preferred composition (A) according to the invention has a molar ratio of metal ions (M) selected from ions of at least one of nickel, cobalt, molybdenum, iron or tin to water-soluble compounds containing sulfur of not greater than 1: 1, preferably not greater than 2: 3 but not less than 1: 5. Above this preferred molar ratio of 1: 1, the formation of the thin layer containing the elements of the metal ions (M) is slower, so that in particular for the application of
- a coating process is preferably those compositions (A) in which a sufficient amount of water-soluble compounds containing sulfur relative to the total amount of metal ions (M) is present.
- a molar ratio of metal ions (M) to water-soluble compounds containing sulfur below 1: 5 may be detrimental to the stability of compositions (A) of the invention because the reducing sulfur compounds can then cause precipitation of the containing metals in colloidal form.
- compositions (A) according to the invention it may be advantageous to add electropositive metal cations in order to accelerate the layer formation.
- electropositive metal cations for compositions (A) according to the invention, it may be advantageous to add electropositive metal cations in order to accelerate the layer formation.
- Embodiment of the invention therefore additionally contains copper ions and / or silver ions, preferably copper ions, in an amount of at least 1 ppm, but not more than 100 ppm. Above 100 ppm, the deposition of the electropositive metal in elemental form on the steel and / or galvanized steel surfaces dominate so far that the layer formation based on the metal ions (M) is pushed back so far that the paint adhesion applied subsequently in the process according to the invention organic paints is significantly deteriorated or inhomogeneous layer coatings are produced after step ii) of the method according to the invention, which offer a poorer corrosion protection.
- M metal ions
- Preferred water-soluble compounds that release copper ions are all
- water-soluble copper salts containing no chloride ions and all water-soluble silver salts Particular preference is given to sulfates, nitrates and acetates.
- composition (A) according to the invention may be preferred, wherein the
- Concentration of total fluoride in the composition (A) is preferably at least 50 ppm but not more than 2000 ppm.
- the addition of fluoride is particularly advantageous when, in a process according to the invention, step ii), with or without a rinsing step between them, immediately follows the purification step i) and in particular when hot-dip galvanized steel surfaces are treated. In such a case, the pickling rate on the metal surfaces and faster deposition kinetics of the thin increases
- Coating consisting of elements of metal ions (M) and a more homogeneous
- Preferred water-soluble compounds which serve as a source of fluoride ions are hydrogen fluoride, alkali fluorides, ammonium fluoride and / or
- a cleaning and degreasing of the metal surface is necessary for a homogeneous formation of the passivating coating according to process steps ii) and iii).
- those purification steps i) are preferred according to the invention, which are carried out by means of an aqueous cleaning solution, wherein the cleaning a Beizabtrag of at least 0.4 g / m 2 , but not more than 0.8 g / m 2 of zinc based on a surface of Electrolytic galvanized steel causes.
- cleaners which have a corresponding pickling rate for a given cleaning time. It has surprisingly been found that such a preferred purification leads to better results in terms of corrosion protection and paint adhesion of the steel and / or galvanized steel surfaces treated according to the invention.
- compositions (B) are preferably free of chromium, i. they contain less than 10 ppm, preferably less than 1 ppm of chromium, in particular no chromium (VI). Furthermore, the acidic compositions (B) in the process according to the invention preferably contain a total of 20 to 1000 ppm of water-soluble compounds of the elements zirconium, titanium and / or hafnium based on the elements zirconium, titanium and / or hafnium.
- metal surface may be the result so that only small amounts of hydroxides and / or oxides of these elements deposited and the passivating effect is too low.
- a further improvement in the corrosion properties of the metal surfaces treated according to the invention can not be determined.
- compositions (B) in the process according to the invention which contain, as water-soluble compounds of the elements zirconium, titanium and / or hafnium, only water-soluble compounds of the elements zirconium and / or titanium, more preferably water-soluble compounds of the element zirconium.
- Preferred water-soluble compounds of the elements zirconium, titanium and / or hafnium are compounds which dissociate in aqueous solution into anions of fluorocomplexes of the elements zirconium, titanium and / or hafnium.
- Such preferred compounds are, for example, H 2 ZrF 6 , K 2 ZrF 6 , Na 2 ZrF 6 and (NH 4 ) 2 ZrF 6 and the analogous titanium compounds.
- fluorine-free compounds of the elements zirconium, titanium and / or hafnium can be used as water-soluble
- a composition (B) in step iii) of the process according to the invention may contain 1 to 100 ppm of copper ions and optionally up to 200 ppm of free fluoride.
- copper ions accelerates the conversion of the purified or treated in step ii) metal surfaces and also increases the passivating effect. Especially in the event that first the passivating treatment of steel and / or galvanized
- Preferred water-soluble compounds that release copper ions are all water-soluble copper salts that do not contain chloride ions. Particular preference is given to sulfates, nitrates and acetates.
- Preferred water-soluble compounds which serve as a source of fluoride ions are hydrogen fluoride, alkali fluorides, ammonium fluoride and / or ammonium bifluoride.
- the treatment temperature and the duration of the respective treatment are different in the individual steps i-iii) of the process according to the invention and strongly dependent on the bath system and the type of application, but can be varied over a wide range, without sacrificing corrosion properties.
- the treatment in steps i-iii) should be carried out as follows:
- the concrete conditions for bringing the metal surfaces into contact with the aqueous treatment stages ii) and iii) are preferably to be selected such that in step ii) a layer coverage of at least 30 mg / 2 , more preferably at least 50 mg / m2 of one or more of the metal ions (M) on the surfaces of zinc, while the temperature and duration of treatment in step iii) are to be adjusted such that a coating of at least 10 mg / m 2 zirconium and / or titanium, more preferably at least 25 mg / m 2 zirconium and / or titanium on the surfaces of zinc results.
- the corrosion protection properties of the pretreatment are usually insufficient.
- a first step the layer formation based on the elements of the metal ions (M) is carried out and then a conversion of the metal surface treated in this way is carried out with the aid of the zirconium- and / or titanium-containing composition (B).
- the method according to the invention is suitable for metallic components which have iron, steel and / or galvanized steel surfaces and the corresponding pre-phosphated surfaces. Irrespective of the sequence of steps ii) and iii), sufficient layer formation on the basis of the elements of the metal ions (M) always takes place on these surfaces, which in turn is a prerequisite for the outstanding properties with respect to corrosion and paint adhesion. Likewise, surfaces of aluminum are passivated in step iii) in the process according to the invention, so that the process is particularly suitable for the corrosion-protective pretreatment of multi-metal construction surfaces, for example.
- aqueous compositions in steps i-iii) can be brought into contact with the metal surfaces in both immersion and spraying processes.
- the method can also be used in the pretreatment of metal strip and there, for example, by means of the roller application method known to those skilled in the art.
- the process of the invention is usually followed by the application of a coating system, so that after passing through the process steps i-iii) with or without intermediate rinsing and / or drying step preferably a dip coating or a
- Powder coating particularly preferably a dip coating, in particular a cathodic dip coating follows.
- the present invention further comprises a metal surface of iron and / or steel with passive layer system comprising at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium, preferably at least 10 mg / m 2 zirconium, and sulfur wherein nickel is at least 30 at.% in metallic form, obtainable in a preferred one
- step i) in which step i) with or without intermediate rinsing step directly followed by the electroless treatment according to step ii), the composition (A) in process step ii) at least 100 ppm, but not more than 5 g / l Nickel ions and at least 1 mM sulfurous acid and / or salt thereof and the iron and / or steel surface at a treatment temperature in the range of 20 to 50 ° C is brought into contact with such a composition (A) for at least one minute.
- the present invention comprises a metal surface of zinc and / or galvanized steel with a passive layer system comprising at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium, preferably at least 10 mg / m 2 zirconium, and Contains sulfur, wherein nickel is at least 30 at .-% in metallic form, obtainable in a process according to the invention, in which the process step ii) with or without intermediate rinsing step immediately following the process step iii) and in which the inventive
- Composition (A) in process step ii) comprises at least 100 ppm, but not more than 5 g / l of nickel ions and at least 1 mM sulphurous acid and / or salt thereof and the zinc and / or galvanized steel surface at a treatment temperature in the range of 20 to 50 ° C is brought into contact with such a composition (A) for at least one minute.
- the invention additionally relates to the use of the metallic components treated according to the invention or of the metal strip treated according to the invention in the manufacture of
- the preferred composition (A) according to the invention has a pH of 3.7 and following
- composition (Examples B1 and B2):
- a cleaning and degreasing with a cleaning solution as in Example B2 causes a pickling of 0.5 g / m 2 on electrolytically galvanized substrates, while a
- the metal sheets treated according to the invention and the comparative sheets were dried with compressed air after the last rinsing step and electrocoated with the following cathodic dip coating: Aqua® 3000 (Dupont Co., KTL layer thickness: 20 ⁇ m, determined nondestructively using a commercially available layer thickness gauge)
- Cleaning solution a further significantly improved performance of the present invention treated and coated with the dip coating zinc surfaces (B2 vs. B1) causes in the stone impact test.
- Such an improvement on zinc surfaces by the cleaning effect of the cleaner occurs only in the process according to the invention and is omitted both in the exclusive zirconium-based conversion treatment (V4 vs. V3) and the exclusive trication zinc phosphating (V2 vs. V1).
- Table 1
- the nickel layer coating was determined by means of X-ray fluorescence analysis after the individual step iii)
- XPS X-ray photoelectron spectroscopy
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Abstract
Description
„Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit "Multistage pretreatment process for metallic components with
Zink- und Eisenoberflächen" Zinc and iron surfaces "
Die vorliegende Erfindung betrifft eine saure wässrige, chromfreie Zusammensetzung (A) für die korrosionsschützenden Behandlung von Stahl- und/oder verzinkten Stahloberflächen, umfassend Metall-Ionen (M) ausgewählt aus Ionen mindestens eines der Elemente Nickel, Kobalt, Molybdän, Eisen oder Zinn, sowie ein mehrstufiges Verfahren unter Anwendung der Zusammensetzung (A) für die korrosionsschützende Vorbehandlung von metallischen Bauteilen, die Oberflächen von Stahl- und/oder verzinktem Stahl aufweisen. Ferner betrifft die Erfindung metallische Oberflächen von Zink oder Eisen, die ein Passivschichtsystem enthaltend zumindest 30 mg/m2 Nickel und zumindest 10 mg/m2 Zirkon, Titan und/oder Hafnium sowie Schwefel aufweisen, wobei Nickel zumindest zu 30 At.-% in metallischer Form vorliegt, erhältlich in einem erfindungsgemäßen Verfahren. The present invention relates to an acidic, aqueous, chromium-free composition (A) for the anticorrosive treatment of steel and / or galvanized steel surfaces, comprising metal ions (M) selected from ions of at least one of the elements nickel, cobalt, molybdenum, iron or tin, and a multi-stage process using the composition (A) for the anticorrosive pretreatment of metallic components having surfaces of steel and / or galvanized steel. Furthermore, the invention relates to metallic surfaces of zinc or iron, which have a passive layer system containing at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium and sulfur, wherein nickel is at least 30 at .-% in metallic form, obtainable in a method according to the invention.
Korrosionsschutzmittel, die eine saure wässrige Lösung von Fluoro-Komplexen darstellen, sind seit langem bekannt und substituieren die im Stand der Technik lange eingesetzten Corrosion inhibitors, which are an acidic aqueous solution of fluoro complexes, have long been known and substitute those long used in the art
Chromatierverfahren zur passivierenden Vorbehandlung. Neuerdings werden derartige Chromating process for passivating pretreatment. Recently, such
Korrosionsschutzmittel, die lediglich ein dünne Konversionsschicht auf den behandelten Corrosion inhibitor, which only a thin conversion layer on the treated
Metalloberflächen hervorrufen, auch als Ersatz für Phosphatierverfahren diskutiert und Metal surfaces, also discussed as a replacement for Phosphatierverfahren and
insbesondere in der Automobilzulieferindustrie eingesetzt, um das mehrstufige especially in the automotive supply industry used to multi-level
Phosphatierverfahren, das mit hohen Stoffumsätzen verbunden ist, gegen Verfahren mit niedrigerem Stoffumsatz und niedrigerem verfahrenstechnischen Aufwand zu substituieren. In der Regel enthalten derartige Lösungen von Fluoro-Komplexen weitere korrosionsschützende Substituting phosphating, which is associated with high substance conversions, against methods with lower material conversion and lower process complexity. As a rule, such solutions of fluoro-complexes contain further corrosion-protecting
Wirkstoffe, die Korrosionsschutzwirkung und Lackhaftung weiter verbessern. Active substances that further improve the corrosion protection effect and paint adhesion.
Beispielsweise beschreibt die WO 07/065645 wässrige Zusammensetzungen, die Fluorokomplexe von unter anderem Titan- und/oder Zirkon enthalten, wobei zusätzlich eine weitere Komponente enthalten ist, die ausgewählt ist aus: Nitrat-Ionen, Kupfer-Ionen, Silber-Ionen, Vanadium- oder Vanadat-Ionen, Wismut-Ionen, Magnesium-Ionen, Zink-Ionen, Mangan-Ionen, Kobalt-Ionen, Nickel-Ionen, Zinn-Ionen, Puffersystemen für den pH-Bereich von 2,5 bis 5,5, aromatischen Carbonsäuren mit mindestens zwei Gruppen, die Donoratome enthalten, oder Derivaten solcher Carbonsäuren, Kieselsäure-Partikel mit einer mittleren Teilchengröße unterhalb von 1 μιη. For example, WO 07/065645 describes aqueous compositions containing fluorocomplexes of, inter alia, titanium and / or zirconium, wherein in addition a further component is present, which is selected from: nitrate ions, copper ions, silver ions, vanadium or vanadate ions, bismuth ions, magnesium ions, zinc ions, manganese ions, cobalt ions, nickel ions, tin ions, buffer systems for the pH range from 2.5 to 5.5, aromatic carboxylic acids with at least two groups containing donor atoms, or derivatives of such carboxylic acids, silica particles having a mean particle size below 1 μιη.
Es besteht ein Bedarf die korrosionsschützende Vorbehandlung von Metalloberflächen weiter voranzutreiben und an die Leistungsmerkmale hinsichtlich Korrosionsschutz und Lackhaftung einer Trikation-Zinkphosphatierung heranzuführen. Hierbei ist nicht mehr allein die Anzahl der einzelnen Verfahrensschritte für den Erfolg einer Vorbehandlung ausschlaggebend, sondern die Performance der Beschichtung insbesondere in Hinblick auf die Vorbehandlung von Bauteilen, die aus den Werkstoffen Stahl, verzinktem Stahl und Aluminium zusammengesetzt sind. Aus der Offenlegungsschrift WO 2009045845 ist eine außenstromlose metallisierende There is a need to further advance the anticorrosive pretreatment of metal surfaces and to introduce them to the corrosion protection and paint adhesion performance of a trication zinc phosphating. It is no longer the number of individual process steps that is decisive for the success of a pretreatment, but the performance of the coating, in particular with regard to the pretreatment of components composed of the materials steel, galvanized steel and aluminum. From the published patent WO 2009045845 is an electroless metallizing
Vorbehandlung vor einer Zirkon-basierten Konversionsbehandlung von Metalloberflächen, insbesondere von Stahl und verzinktem Stahl, bekannt. Hierbei wird vor der Konversionsbehandlung eine Vorbehandlung mit einer sauren wässrigen Zusammensetzung enthaltend wasserlösliche Salze elektropositiver Metalle ausgewählt aus Nickel, Kupfer, Silber und/oder Gold vorgenommen. Eine solche Zusammensetzung zur Metallisierung kann zusätzlich Entschäumer und Benetzungsmittel enthalten. Bei Verwendung schwerlöslicher Kupfer-Salze wird in der WO 2009045845 vorgeschlagen Komplexbildner einzusetzen, um die Konzentration von Kupfer-Ionen in der metallisierenden Zusammensetzung zu erhöhen. Es zeigt sich, dass die in der WO Pretreatment before a zirconium-based conversion treatment of metal surfaces, in particular of steel and galvanized steel, known. In this case, a pretreatment with an acidic aqueous composition containing water-soluble salts of electropositive metals selected from nickel, copper, silver and / or gold is carried out before the conversion treatment. Such a composition for metallization may additionally contain defoamers and wetting agents. When using sparingly soluble copper salts, it is proposed to use complexing agents in WO 2009045845 in order to increase the concentration of copper ions in the metallizing composition. It turns out that in the WO
2009045845 vorgeschlagene Metallisierung vor einer Konversionsbehandlung nicht an diejenige Lackhaftung und Korrosionsbeständigkeit heranreicht, die durch eine Zinkphosphatierung und nachträgliche Tauchlackierung erzielt werden kann. 2009045845 proposed before a conversion treatment does not reach the paint adhesion and corrosion resistance, which can be achieved by zinc phosphating and subsequent dip coating.
Die Offenlegungsschrift US 5032236 beschreibt die elektrolytische Schichtbildung auf The publication US 5032236 describes the electrolytic layer formation
Stahloberflächen zur Ausbildung schwarzer Überzüge unter Verwendung von weitgehend Steel surfaces to form black coatings using largely
Chrom(VI)-freien Elektrolyten enthaltend zumindest 50 g/l an Zink-Ionen sowie zumindest 50-300 g/l an Metall-Kationen ausgewählt aus Kationen der Elemente Eisen, Kobalt und/oder Nickel. Zusätzlich kann die wässrige Zusammensetzung elektropositive Metall-Kationen der Elemente Kupfer, Silber, Zinn und/oder Wismut enthalten. Weitere Bestandteile der in der US 5032236 offenbarten Zusammensetzungen zur elektrolytischen Schichtbildung sind ionogene Verbindungen, die die Schichtbildung verbessern, unter anderem eignen sich hierfür anorganische und organische Schwefelverbindungen. Gemäß der Lehre der US 5032236 kann einer solchen elektrolytischen Schichtbildung eine Chromatierung und anschließend die Abscheidung eines Tauchlackes zum Aufbau eines vor Korrosion schützenden Schichtsystems auf Stahloberflächen folgen, wobei gemäß dieser Verfahrensfolge beschichtete Stahloberflächen einen guten Schutz vor Korrosion bei guten Lackhaftungswerten bieten. Als Nachteil dieses elektrolytischen Verfahrens erweisen sich zum einen der Verbrauch elektrischer Energie und zum anderen die für das Verfahren Chromium (VI) -free electrolyte containing at least 50 g / l of zinc ions and at least 50-300 g / l of metal cations selected from cations of the elements iron, cobalt and / or nickel. In addition, the aqueous composition may contain electropositive metal cations of the elements copper, silver, tin and / or bismuth. Further constituents of the electrolytic layer formation compositions disclosed in US Pat. No. 5,032,236 are ionogenic compounds which improve the formation of layers, including inorganic and organic sulfur compounds. According to the teaching of US Pat. No. 5,032,236, such an electrolytic layer formation can be followed by a chromating followed by the deposition of an immersion varnish to build up a corrosion-protecting layer system on steel surfaces, wherein according to this process sequence coated steel surfaces offer a good protection against corrosion with good paint adhesion values. As a disadvantage of this electrolytic process, on the one hand prove the consumption of electrical energy and the other for the process
notwendigen hohen Konzentrationen der ionogenen Bestandteile, die den Einsatz von necessary high concentrations of the ionogenic constituents, the use of
Badstabilisatoren und eine apparativ aufwendige Badpflege hinsichtlich Regenerierung seiner Aktivkomponenten und der Entsorgung von nicht vermeidbaren Schwermetallschlämmen erfordern. Badstabilisatoren and a complex apparatus bathroom care in terms of regeneration of its active components and the disposal of unavoidable heavy metal sludge require.
Aus der US 4278477 entnimmt der Fachmann eine alkalische wässrige Zusammensetzung enthaltend Metall-Kationen ausgewählt aus Ionen der Elemente Kobalt, Nickel, Eisen und/oder Zinn in einer Menge von 0,01-1 g/l, einem Komplexbildner ausgewählt aus Pyrophosphat und/oder Nitrilotriessigsäure zur Verhinderung der Ausfällung schwerlöslicher Schwermetallsalze sowie optional ein Reduktionsmittel, vorzugsweise Sulfit. Derartige alkalische Zusammensetzungen eignen sich gemäß der Lehre der US 4278477 zur außenstromlosen Beschichtung von From the US 4278477 the expert takes an alkaline aqueous composition containing metal cations selected from ions of the elements cobalt, nickel, iron and / or tin in an amount of 0.01-1 g / l, a complexing agent selected from pyrophosphate and / or Nitrilotriacetic acid for preventing the precipitation of sparingly soluble heavy metal salts and optionally a reducing agent, preferably sulfite. Such alkaline compositions are suitable according to the teaching of US 4278477 for electroless coating of
Zinkoberflächen, wobei eine derartig beschichtete Zinkoberfläche nach Chromatierung und Aufbringung eines Lacksystems eine hohe Korrosionsbeständigkeit bei guten Lackhaftungswerten aufweist. Aufgrund der niedrigen ionalen Konzentrationen und der Anwesenheit des Komplexbildners wird eine hohe Badstabilität gewährleistet. Allerdings erlaubt das in der Zinc surfaces, wherein such a coated zinc surface after chromating and application of a paint system high corrosion resistance at good paint adhesion values having. Due to the low ionic concentrations and the presence of the complexing agent, a high bath stability is ensured. However, that allows in the
US 4278477 offenbarte Verfahren keine zufrieden stellende Vorbehandlung von Stahloberflächen und die Zusammensetzungen enthalten relativ hohe Mengen an komplexierenden Phosphaten und/oder Nitrilotriessigsäure, die aus ökologischen Gesichtspunkten bedenklich sind. US 4,278,477, does not disclose satisfactory pretreatment of steel surfaces and the compositions contain relatively high levels of complexing phosphates and / or nitrilotriacetic acid, which are of environmental concern.
Im Stand der Technik existiert demnach kein mehrstufiges Verfahren zur korrosionsschützenden Vorbehandlung von sowohl Zink- als auch Stahloberflächen, das hinsichtlich Accordingly, there is no multistage process for anticorrosive pretreatment of both zinc and steel surfaces in the prior art
Korrosionsschutzwirkung und Lackhaftungseigenschaften einer Trikation-Zinkphosphatierung zumindest gleichwertig ist und ressourcenschonend betrieben werden kann. Corrosion protection and paint adhesion properties of a trication zinc phosphating is at least equivalent and can be operated in a resource-saving manner.
Die Aufgabe der vorliegenden Erfindung besteht demnach darin, ein Verfahren zur The object of the present invention is therefore to provide a method for
korrosionsschützenden Vorbehandlung zu etablieren, das sich für die nachträgliche Aufbringung organischer Lacksysteme eignet, keine elektrolytischen Verfahrensschritte umfasst und in dem für einen effektiven Korrosionsschutz die Abscheidung geringer Mengen an Aktivkomponenten ausreichend ist, ohne dass sich signifikante Mengen an diesen Aktivkomponenten durch to establish corrosion-protective pretreatment, which is suitable for the subsequent application of organic coating systems, does not comprise electrolytic process steps and in which the deposition of small amounts of active components is sufficient for effective corrosion protection, without significant amounts of these active components through
Ausfällungsreaktionen verfahrensbedingt im Behandlungsbad absetzen und ggf. aufgearbeitet werden müssen. Zusätzlich sollte es möglich sein, in einem erfindungsgemäßen Verfahren, unterschiedliche Metalloberflächen eines Bauteils, die Oberflächen von Stahl, verzinktem Stahl und Aluminium darstellen, gleichsam mit einem korrosionsschützenden Überzug zu versehen, der einer Trikation-Zinkphosphatierung zumindest gleichwertig ist. Settle precipitation reactions due to the process in the treatment and must be worked up if necessary. In addition, in a method according to the invention, it should be possible, as it were, to provide different metal surfaces of a component, which are surfaces of steel, galvanized steel and aluminum, with an anticorrosive coating at least equivalent to a trication zinc phosphating.
Diese Aufgabe wird gelöst von einem mehrstufigen Verfahren zur korrosionsschützenden This problem is solved by a multi-stage process for corrosion protection
Vorbehandlung von metallischen Bauteilen, die Oberflächen von Stahl und/oder verzinktem Stahl aufweisen, umfassend die Verfahrensschritte i-iii), die jeweils das In-Kontakt-bringen des metallischen Bauteils mit einer wässrigen Behandlungslösung beinhalten, wobei die jeweiligen Verfahrensschritte i-iii) wie folgt charakterisiert sind: Pretreatment of metallic components having surfaces of steel and / or galvanized steel, comprising the method steps i-iii), each of which involve contacting the metallic component with an aqueous treatment solution, wherein the respective method steps i-iii) follows are characterized:
i) Reinigung und Entfettung der Metalloberfläche; i) cleaning and degreasing the metal surface;
ii) außenstromlose Behandlung durch In-Kontakt-bringen der Metalloberfläche mit einer ii) electroless treatment by contacting the metal surface with a
erfindungsgemäßen sauren wässrigen, chromfreien Zusammensetzung (A); acidic aqueous, chromium-free composition (A) according to the present invention;
iii) passivierende Behandlung durch In-Kontakt-bringen der Metalloberfläche mit einer sauren wässrigen Zusammensetzung (B) enthaltend iii) containing passivating treatment by contacting the metal surface with an acidic aqueous composition (B)
a) zumindest eine wasserlösliche Verbindung der Elemente Zr, Ti und/oder Hf in einer a) at least one water-soluble compound of the elements Zr, Ti and / or Hf in one
Konzentration von zumindest 5 ppm bezogen auf die Elemente Zr und/oder Ti, wobei die Verfahrensschritte ii) und iii) mit oder ohne dazwischen liegendem Spülschritt stets nach der Reinigung und Entfettung der Metalloberfläche, aber in beliebiger Reihenfolge vorgenommen werden. Concentration of at least 5 ppm based on the elements Zr and / or Ti, the process steps ii) and iii) are carried out with or without intermediate rinsing step always after cleaning and degreasing of the metal surface, but in any order.
Eine erfindungsgemäße saure wässrige, chromfreie Zusammensetzung (A), die bei In-Kontakt- bringen mit Stahl und/oder verzinktem Stahl in einem erfindungsgemäßen Verfahren einen effektiven Korrosionsschutz bereits durch Abscheidung geringer Mengen an Aktivkomponenten bewirkt, enthält An acidic aqueous, chromium-free composition (A) according to the invention which, when brought into contact with steel and / or galvanized steel, in a process according to the invention effective corrosion protection already effected by deposition of small amounts of active components contains
a) zumindest 100 ppm an Metall-Ionen (M) ausgewählt aus Ionen mindestens eines der a) at least 100 ppm of metal ions (M) selected from ions of at least one of
Elemente Nickel, Kobalt, Molybdän, Eisen oder Zinn, Elements nickel, cobalt, molybdenum, iron or tin,
b) zumindest eine wasserlösliche Verbindung enthaltend Schwefel in einer Oxidationsstufe b) at least one water-soluble compound containing sulfur in an oxidation state
kleiner als +6, less than +6,
c) weniger als 10 g/l an Zink-Ionen, c) less than 10 g / l of zinc ions,
d) insgesamt weniger als 1 g/l an gelösten Phosphaten berechnet als P04, d) a total of less than 1 g / l of dissolved phosphates calculated as P0 4 ,
und weist vorzugsweise einen pH-Wert im Bereich von 3,0 bis 6,5 auf. and preferably has a pH in the range of 3.0 to 6.5.
Werden in erfindungsgemäßen Verfahren metallische Bauteile umfassend Stahl und verzinkten Stahl mit einer erfindungsgemäßen Zusammensetzung (A) behandelt, wobei die Oberfläche des metallischen Bauteils zumindest zu 10% aus verzinkten Stahloberflächen besteht, so liegt der pH- Wert vorzugsweise in einem Bereich von 4,0 bis 7,0, besonders bevorzugt in einem Bereich von 5,0 bis 7,0, insbesondere im Bereich von 6,0 bis 6,8. If, in the process according to the invention, metallic components comprising steel and galvanized steel are treated with a composition (A) according to the invention, the surface of the metallic component consisting of at least 10% galvanized steel surfaces, the pH is preferably in the range from 4.0 to 7.0, more preferably in a range of 5.0 to 7.0, especially in the range of 6.0 to 6.8.
Erfindungsgemäß ist die Zusammensetzung (A) chromfrei, wenn weniger als 10 ppm, According to the invention, the composition (A) is chromium-free, if less than 10 ppm,
vorzugsweise weniger als 1 ppm Chrom, insbesondere überhaupt kein Chrom(VI) enthalten sind. preferably less than 1 ppm of chromium, in particular no chromium (VI) are contained.
Durch die außenstromlose Behandlung der Metalloberflächen nach der Entfettungsstufe und vor oder nach der passivierenden Behandlung des erfindungsgemäßen Verfahrens mit einer By the electroless treatment of the metal surfaces after the degreasing stage and before or after the passivating treatment of the method according to the invention with a
Zusammensetzung (A) wird eine Abscheidung der Metall-Ionen (M) (Aktivkomponente) auf den Metalloberflächen herbeigeführt. Die Schichtbildung erfolgt dabei zumindest teilweise in Form metallischer Phasen der Elemente Nickel, Kobalt, Molybdän, Eisen oder Zinn. Composition (A) causes deposition of the metal ions (M) (active component) on the metal surfaces. The layer formation takes place at least partially in the form of metallic phases of the elements nickel, cobalt, molybdenum, iron or tin.
Die schichtbildende Abscheidung der Metall-Ionen (M) in Gegenwart der reduzierend wirkenden wasserlöslichen Verbindung enthaltend Schwefel in einer Oxidationsstufe kleiner als +6 wird in Anwesenheit von Zink-Ionen inhibiert. Die erfindungsgemäße Zusammensetzung (A) enthält daher weniger als 10 g/l. The layer-forming deposition of the metal ions (M) in the presence of the reducing water-soluble compound containing sulfur in an oxidation state less than +6 is inhibited in the presence of zinc ions. The composition (A) according to the invention therefore contains less than 10 g / l.
Die Zusammensetzung (A) kann in einer bevorzugten Ausführungsform zusätzlich chelatisierende organische Verbindungen enthalten, die mindestens zwei funktionelle Gruppen mit Sauerstoff- und/oder Stickstoff-Atomen ausgewählt aus Carboxyl-, Hydroxyl-, Amin-, Phosphorsäure- oder Phosphonsäure-Gruppen aufweisen. Besonders bevorzugt sind chelatisierende organische Verbindungen, die Phosphorsäure-, Phosphonsäure- und/oder Hydroxyl-Gruppen enthalten, bspw. 1-Hydroxyethan-(1 ,1 -diphosphonsäure). Es hat sich herausgestellt, dass derartige Chelatbildner in der erfindungsgemäßen Zusammensetzung (A) vornehmlich Zink-Ionen komplexieren und daher die Inhibierung der Abscheidung der Metall-Ionen (M) auf den Metalloberflächen abschwächen. Die chelatisierenden organischen Verbindungen sind vorzugsweise in einer solchen Menge enthalten, dass der molare Überschuss an Zink-Ionen bezogen auf die chelatisierenden organischen Verbindungen nicht größer als 2 g/l, vorzugsweise nicht größer als 1 g/l, besonders bevorzugt nicht größer als 0,5 g/l an Zink-Ionen ist. In a preferred embodiment, the composition (A) may additionally contain chelating organic compounds which have at least two functional groups with oxygen and / or nitrogen atoms selected from carboxyl, hydroxyl, amine, phosphoric acid or phosphonic acid groups. Particularly preferred are chelating organic compounds containing phosphoric acid, phosphonic acid and / or hydroxyl groups, for example, 1-hydroxyethane (1, 1 -diphosphonic acid). It has been found that such chelating agents in the composition (A) according to the invention mainly complex zinc ions and therefore weaken the inhibition of the deposition of the metal ions (M) on the metal surfaces. The chelating organic compounds are preferably contained in such an amount that the molar excess of zinc ions relative to the chelating organic Compounds not greater than 2 g / l, preferably not greater than 1 g / l, more preferably not greater than 0.5 g / l of zinc ions.
Insgesamt sind jedoch solche Zusammensetzungen (A) bevorzugt, deren Gehalt an Zink-Ionen nicht größer als 2 g/l, vorzugsweise nicht größer als 1 g/l, besonders bevorzugt nicht größer als 0,5 g/l an Zink-Ionen ist. Overall, however, those compositions (A) are preferred whose content of zinc ions is not greater than 2 g / l, preferably not greater than 1 g / l, more preferably not greater than 0.5 g / l of zinc ions.
Auch die Menge an Phosphat-Ionen ist in der erfindungsgemäßen Zusammensetzungen (A) limitiert, da höhere Anteile die Ausbildung einer dünnen Phosphat-Passivierung bedingen können, die nachteilig für die Abscheidung der Metall-Ionen (M) auf den Metalloberflächen ist. Dies ist insofern überraschend als die passivierende Behandlung der Metalloberfläche mit einer The amount of phosphate ions is limited in the compositions (A) according to the invention, since higher proportions can cause the formation of a thin phosphate passivation, which is disadvantageous for the deposition of the metal ions (M) on the metal surfaces. This is surprising as the passivating treatment of the metal surface with a
Zusammensetzung auf Basis von Zirkon, Titan und/oder Hafnium, analog zum erfindungsgemäßen Behandlungsschritt iii), nicht nachteilig für die schichtbildende Abscheidung der Metall-Ionen (M) ist. Es sind daher solche erfindungsgemäßen Zusammensetzungen (A) bevorzugt, in denen der Anteil an gelösten Phosphat nicht mehr als 500 ppm, besonders bevorzugt nicht mehr als Composition based on zirconium, titanium and / or hafnium, analogously to the treatment step iii) according to the invention, is not detrimental to the layer-forming deposition of the metal ions (M). Therefore, such compositions (A) according to the invention are preferred in which the proportion of dissolved phosphate is not more than 500 ppm, more preferably not more than
200 ppm, insbesondere bevorzugt nicht mehr als 50 ppm berechnet als P04 beträgt. 200 ppm, more preferably not more than 50 ppm calculated as P0 4 .
Die Anwesenheit von wasserlöslichen Verbindungen der Elemente Zirkon, Titan und/oder Hafnium in einer erfindungsgemäßen Zusammensetzung (A) kann die Abscheidung der Metall-Ionen (M) auf den Stahloberflächen inhibieren. Zusätzlich resultiert aus derartigen Zusammensetzungen (A) keine Abscheidung von Zirkon, Titan und/oder Hafnium, so dass der Einsatz dieser Verbindungen keinen Vorteil erbringt und unwirtschaftlich ist. Bevorzugt sind demnach erfindungsgemäße Zusammensetzungen (A) deren Anteil an Zirkon, Titan und/oder Hafnium in Form wasserlöslicher Verbindungen insgesamt weniger als 20 ppm, besonders bevorzugt weniger als 5 ppm beträgt. The presence of water-soluble compounds of the elements zirconium, titanium and / or hafnium in a composition (A) according to the invention can inhibit the deposition of the metal ions (M) on the steel surfaces. In addition, such compositions (A) do not result in precipitation of zirconium, titanium and / or hafnium so that the use of these compounds provides no advantage and is uneconomical. According to the invention, preference is given to compositions (A) according to the invention whose content of zirconium, titanium and / or hafnium in the form of water-soluble compounds is in total less than 20 ppm, more preferably less than 5 ppm.
Die zumindest eine wasserlösliche Verbindung enthaltend Schwefel in einer Oxidationsstufe kleiner als +6 ist vorzugsweise ausgewählt aus anorganischen Verbindungen, besonders bevorzugt aus Oxosäuren von Schwefel wie schwefliger Säure, Thioschwefelsäure, Dithionsäure, Polythionsäure, schweflige Säure, dischweflige Säure und/oder Dithionsäure sowie deren Salze, insbesondere bevorzugt aus schwefliger Säure. Die wasserlösliche Verbindung enthaltend Schwefel kann zudem auch ausgewählt sein aus Salzen der organischen Säuren Thiocyansäure und/oder Thioharnstoff, wobei die zuvor genannten wasserlöslichen anorganischen Verbindungen enthaltend Schwefel den organischen Säuren und Salzen vorzuziehen sind. The at least one water-soluble compound containing sulfur in an oxidation state of less than +6 is preferably selected from inorganic compounds, more preferably from oxo acids of sulfur such as sulphurous acid, thiosulphuric acid, dithionic acid, polythionic acid, sulphurous acid, dibasic acid and / or dithionic acid and their salts, especially preferably from sulphurous acid. The water-soluble compound containing sulfur may also be selected from salts of the organic acids thiocyanic acid and / or thiourea, with the aforementioned water-soluble inorganic compounds containing sulfur being preferred over organic acids and salts.
Die Oxidationsstufe ist im Zusammenhang mit der vorliegenden Erfindung gemäß lUPAC-Regel I- 5.5.2.1 ("Nomenclature of Inorganic Chemistry - Recommendations 1990", Blackwell: Oxford, 1990) definiert und bezeichnet die hypothetische Ladung, die einem Element in einem Molekül zugeteilt werden würde, wenn diesem Element sämtliche mit anderen Elementen des Moleküls geteilten Elektronen zuzuordnen wären, für die das Element eine höhere Elektronegativität aufweist als diejenige des Elements, mit dem es die Elektronen teilt. Die bevorzugte Konzentration an wasserlöslichen Verbindungen enthaltend Schwefel in einer Oxidationsstufe kleiner als +6 beträgt zumindest 1 mM, vorzugsweise zumindest 5 mM, aber nicht mehr als 100 mM, vorzugsweise nicht mehr als 50 mM. Unterhalb von 1 mM ist eine The oxidation state, in the context of the present invention, is defined according to IUPL Rule I-5.5.2.1 ("Nomenclature of Inorganic Chemistry - Recommendations 1990", Blackwell: Oxford, 1990) and designates the hypothetical charge assigned to an element in a molecule would be if this element were to be assigned all the electrons shared with other elements of the molecule for which the element has a higher electronegativity than that of the element with which it shares the electrons. The preferred concentration of water-soluble compounds containing sulfur in an oxidation state less than +6 is at least 1 mM, preferably at least 5 mM, but not more than 100 mM, preferably not more than 50 mM. Below 1 mM is one
schichtbildende Abscheidung der Metall-Ionen (M) in typischen Behandlungszeiten von wenigen Minuten nicht gegeben oder erfolgt nicht. Oberhalb von 100 mM wird zum einen keine weitere Beschleunigung der Schichtbildung bei In-Kontakt-bringen einer gereinigten Stahloberfläche mit einer solchen Zusammensetzung (A) festgestellt und zum anderen sind höhere Mengen an schwefelhaltigen Verbindungen aus wirtschaftlichen und arbeitshygienischen Gründen abzulehnen. Layer-forming deposition of metal ions (M) in typical treatment times of a few minutes is not given or does not occur. Above 100 mM, on the one hand, no further acceleration of the layer formation on contacting a cleaned steel surface with such a composition (A) is found, and on the other hand, higher amounts of sulfur-containing compounds are rejected for economic and occupational hygiene reasons.
Andere Reduktionsmittel auf Basis wasserlöslicher Verbindungen enthaltend Phosphor und/oder Stickstoff in einer Oxidationsstufe kleiner als +5 erweisen sich überraschenderweise als ungeeignet für die Abscheidung der Metall-Ionen (M), insbesondere für die Abscheidung von Nickel- und/oder Kobalt-Ionen, so dass diese Reduktionsmittel in der Zusammensetzung (A) aus wirtschaftlichen Gründen vorzugsweise nicht oder nur in sehr geringen Mengen unterhalb von 50 ppm enthalten sind. Other reducing agents based on water-soluble compounds containing phosphorus and / or nitrogen in an oxidation state of less than +5 are surprisingly unsuitable for the deposition of the metal ions (M), in particular for the deposition of nickel and / or cobalt ions that these reducing agents in the composition (A) for economic reasons, preferably not or only in very small amounts below 50 ppm are included.
In erfindungsgemäßen Zusammensetzungen (A) sind vorzugsweise zumindest 0,2 g/l, aber nicht mehr als 5 g/l, vorzugsweise nicht mehr als 2 g/l an Metall-Ionen (M) ausgewählt aus Ionen mindestens eines der Elemente Nickel, Kobalt, Molybdän, Eisen oder Zinn, enthalten. Wird dieser Wert unterschritten ist die Aktivität der Metall-Ionen (M) in der Zusammensetzung (A) für eine hinreichende Abscheidung meist zu niedrig. Oberhalb von 5 g/l ist kein zusätzlicher Vorteil gegeben, wohingegen die vermehrte Ausfällung unlöslicher Salze der Metall-Ionen (M) zunimmt, so dass derart hohe Konzentrationen an Metall-Ionen (M) in Behandlungsbädern gemäß Schritt ii) des erfindungsgemäßen Verfahrens unwirtschaftlich sind und zudem erhöhte Aufarbeitungskosten bedingen. In inventive compositions (A) are preferably at least 0.2 g / l, but not more than 5 g / l, preferably not more than 2 g / l of metal ions (M) selected from ions of at least one of the elements nickel, cobalt , Molybdenum, iron or tin. If this value is undershot, the activity of the metal ions (M) in the composition (A) is usually too low for adequate deposition. Above 5 g / l there is no additional benefit, whereas the increased precipitation of insoluble salts of the metal ions (M) increases, so that such high concentrations of metal ions (M) in treatment baths according to step ii) of the process according to the invention are uneconomical and also require increased processing costs.
Als Metall-Ionen (M), die auf der Metalloberflächen im Verfahrensschritt ii) aus der sauren wässrigen Zusammensetzung (A) abgeschieden werden, eignen sich in einer bevorzugten Ausführungsform insbesondere Nickel und/oder Kobalt, besonders bevorzugt Nickel. As metal ions (M) which are deposited on the metal surfaces in process step ii) from the acidic aqueous composition (A), in a preferred embodiment, in particular nickel and / or cobalt, more preferably nickel.
Metalloberflächen von Stahl- und/oder verzinktem Stahl, die unabhängig von der Reihenfolge der Verfahrensschritte ii) und iii), mit einer wässrigen Zusammensetzung (A) enthaltend Nickel- und/oder Kobalt-Ionen, besonders bevorzugt Nickel-Ionen in Kontakt gebracht werden, werden innerhalb kurzer Behandlungszeit mit einer dünnen Schicht enthaltend die Elemente Nickel und/oder Kolbalt versehen, die eine ausgezeichnete Lackhaftung zu nachträglich aufgebrachten organischen Lacksystemen vermittelt und dabei höchsten Anforderungen an den Korrosionsschutz genügt. Metal surfaces of steel and / or galvanized steel, which are brought into contact with an aqueous composition (A) containing nickel and / or cobalt ions, particularly preferably nickel ions, independently of the sequence of process steps ii) and iii) are provided within a short treatment time with a thin layer containing the elements nickel and / or Kolbalt, which gives an excellent paint adhesion to subsequently applied organic paint systems and thereby meets the highest standards of corrosion protection.
Bevorzugte wasserlösliche Verbindungen, die Metall-Ionen (M) freisetzen, sind sämtliche wasserlöslichen Salze, die keine Chlorid-Ionen enthalten. Insbesondere bevorzugt sind Sulfate, Nitrate und Acetate. Eine bevorzugte erfindungsgemäße Zusammensetzung (A) weist ein molares Verhältnis von Metall-Ionen (M) ausgewählt aus Ionen mindestens eines der Elemente Nickel, Kobalt, Molybdän, Eisen oder Zinn zu wasserlöslichen Verbindungen enthaltend Schwefel von nicht größer als 1 : 1 , vorzugsweise nicht größer als 2 : 3, aber nicht kleiner als 1 : 5 ist. Oberhalb dieses bevorzugten molaren Verhältnisses von 1 : 1 verläuft die Ausbildung der dünnen Schicht enthaltend die Elemente der Metall-Ionen (M) langsamer, so dass insbesondere für die Anwendung der Preferred water-soluble compounds which release metal ions (M) are all water-soluble salts which do not contain chloride ions. Particular preference is given to sulfates, nitrates and acetates. A preferred composition (A) according to the invention has a molar ratio of metal ions (M) selected from ions of at least one of nickel, cobalt, molybdenum, iron or tin to water-soluble compounds containing sulfur of not greater than 1: 1, preferably not greater than 2: 3 but not less than 1: 5. Above this preferred molar ratio of 1: 1, the formation of the thin layer containing the elements of the metal ions (M) is slower, so that in particular for the application of
Zusammensetzung (A) im Verfahrensschritt ii) eines erfindungsgemäßen Composition (A) in process step ii) of an inventive
Bandbeschichtungsverfahrens solche Zusammensetzungen (A) bevorzugt sind, in denen relativ zur Gesamtmenge an Metall-Ionen (M) eine hinreichende Menge an wasserlöslichen Verbindungen enthaltend Schwefel anwesend ist. Umgekehrt kann ein molares Verhältnis von Metall-Ionen (M) zu wasserlöslichen Verbindungen enthaltend Schwefel unterhalb von 1 : 5 für die Stabilität erfindungsgemäßer Zusammensetzungen (A) nachteilig sein, da die reduzierend wirkenden Schwefelverbindungen dann eine Ausscheidung der enthaltenden Metalle in kolloidaler Form herbeiführen können. A coating process is preferably those compositions (A) in which a sufficient amount of water-soluble compounds containing sulfur relative to the total amount of metal ions (M) is present. Conversely, a molar ratio of metal ions (M) to water-soluble compounds containing sulfur below 1: 5 may be detrimental to the stability of compositions (A) of the invention because the reducing sulfur compounds can then cause precipitation of the containing metals in colloidal form.
Für erfindungsgemäße Zusammensetzungen (A) kann ein Zusatz von elektropositiven Metall- Kationen von Vorteil sein, um die Schichtbildung zu beschleunigen. Eine bevorzugte For compositions (A) according to the invention, it may be advantageous to add electropositive metal cations in order to accelerate the layer formation. A preferred
Ausführungsform der Erfindung enthält daher zusätzlich Kupfer-Ionen und/oder Silber-Ionen, vorzugsweise Kupfer-Ionen, in einer Menge von zumindest 1 ppm, aber nicht mehr als 100 ppm. Oberhalb von 100 ppm kann die Abscheidung des elektropositiven Metalls in elementarer Form auf den Stahl- und/oder verzinkten Stahloberflächen soweit dominieren, dass die Schichtbildung basierend auf den Metall-Ionen (M) soweit zurückgedrängt wird, dass die Lackhaftung zu im erfindungsgemäßen Verfahren nachträglich aufgebrachten organischen Lacken deutlich verschlechtert wird oder inhomogene Schichtüberzüge nach Schritt ii) des erfindungsgemäßen Verfahrens erzeugt werden, die einen schlechteren Korrosionsschutz bieten. Embodiment of the invention therefore additionally contains copper ions and / or silver ions, preferably copper ions, in an amount of at least 1 ppm, but not more than 100 ppm. Above 100 ppm, the deposition of the electropositive metal in elemental form on the steel and / or galvanized steel surfaces dominate so far that the layer formation based on the metal ions (M) is pushed back so far that the paint adhesion applied subsequently in the process according to the invention organic paints is significantly deteriorated or inhomogeneous layer coatings are produced after step ii) of the method according to the invention, which offer a poorer corrosion protection.
Bevorzugte wasserlösliche Verbindungen, die Kupfer-Ionen freisetzen, sind sämtliche Preferred water-soluble compounds that release copper ions are all
wasserlöslichen Kupfersalze, die keine Chlorid-Ionen enthalten, sowie alle wasserlöslichen Silbersalze. Insbesondere bevorzugt sind Sulfate, Nitrate und Acetate. water-soluble copper salts containing no chloride ions and all water-soluble silver salts. Particular preference is given to sulfates, nitrates and acetates.
Ebenso kann der Zusatz von wasserlöslichen Verbindungen, die eine Quelle für Fluorid-Ionen darstellen, zu einer erfindungsgemäßen Zusammensetzung (A) bevorzugt sein, wobei die Likewise, the addition of water-soluble compounds, which are a source of fluoride ions, to a composition (A) according to the invention may be preferred, wherein the
Konzentration an Gesamtfluorid in der Zusammensetzung (A) vorzugsweise zumindest 50ppm, aber nicht größer als 2000 ppm ist. Der Zusatz von Fluorid ist insbesondere dann vorteilhaft, wenn in einem erfindungsgemäßen Verfahren der Schritt ii) mit oder ohne dazwischen liegendem Spülschritt dem Reinigungsschritt i) unmittelbar nachfolgt und insbesondere dann, wenn schmelztauchverzinkte Stahloberflächen behandelt werden. In einem solchen Fall erhöht sich die Beizrate auf den Metalloberflächen und eine schnellere Abscheidungskinetik der dünnen Concentration of total fluoride in the composition (A) is preferably at least 50 ppm but not more than 2000 ppm. The addition of fluoride is particularly advantageous when, in a process according to the invention, step ii), with or without a rinsing step between them, immediately follows the purification step i) and in particular when hot-dip galvanized steel surfaces are treated. In such a case, the pickling rate on the metal surfaces and faster deposition kinetics of the thin increases
Beschichtung bestehend aus Elementen der Metall-Ionen (M) sowie eine homogenere Coating consisting of elements of metal ions (M) and a more homogeneous
Beschichtung der Metalloberfläche ist die unmittelbare Folge. Unterhalb einer Gesamtfluoridmenge von 50 ppm ist dieser zusätzliche positive Effekt kaum ausgeprägt, während oberhalb von 2000 ppm keine weitere Steigerung der Abscheidungskinetik erfolgt, aber die Ausfällung unlöslicher Fluoride nachteilig wird. Bevorzugte wasserlösliche Verbindungen, die als Quelle für Fluorid-Ionen dienen, sind Fluorwasserstoff, Alkalifluoride, Ammoniumfluorid und/oder Coating the metal surface is the immediate consequence. Below a total fluoride amount of 50 ppm, this additional positive effect is hardly pronounced, while above 2000 ppm no further increase in the deposition kinetics, but the precipitation of insoluble fluorides is disadvantageous. Preferred water-soluble compounds which serve as a source of fluoride ions are hydrogen fluoride, alkali fluorides, ammonium fluoride and / or
Ammoniumbifluorid. Ammonium.
In erfindungsgemäßen Verfahren umfassend die einzelnen Schritte i-iii) ist eine Reinigung und Entfettung der Metalloberfläche für eine homogene Ausbildung der passivierenden Beschichtung gemäß den Verfahrensschritten ii) und iii) notwendig. Insbesondere sind solche Reinigungsschritte i) erfindungsgemäß bevorzugt, die mittels einer wässrigen Reinigungslösung durchgeführt werden, bei der die Reinigung einen Beizabtrag von zumindest 0,4 g/m2, aber nicht mehr als 0,8 g/m2 Zink bezogen auf eine Oberfläche von elektrolytisch verzinktem Stahl hervorruft. Der Fachmann kennt Reiniger, die bei vorgegebener Reinigungsdauer eine entsprechende Beizrate besitzen. Es zeigt sich überraschend, dass eine solche bevorzugte Reinigung zu besseren Ergebnissen hinsichtlich Korrosionsschutz und Lackhaftung der erfindungsgemäß behandelten Stahl- und/oder verzinkten Stahloberflächen führt. In methods according to the invention comprising the individual steps i-iii), a cleaning and degreasing of the metal surface is necessary for a homogeneous formation of the passivating coating according to process steps ii) and iii). In particular, those purification steps i) are preferred according to the invention, which are carried out by means of an aqueous cleaning solution, wherein the cleaning a Beizabtrag of at least 0.4 g / m 2 , but not more than 0.8 g / m 2 of zinc based on a surface of Electrolytic galvanized steel causes. The person skilled in the art knows cleaners which have a corresponding pickling rate for a given cleaning time. It has surprisingly been found that such a preferred purification leads to better results in terms of corrosion protection and paint adhesion of the steel and / or galvanized steel surfaces treated according to the invention.
Die im Schritt iii) des erfindungsgemäßen Verfahrens eingesetzten sauren wässrigen The acidic aqueous used in step iii) of the process according to the invention
Zusammensetzungen (B) sind vorzugsweise chromfrei, d.h. sie enthalten weniger als 10 ppm, vorzugsweise weniger als 1 ppm Chrom, insbesondere kein Chrom(VI). Des Weiteren enthalten die sauren Zusammensetzungen (B) im erfindungsgemäßen Verfahren vorzugsweise insgesamt 20 bis 1000 ppm an wasserlöslichen Verbindungen der Elemente Zirkon, Titan und/oder Hafnium bezogen auf die Elemente Zirkon, Titan und/oder Hafnium. Sind weniger als 20 ppm bezogen auf die Elemente Zirkon, Titan und/oder Hafnium enthalten, kann eine unzureichende Konversion der gereinigten oder der im Schritt ii) behandelten Metalloberfläche die Folge sein, so dass nur geringe Mengen an Hydroxiden und/oder Oxiden dieser Elemente abgeschieden werden und die passivierende Wirkung zu gering ausfällt. Oberhalb von 1000 ppm bezogen auf die Elemente Zirkon, Titan und/oder Hafnium in der Zusammensetzung (B) kann jedoch eine weitergehende Verbesserung der Korrosionseigenschaften der erfindungsgemäß behandelten Metalloberflächen nicht festgestellt werden. Compositions (B) are preferably free of chromium, i. they contain less than 10 ppm, preferably less than 1 ppm of chromium, in particular no chromium (VI). Furthermore, the acidic compositions (B) in the process according to the invention preferably contain a total of 20 to 1000 ppm of water-soluble compounds of the elements zirconium, titanium and / or hafnium based on the elements zirconium, titanium and / or hafnium. If less than 20 ppm of the elements zirconium, titanium and / or hafnium contain an insufficient conversion of the purified or treated in step ii) metal surface may be the result so that only small amounts of hydroxides and / or oxides of these elements deposited and the passivating effect is too low. Above 1000 ppm, based on the elements zirconium, titanium and / or hafnium in the composition (B), however, a further improvement in the corrosion properties of the metal surfaces treated according to the invention can not be determined.
Weiterhin bevorzugt sind solche säure wässrige Zusammensetzung (B) im erfindungsgemäßen Verfahren, die als wasserlösliche Verbindungen der Elemente Zirkon, Titan und/oder Hafnium, lediglich wasserlösliche Verbindungen der Elemente Zirkon und/oder Titan, besonders bevorzugt wasserlösliche Verbindungen des Elements Zirkon enthalten. Preference is furthermore given to those acidic aqueous compositions (B) in the process according to the invention which contain, as water-soluble compounds of the elements zirconium, titanium and / or hafnium, only water-soluble compounds of the elements zirconium and / or titanium, more preferably water-soluble compounds of the element zirconium.
Bevorzugte wasserlösliche Verbindungen der Elemente Zirkon, Titan und/oder Hafnium sind Verbindungen, die in wässriger Lösung in Anionen von Fluorokomplexen der Elemente Zirkon, Titan und/oder Hafnium dissozieren. Solche bevorzugten Verbindungen sind beispielsweise H2ZrF6, K2ZrF6, Na2ZrF6 und (NH4)2ZrF6 und die analogen Titan-Verbindungen. Auch fluorfreie Verbindungen der Elemente Zirkon, Titan und/oder Hafnium können als wasserlösliche Preferred water-soluble compounds of the elements zirconium, titanium and / or hafnium are compounds which dissociate in aqueous solution into anions of fluorocomplexes of the elements zirconium, titanium and / or hafnium. Such preferred compounds are, for example, H 2 ZrF 6 , K 2 ZrF 6 , Na 2 ZrF 6 and (NH 4 ) 2 ZrF 6 and the analogous titanium compounds. Also, fluorine-free compounds of the elements zirconium, titanium and / or hafnium can be used as water-soluble
Verbindungen erfindungsgemäß eingesetzt werden, beispielsweise (NH4)2Zr(OH)2(C03)2 oder TiO(S04). Zusätzlich kann eine Zusammensetzung (B) im Schritt iii) des erfindungsgemäßen Verfahrens 1 bis 100 ppm an Kupfer-Ionen enthalten sowie gegebenenfalls bis zu 200 ppm freies Fluorid. Der Zusatz von Kupfer-Ionen beschleunigt die Konversion der gereinigten oder der im Schritt ii) behandelten Metalloberflächen und erhöht zudem die passivierende Wirkung. Insbesondere für den Fall, dass zunächst die passivierende Behandlung der Stahl- und/oder verzinkten Compounds are used according to the invention, for example (NH 4 ) 2 Zr (OH) 2 (C0 3 ) 2 or TiO (S0 4 ). In addition, a composition (B) in step iii) of the process according to the invention may contain 1 to 100 ppm of copper ions and optionally up to 200 ppm of free fluoride. The addition of copper ions accelerates the conversion of the purified or treated in step ii) metal surfaces and also increases the passivating effect. Especially in the event that first the passivating treatment of steel and / or galvanized
Stahloberflächen erfolgt, kann eine deutliche Verbesserung der Schichtbildung im nachfolgenden Schritt ii) festgestellt werden und damit verbesserte Korrosionsschutzeigenschaften. Bevorzugte wasserlösliche Verbindungen, die Kupfer-Ionen freisetzen, sind sämtliche wasserlöslichen Kupfersalze, die keine Chlorid-Ionen enthalten. Insbesondere bevorzugt sind Sulfate, Nitrate und Acetate. Steel surfaces, a significant improvement of the film formation in the subsequent step ii) can be found and thus improved corrosion protection properties. Preferred water-soluble compounds that release copper ions are all water-soluble copper salts that do not contain chloride ions. Particular preference is given to sulfates, nitrates and acetates.
Die optionale Zugabe von Fluorid-Ionen in den bevorzugten Mengenbereich bezogen auf freies Fluorid, das wiederum mittels einer ionensensitiven Messelektrode bestimmt werden kann, erleichtert die homogene Konversion der gereinigten oder der im Schritt ii) behandelten The optional addition of fluoride ions in the preferred amount range based on free fluoride, which in turn can be determined by means of an ion-sensitive measuring electrode, facilitates the homogeneous conversion of the purified or treated in step ii)
Metalloberflächen. Bevorzugte wasserlösliche Verbindungen, die als Quelle für Fluorid-Ionen dienen, sind Fluorwasserstoff, Alkalifluoride, Ammoniumfluorid und/oder Ammoniumbifluorid. Metal surfaces. Preferred water-soluble compounds which serve as a source of fluoride ions are hydrogen fluoride, alkali fluorides, ammonium fluoride and / or ammonium bifluoride.
Die Behandlungstemperatur und die Dauer der jeweiligen Behandlung sind in den einzelnen Schritten i-iii) des erfindungsgemäßen Verfahrens unterschiedlich und stark abhängig von der Badanlage und der Applikationsart, können aber über einen weiten Bereich variiert werden, ohne dass Einbußen hinsichtlich der Korrosionseigenschaften hingenommen werden müssen. The treatment temperature and the duration of the respective treatment are different in the individual steps i-iii) of the process according to the invention and strongly dependent on the bath system and the type of application, but can be varied over a wide range, without sacrificing corrosion properties.
Vorzugsweise sollte die Behandlung in den Schritten i-iii) wie folgt vorgenommen werden: Preferably, the treatment in steps i-iii) should be carried out as follows:
Verfahrensschritt i): 2-10 Minuten bei 30 - 70 °C Process step i): 2-10 minutes at 30-70 ° C
Verfahrensschritt ii): 10-300 Sekunden bei 20 - 50 °C Process step ii): 10-300 seconds at 20-50 ° C
Verfahrensschritt iii): 0,5-10 Minuten bei 20 - 50 °C Process step iii): 0.5-10 minutes at 20-50 ° C
Die konkreten Bedingungen für das In-Kontakt-bringen der Metalloberflächen mit den wässrigen Behandlungsstufen ii) und iii) sind vorzugsweise derart auszuwählen, dass im Schritt ii) eine Schichtauflage von zumindest 30 mg/2, besonders bevorzugt zumindest 50 mg/m2 eines oder mehrerer der Metall-Ionen (M) auf den Oberflächen von Zink resultiert, während Temperatur und Behandlungsdauer im Schritt iii) so anzupassen sind, dass eine Schichtauflage von zumindest 10 mg/m2 Zirkon und/oder Titan, besonders bevorzugt von zumindest 25 mg/m2 Zirkon und/oder Titan auf den Oberflächen von Zink resultiert. Unterhalb dieser bevorzugten Schichtauflagen sind die korrosionsschützenden Eigenschaften der Vorbehandlung zumeist nicht ausreichend. The concrete conditions for bringing the metal surfaces into contact with the aqueous treatment stages ii) and iii) are preferably to be selected such that in step ii) a layer coverage of at least 30 mg / 2 , more preferably at least 50 mg / m2 of one or more of the metal ions (M) on the surfaces of zinc, while the temperature and duration of treatment in step iii) are to be adjusted such that a coating of at least 10 mg / m 2 zirconium and / or titanium, more preferably at least 25 mg / m 2 zirconium and / or titanium on the surfaces of zinc results. Below these preferred layer coverings, the corrosion protection properties of the pretreatment are usually insufficient.
Die einzelnen Schritte i-iii) des erfindungsgemäßen Verfahrens können mit oder ohne dazwischen liegendem Spülschritt durchgeführt werden. Bevorzugt ist jedoch, dass nach dem Reinigungsschritt i) zumindest ein zusätzlicher Spülschritt mit Stadtwasser oder entionisiertem Wasser (κ < 1 μ8ϋΐη" ) erfolgt. Überraschenderweise können außergewöhnlich gute Ergebnisse hinsichtlich Korrosionsschutzeigenschaften und der Lackhaftung unabhängig von der Reihenfolge der Schritte ii) und iii) im erfindungsgemäßen Verfahren erzielt werden. In einer bevorzugten Ausführungsform erfolgt die außenstromlose Behandlung gemäß Verfahrensschritt ii) jedoch unmittelbar, d.h. mit oder ohne dazwischen liegendem Spülschritt, nach dem Reinigungsschritt i). Für diese bevorzugte The individual steps i-iii) of the process according to the invention can be carried out with or without an intermediate rinsing step. However, it is preferred that after the purification step i) at least one additional rinsing step with city water or deionized water (κ <1 μ8ϋΐη " ) takes place. Surprisingly, exceptionally good results with regard to corrosion protection properties and paint adhesion can be achieved independently of the sequence of steps ii) and iii) in the process according to the invention. In a preferred embodiment, however, the electroless treatment according to method step ii) takes place directly, ie with or without an intermediate rinsing step, after the purification step i). For these preferred
Verfahrweise wird zunächst die Schichtbildung auf Basis der Elemente der Metall-Ionen (M) vollzogen und anschließend eine Konversion der so behandelten Metalloberfläche mit Hilfe der Zirkon- und/oder Titanhaitigen Zusammensetzung (B) vorgenommen. In a first step, the layer formation based on the elements of the metal ions (M) is carried out and then a conversion of the metal surface treated in this way is carried out with the aid of the zirconium- and / or titanium-containing composition (B).
Das erfindungsgemäße Verfahren eignet sich für metallische Bauteile, die Eisen-, Stahl- und/oder verzinkte Stahloberflächen sowie die entsprechenden vorphosphatierten Oberflächen aufweisen. Auf diesen Oberflächen findet unabhängig von der Reihenfolge der Schritte ii) und iii) im erfindungsgemäßen Verfahren stets eine hinreichende Schichtbildung auf Basis der Elemente der Metall-Ionen (M) statt, die wiederum Voraussetzung für die hervorragenden Eigenschaften hinsichtlich Korrosion und Lackhaftung ist. Ebenso werden im erfindungsgemäßen Verfahren auch Oberflächen von Aluminium im Schritt iii) passiviert, so dass sich das Verfahren insbesondere für die korrosionsschützende Vorbehandlung von in Multi-Metall-Bauweise zusammengesetzten Oberflächen, bspw. Karosserien in der Automobilindustrie, eignet. The method according to the invention is suitable for metallic components which have iron, steel and / or galvanized steel surfaces and the corresponding pre-phosphated surfaces. Irrespective of the sequence of steps ii) and iii), sufficient layer formation on the basis of the elements of the metal ions (M) always takes place on these surfaces, which in turn is a prerequisite for the outstanding properties with respect to corrosion and paint adhesion. Likewise, surfaces of aluminum are passivated in step iii) in the process according to the invention, so that the process is particularly suitable for the corrosion-protective pretreatment of multi-metal construction surfaces, for example.
Die wässrigen Zusammensetzungen in den Schritten i-iii) können sowohl in Tauch- als auch in Spritzverfahren mit den Metalloberflächen in Kontakt gebracht werden. Das Verfahren kann ebenfalls in der Vorbehandlung von Metallband eingesetzt werden und dort bspw. auch mittels der dem Fachmann bekannten Walzenauftragsverfahren. The aqueous compositions in steps i-iii) can be brought into contact with the metal surfaces in both immersion and spraying processes. The method can also be used in the pretreatment of metal strip and there, for example, by means of the roller application method known to those skilled in the art.
Dem erfindungsgemäßen Verfahren folgt üblicherweise die Auftragung eines Lacksystems, so dass nach dem Durchlaufen der Verfahrensschritte i-iii) mit oder ohne dazwischen liegendem Spül- und/oder Trocknungsschritt vorzugsweise eine Tauchlackabscheidung oder eine The process of the invention is usually followed by the application of a coating system, so that after passing through the process steps i-iii) with or without intermediate rinsing and / or drying step preferably a dip coating or a
Pulverlackbeschichtung, besonders bevorzugt eine Tauchlackabscheidung, insbesondere eine kathodische Tauchlackabscheidung folgt. Powder coating, particularly preferably a dip coating, in particular a cathodic dip coating follows.
Die vorliegende Erfindung umfasst ferner eine Metalloberfläche von Eisen und/oder Stahl mit Passivschichtsystem, das zumindest 30 mg/m2 Nickel und zumindest 10 mg/m2 Zirkon, Titan und/oder Hafnium, vorzugsweise zumindest 10 mg/m2 Zirkon, sowie Schwefel enthält, wobei Nickel zumindest zu 30 At.-% in metallischer Form vorliegt, erhältlich in einem bevorzugten The present invention further comprises a metal surface of iron and / or steel with passive layer system comprising at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium, preferably at least 10 mg / m 2 zirconium, and sulfur wherein nickel is at least 30 at.% in metallic form, obtainable in a preferred one
erfindungsgemäßen Verfahren, in dem auf den Verfahrensschritt i) mit oder ohne dazwischen liegendem Spülschritt unmittelbar die außenstromlose Behandlung gemäß Schritt ii) folgt, wobei die erfindungsgemäße Zusammensetzung (A) im Verfahrensschritt ii) zumindest 100 ppm, aber nicht mehr als 5 g/l an Nickel-Ionen sowie zumindest 1 mM schweflige Säure und/oder deren Salz umfasst und die Eisen und/oder Stahloberfläche bei einer Behandlungstemperatur im Bereich von 20 bis 50 °C mit einer solchen Zusammensetzung (A) für zumindest eine Minute in Kontakt gebracht wird. process according to the invention, in which step i) with or without intermediate rinsing step directly followed by the electroless treatment according to step ii), the composition (A) in process step ii) at least 100 ppm, but not more than 5 g / l Nickel ions and at least 1 mM sulfurous acid and / or salt thereof and the iron and / or steel surface at a treatment temperature in the range of 20 to 50 ° C is brought into contact with such a composition (A) for at least one minute.
Des Weiteren umfasst vorliegende Erfindung eine Metalloberfläche von Zink und/oder verzinktem Stahl mit Passivschichtsystem, das zumindest 30 mg/m2 Nickel und zumindest 10 mg/m2 Zirkon, Titan und/oder Hafnium, vorzugsweise zumindest 10 mg/m2 Zirkon, sowie Schwefel enthält, wobei Nickel zumindest zu 30 At.-% in metallischer Form vorliegt, erhältlich in einem erfindungsgemäßen Verfahren, bei dem der Verfahrensschritt ii) mit oder ohne dazwischen liegendem Spülschritt unmittelbar dem Verfahrensschritt iii) nachfolgt und bei dem die erfindungsgemäße Furthermore, the present invention comprises a metal surface of zinc and / or galvanized steel with a passive layer system comprising at least 30 mg / m 2 nickel and at least 10 mg / m 2 zirconium, titanium and / or hafnium, preferably at least 10 mg / m 2 zirconium, and Contains sulfur, wherein nickel is at least 30 at .-% in metallic form, obtainable in a process according to the invention, in which the process step ii) with or without intermediate rinsing step immediately following the process step iii) and in which the inventive
Zusammensetzung (A) im Verfahrensschritt ii) zumindest 100 ppm, aber nicht mehr als 5 g/l an Nickel-Ionen sowie zumindest 1 mM schweflige Säure und/oder deren Salz umfasst und die Zink und/oder verzinkte Stahloberfläche bei einer Behandlungstemperatur im Beriech von 20 bis 50 °C mit einer solchen Zusammensetzung (A) für zumindest eine Minute in Kontakt gebracht wird. Composition (A) in process step ii) comprises at least 100 ppm, but not more than 5 g / l of nickel ions and at least 1 mM sulphurous acid and / or salt thereof and the zinc and / or galvanized steel surface at a treatment temperature in the range of 20 to 50 ° C is brought into contact with such a composition (A) for at least one minute.
Die Erfindung betrifft zudem die Verwendung der erfindungsgemäß behandelten metallischen Bauteile oder des erfindungsgemäß behandelten Metallbands in der Fertigung von The invention additionally relates to the use of the metallic components treated according to the invention or of the metal strip treated according to the invention in the manufacture of
Automobilkarosserien. Automobile bodies.
Ausführungsbeispiele: EXAMPLES
Im Folgenden wird die korrosionsschützende Wirkung der erfindungsgemäßen Vorbehandlung für unterschiedliche Materialien anhand einer bevorzugten erfindungsgemäßen Zusammensetzung (A) illustriert. In the following, the anticorrosion effect of the pretreatment according to the invention for different materials is illustrated by means of a preferred composition (A) according to the invention.
Die bevorzugte erfindungsgemäße Zusammensetzung (A) hat eine pH-Wert von 3,7 und folgendeThe preferred composition (A) according to the invention has a pH of 3.7 and following
Zusammensetzung (Beispiele B1 und B2): Composition (Examples B1 and B2):
3,1 g/l Nickelnitratlösung; 3,8 g/l Natriumhydrogensulfit 3.1 g / l nickel nitrate solution; 3.8 g / l sodium bisulfite
Das bevorzugte erfindungsgemäße Verfahren (B1 und B2), gemäß dem Metallbleche von Stahl (CRS), schmelztauchverzinktem Stahl (HDG) und elektrolytisch verzinktem Stahl (ZE) behandelt werden, ist durch folgende Einzelschritte i-iii) charakterisiert: i) Reinigung und Entfettung bei 55 °C für 5 Minuten mit einem alkalischen Reiniger der The preferred process according to the invention (B1 and B2) according to which metal sheets of steel (CRS), hot dip galvanized steel (HDG) and electrolytically galvanized steel (ZE) are treated is characterized by the following individual steps i-iii): i) cleaning and degreasing 55 ° C for 5 minutes with an alkaline cleaner of
Zusammensetzung: Composition:
B1 : 3,0 Gew.-% Ridoline ® 1565 A; 0,4 Gew.-% Ridosol ® 1270 (Fa. Henkel) B1: 3.0% by weight of Ridoline® 1565 A; 0.4% by weight of Ridosol® 1270 (Henkel)
B2: 3,0 Gew.-% Ridoline ® 1574 A; 0,4 Gew.-% Ridosol ® 1270 (Fa. Henkel) B2: 3.0% by weight Ridoline® 1574 A; 0.4% by weight of Ridosol® 1270 (Henkel)
Der Ansatz der Reinigerlösung erfolgt jeweils mit Leitungswasser. The approach of the cleaning solution is always with tap water.
Eine Reinigung und Entfettung mit einer Reinigungslösung wie im Beispiel B2 bewirkt einen Beizabtrag von 0,5 g/m2 auf elektrolytisch verzinkten Substraten, während eine A cleaning and degreasing with a cleaning solution as in Example B2 causes a pickling of 0.5 g / m 2 on electrolytically galvanized substrates, while a
Reinigungslösung gemäß Beispiel B1 Zinkoberflächen nicht anbeizt. ii) außenstromlose Behandlung mit der oben genannten bevorzugten Zusammensetzung (A) bei 30 °C für eine Minute iii) passivierende Behandlung mit einer Zirkon-basierten Vorbehandlungslösung, die auf einen pH-Wert von 4,0 eingestellt wurde und 150 ppm Zirkon, 20 ppm Cu und einen freien Fluorid- Gehalt von 60 ppm aufweist, bei 30 °C für zwei Minuten Cleaning solution according to Example B1 Zinc surfaces not stained. ii) electroless treatment with the above-mentioned preferred composition (A) at 30 ° C for one minute iii) passivating treatment with a zirconium-based pretreatment solution adjusted to a pH of 4.0 and 150 ppm zirconium, 20 ppm Cu and a free fluoride content of 60 ppm, at 30 ° C for two minutes
(TecTalis ® 1800; 0,25 g/l Grano Toner ® 38; Fa. Henkel) (TecTalis® 1800, 0.25 g / l Grano Toner® 38, Henkel)
Nach jedem der Einzelschritte i-iii) folgt ein Spülschritt mit entionisiertem Wasser (κ < 1 μ8ϋΐη" ). After each of the individual steps i-iii) is followed by a rinsing step with deionized water (κ <1 μ8ϋΐη " ).
Zu Vergleichszwecken wurden entsprechende Metallbleche nach einer Reinigung und Entfettung analog zum oben aufgeführten Schritt i) mit einer herkömmlichen Trikation-Phosphatierung (Granodine ® 952, Fa. Henkel; Schichtgewicht auf 2,0 HDG/EG CRS: 2,5 g/m2 bestimmt durch Differenzwägung nach dem Ablösen der Phosphatschicht in wässriger 0,5 Gew.-% Cr03 bei 20°C für 15 min) versehen (Vergleichsbeispiele V1 und V2) oder mit einer Zirkon-basierten Konversionbehandlung analog zum oben aufgeführten Schritt iii) passiviert (Vergleichsbeispiele V3 und V4). For comparison purposes, corresponding metal sheets after cleaning and degreasing were determined analogously to step i) above with a conventional trication-phosphating (Granodine® 952, Fa. Henkel, coating weight to 2.0 HDG / EC CRS: 2.5 g / m 2 by differential weighing after the removal of the phosphate layer in aqueous 0.5 wt .-% Cr0 3 at 20 ° C for 15 min) provided (Comparative Examples V1 and V2) or with a zirconium-based Conversion treatment analogous to the above-mentioned step iii) passivated (Comparative Examples V3 and V4).
Die erfindungsgemäß behandelten Metallbleche und die Vergleichsbleche wurden nach dem letzten Spülschritt mit Pressluft getrocknet und mit folgendem kathodischen Tauchlack elektrotauchlackiert: Aqua ® 3000 (Fa Dupont; KTL-Schichtdicke: 20 μιη zerstörungsfrei bestimmt mit handelsüblichem Schichtdickenmessgerät) The metal sheets treated according to the invention and the comparative sheets were dried with compressed air after the last rinsing step and electrocoated with the following cathodic dip coating: Aqua® 3000 (Dupont Co., KTL layer thickness: 20 μm, determined nondestructively using a commercially available layer thickness gauge)
und der Lack anschließend bei 175 °C für 25 min im Ofen eingebrannt. and then the paint baked at 175 ° C for 25 min in the oven.
Anschließend wurden die Metallbleche einem Wechselklima-Korrosionstest nach VDA 621.415 (10 Runden) oder einem Steinschlagtest nach DIN EN ISO 20567-1 unterworfen. Die resultierenden Testergebnisse sind in der Tabelle 1 zusammengefasst. Subsequently, the metal sheets were subjected to an alternating climate corrosion test according to VDA 621.415 (10 rounds) or a stone impact test according to DIN EN ISO 20567-1. The resulting test results are summarized in Table 1.
Insgesamt geht aus der Tabelle 1 hervor, dass die erfindungsgemäß behandelten Metallbleche (B1 und B2), denen die lediglich eine Zirkon-basierte Konversionsbehandlung erfahren haben (V3 und V4), sowohl hinsichtlich korrosiver Unterwanderung des Lackes (U/2-Werte) als auch im Overall, it can be seen from Table 1 that the metal sheets (B1 and B2) treated according to the invention, which have undergone only a zirconium-based conversion treatment (V3 and V4), both with respect to corrosive infiltration of the paint (U / 2 values) and in the
Steinschlagtest (K-Werte) deutlich überlegen ist. Stone impact test (K values) is clearly superior.
Darüber hinaus zeigen die Korrosionsergebnisse, dass eine der Trikation-Zinkphosphatierung (V1 und V2) zumindest gleichwertige korrosionsschützende Beschichtung mit dem erfindungsgemäßen Verfahren realisiert wird. In addition, the corrosion results show that one of the trication-Zinkphosphatierung (V1 and V2) at least equivalent corrosion-protective coating is realized with the inventive method.
Insgesamt wird insbesondere auf verzinkten Oberflächen, die in einem erfindungsgemäßen Verfahren behandelt werden (B1 und B2), eine deutliche Verbesserung der Overall, especially on galvanized surfaces which are treated in a method according to the invention (B1 and B2), a marked improvement in the
Korrosionseigenschaften und eine Erhöhung der Lackhaftung zum KTL erreicht, die sogar im Vergleich zur Trikation-Zinkphosphatierung deutlich verbessert vorliegen. Corrosion properties and an increase in the paint adhesion to the KTL reached that are significantly improved even compared to the trication zinc phosphating.
Überraschend zeigt sich, dass die Reinigung der Zinkoberflächen mit einer beizenden Surprisingly, it appears that the cleaning of the zinc surfaces with a pickling
Reinigungslösung eine weitere deutlich verbesserte Performance der erfindungsgemäß behandelten und mit dem Tauchlack beschichteten Zinkoberflächen (B2 vs. B1 ) im Steinschlagtest bewirkt. Eine solche Verbesserung auf Zinkoberflächen durch die beizende Wirkung des Reinigers tritt lediglich im erfindungsgemäßen Verfahren auf und unterbleibt sowohl bei der ausschließlichen Zirkon-basierten Konversionsbehandlung (V4 vs. V3) und der ausschließlichen Trikation- Zinkphosphatierung (V2 vs. V1 ). Tab.1 Cleaning solution a further significantly improved performance of the present invention treated and coated with the dip coating zinc surfaces (B2 vs. B1) causes in the stone impact test. Such an improvement on zinc surfaces by the cleaning effect of the cleaner occurs only in the process according to the invention and is omitted both in the exclusive zirconium-based conversion treatment (V4 vs. V3) and the exclusive trication zinc phosphating (V2 vs. V1). Table 1
Unterwanderungswerte und Steinschlagtest Immigrant values and rockfall test
Die Intoleranz des erfindungsgemäßen Verfahrens gegenüber einer zu hohen Menge an Zink- und/oder Phosphat-Ionen ist in den Tabellen 2 und 3 veranschaulicht. The intolerance of the process according to the invention compared to an excessive amount of zinc and / or phosphate ions is illustrated in Tables 2 and 3.
Es zeigt sich, dass die Inhibierung der Abscheidung von Nickel im Verfahrensschritt ii) durch Zink- Ionen weitgehend unabhängig vom Substrat verläuft, wobei das erfindungsgemäße Verfahren noch hinreichend gute Korrosionsschutzwerte liefert, wenn die Schichtauflage bezogen auf das Element Nickel zumindest 30 mg/m2 beträgt. It turns out that the inhibition of the deposition of nickel in process step ii) by zinc ions is largely independent of the substrate, wherein the inventive method still provides sufficiently good corrosion protection values when the layer support based on the element nickel is at least 30 mg / m 2 ,
Tab. 2 Tab. 2
Nickel-Schichtauflage in mg/m2 in Abhängigkeit der Konzentration an Zink-Ionen in einem erfindungsgemäßen Verfahren analog zum Beispiel B1 bei variierendem pH-Wert Nickel layer coating in mg / m 2 as a function of the concentration of zinc ions in a method according to the invention analogously to Example B1 at a varying pH
Die Nickelschichtauflage wurde mittels Röntgenfluoreszenzanalyse nach dem Einzelschritt iii) bestimmt The nickel layer coating was determined by means of X-ray fluorescence analysis after the individual step iii)
Tendenziell wird bei höheren pH-Werten sowohl auf Zink- als auch auf Stahlblechen eine größere Menge an Nickel im erfindungsgemäßen Verfahren analog zum Beispiel B1 abgeschieden, so dass die Toleranz gegenüber Zink-Ionen auf diese Weise erhöht werden kann. Die Inhibierung der Nickel-Abscheidung im Verfahrensschritt ii) durch Phosphat-Ionen ist hingegen auf Zink-Oberflächen wesentlich stärker ausgeprägt als auf Stahl (Tab. 3). Während bei einem pH der Zusammensetzung (A) von 3,7 im Verfahrensschritt ii) auf den Stahlblechen bei einem Phosphat-Gehalt von 0,25 g/l noch 65 mg/m2 Ni abgeschieden werden, was eine hinreichende Menge für einen guten Korrosionsschutz ist, wird auf Zinkblechen unter identischen Bedingungen überhaupt kein Nickel abgeschieden. Eine Erhöhung der Badtemperatur im Verfahrenschritt ii) auf 40 °C bewirkt wiederum eine verstärkte Abscheidung von Nickel, so dass auf Zinkblechen eine Schichtauflage von 92 mg/m2 Nickel gemessen wird. At higher pH values, a larger amount of nickel tends to be deposited on the zinc and steel sheets in the process according to the invention analogously to Example B1, so that the tolerance to zinc ions can be increased in this way. In contrast, the inhibition of nickel deposition in process step ii) by phosphate ions is significantly more pronounced on zinc surfaces than on steel (Table 3). While at a pH of the composition (A) of 3.7 in process step ii) on the steel sheets at a phosphate content of 0.25 g / l still 65 mg / m 2 Ni are deposited, which is a sufficient amount for good corrosion protection is, is deposited on zinc sheets under identical conditions no nickel at all. An increase in the bath temperature in process step ii) to 40 ° C in turn causes an increased deposition of nickel, so that on zinc sheets, a coating layer of 92 mg / m 2 nickel is measured.
Abbildung 1 zeigt ein XPS-Sputterprofil (XPS = Röntgenphotoelektronenspektroskopie) einer Beschichtung auf Stahlblech (CRS), das gemäß dem Beispiel B1 behandeltet wurde. Aus diesem Tiefenprofil geht zum einen hervor, dass die Behandlung von Stahl im erfindungsgemäßen Verfahren Beschichtungen erzeugt, die neben Nickel auch Schwefel enthalten, und zum anderen, dass die Konversionsbehandlung im Schritt iii) eine oberflächliche Zirkonoxidschicht auf der Nickel enthaltenden Beschichtung hervorbringt. Figure 1 shows an XPS sputter profile (XPS = X-ray photoelectron spectroscopy) of a coating on steel sheet (CRS), which was treated according to Example B1. From this depth profile it can be seen that the treatment of steel in the process according to the invention produces coatings containing not only nickel but also sulfur, and that the conversion treatment in step iii) produces a surface zirconium oxide layer on the nickel-containing coating.
Claims
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| PL10776723T PL2507408T3 (en) | 2009-12-04 | 2010-11-15 | Multi-stage pre-treatment method for metal components having zinc and iron surfaces |
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| DE102009047522A DE102009047522A1 (en) | 2009-12-04 | 2009-12-04 | Multi-stage pre-treatment process for metallic components with zinc and iron surfaces |
| PCT/EP2010/067448 WO2011067094A1 (en) | 2009-12-04 | 2010-11-15 | Multi-stage pre-treatment method for metal components having zinc and iron surfaces |
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| EP2507408B1 EP2507408B1 (en) | 2017-07-19 |
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| US (1) | US8715403B2 (en) |
| EP (1) | EP2507408B1 (en) |
| JP (1) | JP5837885B2 (en) |
| CN (1) | CN102639750B (en) |
| BR (1) | BR112012013126B1 (en) |
| DE (1) | DE102009047522A1 (en) |
| ES (1) | ES2642079T3 (en) |
| HU (1) | HUE035823T2 (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021116320A1 (en) * | 2019-12-11 | 2021-06-17 | Salzgitter Flachstahl Gmbh | Metal sheet having adhesion-promoter coating as semi-finished product for the manufacture of metal-thermoplastic composite components, and method for producing a metal sheet of this type |
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| DE102010001686A1 (en) * | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Composition for the alkaline passivation of zinc surfaces |
| EP2503025B1 (en) | 2011-03-22 | 2013-07-03 | Henkel AG & Co. KGaA | Multi-step corrosion-resistant treatment of metallic workpieces having at least partially zinc or zinc alloy surfaces |
| IN2015DN01536A (en) | 2012-08-29 | 2015-07-03 | Ppg Ind Ohio Inc | |
| UA112024C2 (en) | 2012-08-29 | 2016-07-11 | Ппг Індастріз Огайо, Інк. | ZIRCONIUM PRE-PROCESSING COMPOSITIONS CONTAINING MOLYBDEN, APPROPRIATE METHODS OF METAL SUBSTRATE PROCESSING AND APPROPRIATE METALS |
| FR3002545B1 (en) * | 2013-02-22 | 2016-01-08 | Alchimer | PROCESS FOR FORMING A METAL SILICIDE USING A SOLUTION CONTAINING GOLD IONS AND FLUOR IONS |
| ES2824250T3 (en) * | 2013-02-28 | 2021-05-11 | Nippon Steel Coated Sheet Corp | Zinc-plated steel sheet containing aluminum and process for its production |
| US20150021086A1 (en) * | 2013-07-19 | 2015-01-22 | San Diego Gas & Electric Company | Methods for dulling metallic surfaces and related products |
| DE102014206407A1 (en) * | 2014-04-03 | 2015-10-08 | Henkel Ag & Co. Kgaa | Two-stage pre-treatment of aluminum including pickle and passivation |
| PL3031951T3 (en) * | 2014-12-12 | 2018-03-30 | Henkel Ag & Co. Kgaa | Optimized process control in the pretreatment of metals to protect against corrosion on the basis of baths containing fluoride |
| CN105331966B (en) * | 2015-11-30 | 2018-04-27 | 宝山钢铁股份有限公司 | A kind of Chrome-free surface treatment tin plate, its production method and surface conditioning agent |
| RU2729485C1 (en) | 2016-08-24 | 2020-08-07 | Ппг Индастриз Огайо, Инк. | Iron-containing cleaner composition |
| WO2018095684A1 (en) * | 2016-11-23 | 2018-05-31 | Chemetall Gmbh | Composition and method for the chromium-free pretreatment of aluminium surfaces |
| CN106756966B (en) * | 2016-12-09 | 2019-02-05 | 济南大学 | Purple Tin Cobalt Copper Passivation Coloring for Zinc Coatings |
| EP3502311A1 (en) * | 2017-12-20 | 2019-06-26 | Henkel AG & Co. KGaA | Method for the corrosion protection and cleaning pretreatment of metallic components |
| CN108531898A (en) * | 2018-04-11 | 2018-09-14 | 浙江康盛股份有限公司 | A kind of chromium-free passivation liquid |
| CN108707884A (en) * | 2018-04-11 | 2018-10-26 | 浙江康盛股份有限公司 | A kind of chromium-free passivation liquid and its configuration method |
| ES2984399T3 (en) * | 2018-12-05 | 2024-10-29 | Henkel Ag & Co Kgaa | Passivation composition based on mixtures of phosphoric and phosphonic acids |
| US11566330B2 (en) * | 2019-04-16 | 2023-01-31 | Ppg Industries Ohio, Inc. | Systems and methods for maintaining pretreatment baths |
| EP3872231A1 (en) * | 2020-02-28 | 2021-09-01 | voestalpine Stahl GmbH | Method for conditioning the surface of a metal strip coated with a zinc alloy corrosion protection layer |
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- 2010-11-15 WO PCT/EP2010/067448 patent/WO2011067094A1/en active Application Filing
- 2010-11-15 CN CN201080054392.XA patent/CN102639750B/en active Active
- 2010-11-15 PL PL10776723T patent/PL2507408T3/en unknown
- 2010-11-15 ES ES10776723.8T patent/ES2642079T3/en active Active
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| WO2021116320A1 (en) * | 2019-12-11 | 2021-06-17 | Salzgitter Flachstahl Gmbh | Metal sheet having adhesion-promoter coating as semi-finished product for the manufacture of metal-thermoplastic composite components, and method for producing a metal sheet of this type |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112012013126B1 (en) | 2019-08-27 |
| WO2011067094A1 (en) | 2011-06-09 |
| JP5837885B2 (en) | 2015-12-24 |
| HUE035823T2 (en) | 2018-08-28 |
| JP2013513022A (en) | 2013-04-18 |
| ES2642079T3 (en) | 2017-11-15 |
| CN102639750A (en) | 2012-08-15 |
| PL2507408T3 (en) | 2017-12-29 |
| EP2507408B1 (en) | 2017-07-19 |
| DE102009047522A1 (en) | 2011-06-09 |
| US8715403B2 (en) | 2014-05-06 |
| BR112012013126A2 (en) | 2017-03-21 |
| CN102639750B (en) | 2015-03-11 |
| US20120325110A1 (en) | 2012-12-27 |
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