EP2826569B1 - Method for passivating strip black iron plate - Google Patents
Method for passivating strip black iron plate Download PDFInfo
- Publication number
- EP2826569B1 EP2826569B1 EP14175621.3A EP14175621A EP2826569B1 EP 2826569 B1 EP2826569 B1 EP 2826569B1 EP 14175621 A EP14175621 A EP 14175621A EP 2826569 B1 EP2826569 B1 EP 2826569B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel strip
- treatment solution
- strip
- steel
- solution
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 10
- 229910052742 iron Inorganic materials 0.000 title description 5
- 239000000243 solution Substances 0.000 claims description 64
- 229910000831 Steel Inorganic materials 0.000 claims description 51
- 239000010959 steel Substances 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 235000021317 phosphate Nutrition 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002318 adhesion promoter Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 claims 1
- 239000005029 tin-free steel Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 14
- 238000004806 packaging method and process Methods 0.000 description 10
- 235000010210 aluminium Nutrition 0.000 description 9
- 238000007739 conversion coating Methods 0.000 description 9
- 239000005028 tinplate Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 oxo cations Chemical class 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006223 plastic coating Substances 0.000 description 2
- 229920001123 polycyclohexylenedimethylene terephthalate Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241000416335 Acrophylla titan Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 229910001563 bainite Inorganic materials 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/76—Applying the liquid by spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
- C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the invention relates to a method for passivating strip-shaped black sheet, wherein in an initial step by an electrochemical treatment of the black plate an inert layer is formed on the black plate surface and in a further step, an aqueous chromium-free treatment solution on at least one surface of the black plate to form a protective against corrosion Conversion layer is applied, which also forms an adhesive layer for paints and organic coating materials.
- Passivation is understood here to mean the targeted generation of a protective layer (here: conversion layer) on the black sheet, which prevents or at least greatly slows the corrosion of the black sheet.
- the invention further relates to the use of black plates treated according to the invention as packaging steel.
- the metallic surface is provided with a coating of another, usually less noble, metal (such as zinc and chromium). So it is e.g. known steel sheets with zinc or chromium or with tin (which, however, is nobler compared to steel) to coat.
- metal such as zinc and chromium
- tin which, however, is nobler compared to steel
- Tinplate very extensively tinned Feinstbleche
- Tinplates are characterized by a very good corrosion resistance and a good forming behavior and their weldability and are therefore very well suited for the production of packaging, such. Beverage cans.
- Conversion layers are non-metallic, usually inorganic, very thin layers on a metal surface, which are generally produced by chemical reaction of an aqueous treatment solution with the metallic substrate. Conversion coatings ensure a very effective corrosion protection, in particular with fine metal sheets, a good primer for coatings and plastics and they reduce surface friction and abrasion.
- the JP 59089776-A shows a method for Pretreatment of a steel strip in a continuous strip annealing prior to conversion coating with a phosphate-containing treatment solution, the steel strip first annealed in a continuous strip furnace, then cooled with water or steam, optionally pickled and rinsed and then electrochemically treated in an electrolyte with switching the steel strip as the anode to produce a surface suitable for application of the phosphate-containing treatment solution.
- the EP 1 060 032 A2 shows a continuous process for the pretreatment of black plate as packaging steel wherein a cold-rolled, annealed black plate in alkaline NaOH solution is electrolytically cleaned and then applied to the black plate, an aqueous conversion treatment solution with phosphate by spraying or roller coater.
- Chromium-containing conversion layers have proven to be very effective corrosion protection.
- chromating the metallic surface is treated with an acidic solution containing chromium (VI) ions, whereby chromium (VI) is reduced to chromium (III).
- the treatment forms a chromium-containing conversion layer which protects against corrosion on the metal surface.
- chromium (VI) compounds are acutely toxic and carcinogenic.
- the passivation of metal surfaces containing chromium (VI) -containing substances has already been banned in the EU.
- chromium-free conversion layers have been developed in the prior art.
- Processes for producing chromium-free conversion layers on metallic surfaces, in particular of metallic alloys such as steel and of zinc or aluminum surfaces are known, for example from US Pat WO 97/40208 -A and the EP 2532769 A1 .
- the DE 10161383 A1 discloses a method of coating metallic surfaces with aqueous chromium VI-free processing solutions and an organic film former of a polymeric material, cations or fluoro complexes of cations selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron contain an organic compound in particulate form, wherein the aqueous treatment solution is applied, for example.
- Tinplate has excellent properties as a food packaging material and has been manufactured and processed for many decades for this purpose. Tin, which However, with tinplate being the anti-corrosive coating, it has become a relatively valuable material due to the global scarcity of resources.
- electrolytically plated chromium plated steel sheets are known as Tin Free Steel (TFS) or Electrolytic Chromium Coated Steel (ECCS) .
- TFS Tin Free Steel
- ECCS Electrolytic Chromium Coated Steel
- these tin-free steel sheets are distinguished by a good adhesion to paints or organic protective coatings (for example of PP or PET), but on the other hand have considerable advantages in carrying out the coating process because of the toxic and health-endangering properties of the chromium-VI-containing materials used for coating Disadvantages.
- the object of the present invention is therefore to provide a chromium-free packaging steel, which is suitable as a substitute for tin-free steel sheet (TFS or ECCS) and as a replacement for tinplate and in particular both in terms of corrosion resistance and with respect to the adhesion for paints or organic coatings should be with tinplate or tin-free steel.
- This object is achieved by a method for passivation of black belted sheet metal having the features of claim 1.
- an uncoated black plate in strip form of a cold-rolled, annealed and re-rolled steel strip having a weight-based carbon content of 20 to 1000 ppm used and Moving at a belt speed of at least 200 m / min through a belt coater where the steel strip is cleaned and degreased in a pretreatment step by passing the steel strip at a belt speed through a cleaning tank with an alkaline solution of sodium or potassium hydroxide followed by rinsing.
- Electrolyte is a sodium hydroxide or soda solution, which is maintained at temperatures between 20 and 80 ° C.
- the steel strip is rinsed with water or another rinsing liquid, dried and finally coated in a further step with a corrosion-stable conversion coating by an aqueous chromium-free on at least one surface of the black plate in a no-rinse process
- Treatment solution which contains as essential chemical components titanium and zirconium or titanium, zirconium and manganese or titanium, zinc and phosphates or titanium, zinc, manganese and phosphates.
- the steel may, for example, be a ferritic steel or else a multiphase steel which has a plurality of structural constituents, in particular ferrite, martensite, bainite and / or retained austenite.
- Such multiphase steels are characterized by a high strength of more than 500 MPa with simultaneously good elongation at break of more than 10%.
- the grades of the steel sheet defined in DIN EN 10202: 2001: "Cold-rolled packaging sheet products (electrolytically tinned and chromium-plated)" are preferably observed. In this standard are u.a. Analysis and mechanical characteristics of the steel defined. The grades are in particular between TS230 (soft hood furnace grade, yield strength 230 MPa) to TH620 (DO, 620MPa).
- the black plate in strip form is moved at a belt speed of more than 200 m / min.
- a step of forming an inert layer on the surface of the black sheet by an electrochemical treatment is first cleaned in a pretreatment step and in particular degreased, then rinsed, pickled and rinsed again. This is necessary because the cold-rolled and recrystallization-annealed black sheet is usually after the Recrystallization annealing is retreaded or trained, wherein, for example.
- wet-rolling with a water-oil suspension or even duringkowskinachwalzen the black plate surfaces are contaminated by oil, iron abrasion, soaps and other contaminants. This contamination is eliminated by the pretreatment step.
- the black plate is passed into a cleaning tank with an alkaline sodium or potassium hydroxide solution.
- concentration of the alkaline degreasing agent is preferably between 20 and 100 g / l at bath temperatures of 20-70 ° C.
- a degreasing of the black plate is expediently carried out in two steps, wherein in a first step a dipping method and in the second step an electrolytic method with current densities of 2 to 30 A / dm 2 is performed. After degreasing, each band side of the black plate is rinsed, for example, by a triple cascade rinsing with 10-30 m 3 / h of water.
- Removal of oxide residues may, if necessary, be accomplished by passing the blackplate tape into further cleansing tanks having a salt or sulfuric acid pickle at a concentration of, for example, 10 to 120 g / l in two consecutive dives, followed by a dive with a dive.
- the temperatures of the pickling solution and the rinsing water are typically between 20 and 60 ° C.
- a homogeneous, dense, inert steel surface is produced by electrochemical treatment by passing the black metal strip through an electrolyte.
- the electrolyte is alkaline.
- the electrochemical, alkaline treatment of the black plate is used for inerting and for equalizing the surface properties of the steel strip before applying the conversion coating.
- the black plate belt is passed through the belt speed through an electrolytic bath while being connected as an anode at a current density of 2-30 A / dm 2 .
- the electrolyte is either a sodium hydroxide solution or a soda solution.
- the sodium hydroxide solution preferably has a NaOH concentration of 20-100 g / l.
- a sodium hydroxide bath with a 3% NaOH solution may also be used.
- soda solution in particular a 5% sodium carbonate solution (Na 2 CO 3 ) can be used.
- the bath temperatures of the electrolysis bath are maintained between 20 and 80 ° C.
- the black plate is rinsed with water.
- the rinsing can be done by immersing the tape in a water tank or by spraying with water. Preference is given to using demineralized (DI), deionized water, osmosis water or distilled water at temperatures of 20-60 ° C. However, untreated drinking water or other rinsing liquids can also be used. After rinsing, the black plate is dried.
- a conversion layer is applied to at least one surface of the black plate by applying an aqueous chromium-free treatment solution to the surface of the black plate previously rendered inert in the electrochemical treatment.
- the conversion coating is applied in a no-rinse process, that is, a rinsing after generating the conversion layer is omitted.
- the aqueous chromium-free treatment solution which forms the conversion coating is applied, for example, to the surface of the black plate with a coating device which comprises a roller coater, a rotary sprayer or spray nozzles.
- the surface of the black plate to which the conversion layer is to be applied should be as clean and dry as possible. Therefore, at least the surface of the black plate to be coated with the conversion layer is treated with a drying device, e.g. with an air knife, dried.
- a drying device e.g. with an air knife
- the rotary sprayer has a plurality of spray rotors juxtaposed transversely to the belt running direction to which the aqueous treatment solution is supplied and which are rotated by a drive to spray the aqueous treatment solution on the or each surface of the belt in the form of a fine spray jet due to centrifugal force Form wet film of the aqueous solution.
- After application of the wet film of the aqueous treatment solution this is made uniform by means of powered smoothing rollers on the surface of the black plate.
- the smoothing rollers are included expediently with respect to the black plate surface (s) arranged so that they exert only little pressure on the wet film of the aqueous treatment solution and squeeze no or at most a minimum proportion of the applied treatment solution from the surface.
- the amount of treatment solution sprayed with the rotary sprayer is adjusted accordingly so that there is no excess on the blackplate surface. This eliminates the otherwise necessary disposal or treatment of the excess portion of the treatment solution.
- the dry coating of the treatment solution after drying is expediently between 1 and 50 mg / m 2 and is preferably in the range from 10 to 30 mg / m 2 .
- the amount of the aqueous treatment solution fed to the spray rotors of the rotary sprayer per unit time is expediently adapted to the belt speed.
- a constant circulation of the wet film in the range of 2 ml / m 2 to 8 ml / m 2 and preferably of about 5 ml / m 2 per band side can be set independently of the belt speed.
- the belt After applying the wet film of the processing solution, the belt is passed through a belt dryer to dry the wet film. After drying, a dry coating of the conversion layer formed in this way from 2 mg / m 2 to 30 mg / m 2 remains on the surface of the black plate per side.
- the desired dry coverage of the conversion layer can be adjusted by the amount of treatment solution fed to the rotary sprayer per unit of time.
- An advantage of this type of application is that only fresh treatment solution is used and that it can not be contaminated by iron separation by contact and recycling with the steel strip.
- the process is very economical, since only the exact amount needed is applied and no excess is needed, so that excess treatment solution does not have to be collected. This can prevent that post-treated wastewater arise.
- the application of the treatment solution can also Rolling coater by a roller application - also on a previously dried black plate surface - done. Roll coaters are preferably used in the lower speed range of the belt speed and in particular at speeds of less than 200 m / min.
- the application can also be carried out by spraying the treatment solution or by immersing the tape in a bath with the treatment solution. In this case, since the treatment solution is applied in excess to the black plate, it is necessary to achieve a predetermined desired edition of the conversion layer, squeeze off the excess portion of the wet film, for example by means of squeezing rollers, which can be done "wet on wet". In this method, however, the solution is not applied the same constant regardless of the speed and the treatment solution can also be contaminated by iron and must then be renewed and disposed of after exceeding a contamination threshold.
- the wet film of the treatment solution applied with the described application methods is finally dried to form a dry conversion layer.
- This can be done, for example, by passing the black plate through a drying oven in which wet film is dried by means of hot air or IR radiation. The drying is preferably carried out at temperatures of 50-250 ° C.
- the surface of the dry conversion layer with Dioctylsebacat (DOS), acetyltributylcitrate (ATBC), butyl stearate (BSO) or polyalkylene glycol, in particular polyethylene glycol (PEG, preferably having a molecular weight of 6000 g / mol), or combinations thereof oiled or post-treated.
- DOS Dioctylsebacat
- ATBC acetyltributylcitrate
- BSO butyl stearate
- polyalkylene glycol in particular polyethylene glycol (PEG, preferably having a molecular weight of 6000 g / mol
- the treatment solution may further comprise at least one adhesion promoter for lacquers or organic coating materials, the adhesion promoter in particular containing constituents of maleic acid, isophthalic acid and cyclohexanedimethanol (CHDM) or combinations thereof.
- adhesion promoters have been found to be compositions containing polyethylene terephthalate (PET) or polycyclohexylenedimethylene terephthalate (PCT), e.g. glycol-modified polyethylene terephthalate (PET-G containing less than about 30% CHDM) or PCTG (containing more than about 30% CHDM).
- the requirements are for example 1 to 50 mg / m 2 for the respective substances.
- BASF® EFKA ® 4560 modified polyacrylates BASF® - Ti, Zn, Mn phosphate Henkel ® Granodine ® 1456 Ti, Zr Henkel ® GTP 10861 Gardo ® TP Zn phosphates Ti Chemetall ® GB X4744A Gardobond ® (Chemetall ®) Mn, Ti, Zr Chemetall ® GB X4591 A1 Ti, Zr Chemetall ® GB X4744 Ti, Zr Chemetall ®
- the process according to the invention can be carried out without major installation effort into an existing coating installation, e.g. be integrated into a coil coating plant for the production of ECCS (or TFS).
- the belt speed in such belt coating systems is typically 80-600 m / min.
- the inventive method has the advantages of a chromium-free and thus environmentally friendly and not harmful to health and cost-effective coating on conventional black plate, especially in the fine and Feinstblech thickness range.
- by the selected application method (no-rinse method) for applying the conversion layer by eliminating the final rinse effective cost and energy savings can be achieved.
- advantages are achieved by the combination of inorganic passivation and polymer-containing thin-film coating.
- the black sheets treated by the process of the invention are eminently suitable for the production of packaging, in particular cans, and can therefore replace the tinplates and tin-free steel sheets (TFS or ECCS) conventionally used as packaging steel. These black sheets are comparable in their corrosion resistance with tinplate and have similarly good adhesion properties for paints and plastic coatings, for example of PP or PET, on as tin-free steel sheets (TFS or ECCS).
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Passivierung von bandförmigem Schwarzblech, wobei in einem ersten Schritt durch eine elektrochemische Behandlung des Schwarzblechs eine Inertschicht auf der Schwarzblechoberfläche gebildet wird und in einem weiteren Schritt eine wässrige chromfreie Behandlungslösung auf wenigstens eine Oberfläche des Schwarzblechs zur Ausbildung einer vor Korrosion schützenden Konversionsschicht aufgetragen wird, welche außerdem eine Haftschicht für Lacke und organische Beschichtungsmaterialien bildet. Unter Passivierung wird hierbei die gezielte Erzeugung einer Schutzschicht (hier: Konversionsschicht) auf dem Schwarzblech verstanden, welche die Korrosion des Schwarzblechs verhindert oder zumindest stark verlangsamt. Die Erfindung betrifft ferner die Verwendung von erfindungsgemäß behandelten Schwarzblechen als Verpackungsstahl.The invention relates to a method for passivating strip-shaped black sheet, wherein in an initial step by an electrochemical treatment of the black plate an inert layer is formed on the black plate surface and in a further step, an aqueous chromium-free treatment solution on at least one surface of the black plate to form a protective against corrosion Conversion layer is applied, which also forms an adhesive layer for paints and organic coating materials. Passivation is understood here to mean the targeted generation of a protective layer (here: conversion layer) on the black sheet, which prevents or at least greatly slows the corrosion of the black sheet. The invention further relates to the use of black plates treated according to the invention as packaging steel.
Zum Schutz metallischer Oberflächen vor Korrosion sind Verfahren bekannt, in denen die metallische Oberfläche mit einer Beschichtung aus einem anderen, in der Regel unedleren Metall (wie z.B. Zink und Chrom) versehen wird. So ist es z.B. bekannt Stahlbleche mit Zink oder Chrom oder auch mit Zinn (welches allerdings im Vergleich zu Stahl edler ist) zu beschichten. Zur Herstellung von Verpackungen, insbesondere im Lebensmittelbereich, werden bspw. sehr umfangreich verzinnte Feinstbleche (Weißbleche) verwendet. Weißbleche zeichnen sich durch eine sehr gute Korrosionsbeständigkeit und ein gutes Umformverhalten sowie ihre Schweißbarkeit aus und eignen sich deshalb sehr gut zur Herstellung von Verpackungen, wie z.B. Getränkedosen.To protect metallic surfaces from corrosion, methods are known in which the metallic surface is provided with a coating of another, usually less noble, metal (such as zinc and chromium). So it is e.g. known steel sheets with zinc or chromium or with tin (which, however, is nobler compared to steel) to coat. For the production of packaging, in particular in the food industry, for example, very extensively tinned Feinstbleche (tinplate) are used. Tinplates are characterized by a very good corrosion resistance and a good forming behavior and their weldability and are therefore very well suited for the production of packaging, such. Beverage cans.
Um auch die metallische Beschichtung, bspw. die Zinnbeschichtung bei Weißblech, gegen Korrosion zu schützen und einen guten Haftgrund für Lackierungen und Kunststoffbeschichtungen zu erzeugen, werden auf der Oberfläche der metallischen Beschichtung häufig Konversionsschichten aufgebracht.In order also to protect the metallic coating, for example the tin coating in tinplate, against corrosion and to produce a good primer for coatings and plastic coatings, conversion coatings are frequently applied to the surface of the metallic coating.
Unter Konversionsschichten versteht man nichtmetallische, meist anorganische, sehr dünne Schichten auf einer Metalloberfläche, die in der Regel durch chemische Reaktion einer wässrigen Behandlungslösung mit dem metallischen Untergrund erzeugt werden. Konversionsbeschichtungen gewährleisten insbesondere bei Feinstblechen einen sehr wirksamen Korrosionsschutz, einen guten Haftgrund für Lackierungen und Kunststoffen und sie vermindern Oberflächenreibung und Abrieb. Die
In Abhängigkeit vom Substrat unterscheidet man beim Aufbringen von Konversionsschichten zwischen Eisen-, Zink- oder Mangan-Phosphatieren, elektrolytischem Phosphatieren oder Chromat-, Oxalat- und Anodisierungs-Verfahren. Als sehr wirksamer Korrosionsschutz haben sich chromhaltige Konversionsschichten erwiesen. Bei einer Chromatierung wird die metallische Oberfläche mit einer sauren, Chrom(VI)-Ionen enthaltenden Lösung behandelt, wobei Chrom(VI) zu Chrom(III) reduziert wird. Durch die Behandlung bildet sich auf der Metalloberfläche eine vor Korrosion schützende chromhaltige Konversionsschicht.
Chrom(VI)-Verbindungen sind allerdings akut toxisch und karzinogen. Für Anwendungen im Automobilbau und in Haushaltsgeräten wurde in der EU bereits die Passivierung von Metalloberflächen mit Chrom(VI)-haltigen Substanzen verboten. Aus diesem Grund wurden im Stand der Technik chromfreie Konversionsschichten entwickelt. Verfahren zur Erzeugung chromfreier Konversionsschichten auf metallischen Oberflächen, insbesondere von metallischen Legierungen wie Stahl sowie von Zink- bzw. Aluminium-Oberflächen sind bekannt, bspw. aus der
Weißblech besitzt hervorragende Eigenschaften als Verpackungsmaterial für Lebensmittel und wird seit vielen Jahrzehnten zu diesem Zweck hergestellt und verarbeitet. Zinn, welches beim Weißblech die korrosionshemmende Beschichtung darstellt, ist allerdings aufgrund der weltweiten Verknappung der Ressource zu einem relativ wertvollen Material geworden. Als Alternative zu Weißblech sind insbesondere zur Verwendung als Verpackungsstahl aus dem Stand der Technik elektrolytisch mit Chrom beschichtete Stahlbleche bekannt, welche als Zinn-freies Stahlblech ("Tin Free Steel", TFS) oder als "Electrolytic Chromium Coated Steel (ECCS)" bezeichnet werden. Diese zinnfreien Stahlbleche zeichnen sich einerseits durch eine gutes Haftvermögen für Lacke oder organische Schutzbeschichtungen (bspw. aus PP oder PET) aus, weisen andererseits bei der Durchführung des Beschichtungsverfahrens aufgrund der toxischen und gesundheitsgefährdenden Eigenschaften der zur Beschichtung verwendeten Chrom-VI-haltigen Materialien allerdings erhebliche Nachteile auf.
Die Aufgabe der vorliegenden Erfindung besteht daher in der Bereitstellung eines chromfreien Verpackungsstahls, welcher als Ersatz für zinnfreies Stahlblech (TFS bzw. ECCS) und als Ersatz für Weißblech geeignet ist und insbesondere sowohl hinsichtlich der Korrosionsbeständigkeit als auch bezüglich des Haftvermögens für Lacke oder organische Beschichtungen vergleichbar mit Weißblech oder zinnfreiem Stahlblech sein soll.
Gelöst wird diese Aufgabe durch ein Verfahren zur Passivierung von bandförmigem Schwarzblech mit den Merkmalen des Anspruchs 1. Gemäß diesem Verfahren wird ein unbeschichtetes Schwarzblech in Bandform aus einem kaltgewalzten, geglühten und nachgewalzten Stahlband mit einem auf das Gewicht bezogenen Kohlenstoffgehalt von 20 bis 1000 ppm verwendet und mit einer Bandgeschwindigkeit von wenigstens 200 m/min durch eine Bandbeschichtungsanlage bewegt, wo das Stahlband in einem Vorbehandlungsschritt geeinigt und entfettet wird, indem das Stahlband mit der Bandgeschwindigkeit durch einen Reinigungstank mit einer alkalischen Natrium- oder Kaliumhydroxid-Lösung geleitet und anschließend gespült wird. Danach wird die Oberfläche des Stahlbands in einem ersten Verfahrensschritt durch eine elektrochemische Behandlung inertisiert, indem das Stahlband mit der Bandgeschwindigkeit durch einen alkalischen Elektrolyten bei Stromdichten von 2 bis 30 A/dm2 unter Schaltung des Stahlbands als Anode durchgeleitet wird, wobei es sich bei dem Elektrolyten um eine Natriumhydroxid- oder Soda-Lösung handelt, welche auf Temperaturen zwischen 20 und 80°C gehalten wird. Anschließend wird das Stahlband mit Wasser oder einer anderen Spülflüssigkeit gespült, getrocknet und schließlich in einem weiteren Schritt mit einer korrosionsstabilen Konversionsbeschichtung beschichtet, indem auf wenigstens eine Oberfläche des Schwarzblechs in einem no-rinse-Verfahren eine wässrige chromfreie Behandlungslösung aufgebracht wird, welche als Wesentliche chemische Bestandteile Titan und Zirkonium oder Titan, Zirkonium und Mangan oder Titan, Zink und Phosphate oder Titan, Zink, Mangan und Phosphate enthält.Depending on the substrate, a distinction is made when applying conversion layers between iron, zinc or manganese phosphating, electrolytic phosphating or chromate, oxalate and anodization processes. Chromium-containing conversion layers have proven to be very effective corrosion protection. In chromating, the metallic surface is treated with an acidic solution containing chromium (VI) ions, whereby chromium (VI) is reduced to chromium (III). The treatment forms a chromium-containing conversion layer which protects against corrosion on the metal surface.
However, chromium (VI) compounds are acutely toxic and carcinogenic. For automotive and home appliance applications, the passivation of metal surfaces containing chromium (VI) -containing substances has already been banned in the EU. For this reason, chromium-free conversion layers have been developed in the prior art. Processes for producing chromium-free conversion layers on metallic surfaces, in particular of metallic alloys such as steel and of zinc or aluminum surfaces are known, for example from US Pat
Tinplate has excellent properties as a food packaging material and has been manufactured and processed for many decades for this purpose. Tin, which However, with tinplate being the anti-corrosive coating, it has become a relatively valuable material due to the global scarcity of resources. As an alternative to tinplate, especially for use as packaging steel of the prior art, electrolytically plated chromium plated steel sheets are known as Tin Free Steel (TFS) or Electrolytic Chromium Coated Steel (ECCS) , On the one hand, these tin-free steel sheets are distinguished by a good adhesion to paints or organic protective coatings (for example of PP or PET), but on the other hand have considerable advantages in carrying out the coating process because of the toxic and health-endangering properties of the chromium-VI-containing materials used for coating Disadvantages.
The object of the present invention is therefore to provide a chromium-free packaging steel, which is suitable as a substitute for tin-free steel sheet (TFS or ECCS) and as a replacement for tinplate and in particular both in terms of corrosion resistance and with respect to the adhesion for paints or organic coatings should be with tinplate or tin-free steel.
This object is achieved by a method for passivation of black belted sheet metal having the features of claim 1. According to this method, an uncoated black plate in strip form of a cold-rolled, annealed and re-rolled steel strip having a weight-based carbon content of 20 to 1000 ppm used and Moving at a belt speed of at least 200 m / min through a belt coater where the steel strip is cleaned and degreased in a pretreatment step by passing the steel strip at a belt speed through a cleaning tank with an alkaline solution of sodium or potassium hydroxide followed by rinsing. Thereafter, the surface of the steel strip is rendered inert in a first process step by electrochemical treatment by passing the steel strip at the strip speed through an alkaline electrolyte at current densities of 2 to 30 A / dm 2 with switching of the steel strip as the anode Electrolyte is a sodium hydroxide or soda solution, which is maintained at temperatures between 20 and 80 ° C. Subsequently, the steel strip is rinsed with water or another rinsing liquid, dried and finally coated in a further step with a corrosion-stable conversion coating by an aqueous chromium-free on at least one surface of the black plate in a no-rinse process Treatment solution is applied, which contains as essential chemical components titanium and zirconium or titanium, zirconium and manganese or titanium, zinc and phosphates or titanium, zinc, manganese and phosphates.
Weitere besondere Ausführungsformen des Verfahrens sind in den abhängigen Ansprüchen definiert.Further particular embodiments of the method are defined in the dependent claims.
Zum Einsatz kommt kaltgewalztes, geglühtes und nachgewalztes bzw. dressiertes Stahlband aus einem Stahl mit einem Kohlenstoffgehalt von 20 - 1 000 ppm. Zweckmäßig hat das Stahlband (Schwarzblech) folgende Eigenschaften:
- Festigkeit: 300-1000 MPa
- Bruchdehnung: 1-40 %
- Dicke: 0,05-0,49 mm
- Oberflächen-Rauheit: 0,1 - 1 µm.
- Strength: 300-1000 MPa
- Elongation at break: 1-40%
- Thickness: 0.05-0.49 mm
- Surface roughness: 0.1 - 1 μm.
Bei dem Stahl kann es sich bspw. um einen ferritischen Stahl oder auch um einen mehrphasigen Stahl handeln, der mehrere Gefügebestandteile aufweist, insbesondere Ferrit, Martensit, Bainit und/oder Restaustenit. Solche mehrphasigen Stähle zeichnen sich durch eine hohe Festigkeit von mehr als 500 MPa bei gleichzeitig guter Bruchdehnung von mehr als 10% aus. Im Hinblick auf die vorgesehene Verwendung des erfindungsgemäß behandelten Schwarzblechs als Verpackungsstahl werden bevorzugt die in der DIN EN 10202:2001: "Kaltgewalzte Verpackungsblecherzeugnisse (elektrolytisch verzinnt und verchromt)" definierten Güten des Stahlblechs eingehalten. In dieser Norm sind u.a. Analyse und mechanische Kennwerte des Stahls definiert. Die Güten liegen insbesondere zwischen TS230 (weiche Haubenofengüte, Streckgrenze 230 MPa) bis TH620 (DO, 620MPa).The steel may, for example, be a ferritic steel or else a multiphase steel which has a plurality of structural constituents, in particular ferrite, martensite, bainite and / or retained austenite. Such multiphase steels are characterized by a high strength of more than 500 MPa with simultaneously good elongation at break of more than 10%. With regard to the intended use of the black plate treated according to the invention as packaging steel, the grades of the steel sheet defined in DIN EN 10202: 2001: "Cold-rolled packaging sheet products (electrolytically tinned and chromium-plated)" are preferably observed. In this standard are u.a. Analysis and mechanical characteristics of the steel defined. The grades are in particular between TS230 (soft hood furnace grade, yield strength 230 MPa) to TH620 (DO, 620MPa).
Zur Durchführung des Verfahrens gemäß der Erfindung wird das in Bandform vorliegende Schwarzblech mit einer Bandgeschwindigkeit von mehr als 200 m/min bewegt. Zunächst erfolgt ein Schritt zur Bildung einer Inertschicht auf der Oberfläche des Schwarzblechs durch eine elektrochemische Behandlung. Zur Vorbereitung der elektrochemischen Behandlung wird das bewegte Schwarzblechband zunächst in einem Vorbehandlungsschritt gereinigt und insbesondere entfettet, danach gespült, gebeizt und wiederum gespült. Dies ist erforderlich, weil das kaltgewalzte und rekristallisationsgeglühte Schwarzblech in der Regel nach dem Rekristallisationsglühen nachgewalzt bzw. dressiert wird, wobei bspw. beim Nassnachwalzen mit einer Wasser-Öl-Suspension oder auch beim Trockennachwalzen die Schwarzblechoberflächen durch Öl, Eisenabrieb, Seifen und andere Verschmutzungen kontaminiert werden. Diese Kontamination wird durch den Vorbehandlungsschritt beseitigt.To carry out the method according to the invention, the black plate in strip form is moved at a belt speed of more than 200 m / min. First, a step of forming an inert layer on the surface of the black sheet by an electrochemical treatment. To prepare the electrochemical treatment, the moving black plate strip is first cleaned in a pretreatment step and in particular degreased, then rinsed, pickled and rinsed again. This is necessary because the cold-rolled and recrystallization-annealed black sheet is usually after the Recrystallization annealing is retreaded or trained, wherein, for example. When wet-rolling with a water-oil suspension or even during Trockennachwalzen the black plate surfaces are contaminated by oil, iron abrasion, soaps and other contaminants. This contamination is eliminated by the pretreatment step.
Hierfür wird das Schwarzblech in einen Reinigungstank mit einer alkalischen Natrium- oder Kaliumhydroxid-Lösung geleitet. Die Konzentration des alkalischen Entfettungsmittels liegt bevorzugt zwischen 20 und 100 g/l bei Badtemperaturen von 20 - 70 °C. Eine Entfettung des Schwarzblechs erfolgt zweckmäßig in zwei Schritten, wobei in einem ersten Schritt ein Tauchverfahren und im zweiten Schritt ein elektrolytisches Verfahren mit Stromdichten von 2 bis 30 A/dm2 durchgeführt wird. Nach dem Entfetten wird jede Bandseite des Schwarzblechs bspw. durch eine Dreifachkaskadenspüle mit jeweils 10-30 m3/h Wasser gespült. Ein Entfernen von Oxidresten kann erforderlichenfalls durch Einleiten des Schwarzblechbands in weitere Reinigungstanks mit einer Salz- oder Schwefelsäurebeize mit einer Konzentration von bspw. 10 bis 120 g/l in zwei aufeinanderfolgenden Tauchgängen erfolgen, gefolgt von einer Tauchspüle mit einem Tauchgang. Die Temperaturen der Beizlösung und des Spülwassers liegen typisch zwischen 20 und 60°C.For this purpose, the black plate is passed into a cleaning tank with an alkaline sodium or potassium hydroxide solution. The concentration of the alkaline degreasing agent is preferably between 20 and 100 g / l at bath temperatures of 20-70 ° C. A degreasing of the black plate is expediently carried out in two steps, wherein in a first step a dipping method and in the second step an electrolytic method with current densities of 2 to 30 A / dm 2 is performed. After degreasing, each band side of the black plate is rinsed, for example, by a triple cascade rinsing with 10-30 m 3 / h of water. Removal of oxide residues may, if necessary, be accomplished by passing the blackplate tape into further cleansing tanks having a salt or sulfuric acid pickle at a concentration of, for example, 10 to 120 g / l in two consecutive dives, followed by a dive with a dive. The temperatures of the pickling solution and the rinsing water are typically between 20 and 60 ° C.
Nach der Vorbehandlung wird eine homogene, dichte, inerte Stahloberfläche mittels elektrochemischer Behandlung durch Durchleiten des Schwarzblechbands durch einen Elektrolyten erzeugt. Der Elektrolyt ist alkalisch. Die elektrochemische, alkalische Behandlung des Schwarzblechs dient zur Inertisierung sowie zur Vergleichmäßigung der Oberflächeneigenschaften des Stahlbandes vor dem Auftragen der Konversionbeschichtung.After pretreatment, a homogeneous, dense, inert steel surface is produced by electrochemical treatment by passing the black metal strip through an electrolyte. The electrolyte is alkaline. The electrochemical, alkaline treatment of the black plate is used for inerting and for equalizing the surface properties of the steel strip before applying the conversion coating.
In dem Verfahrensschritt der elektrochemischen Behandlung wird das Schwarzblechband mit der Bandgeschwindigkeit durch ein Elektrolytbad durchgeführt und dabei als Anode geschaltet bei einer Stromdichte von 2-30 A/dm2. Bei dem Elektrolyten handelt es sich entweder um eine Natriumhydroxid-Lösung oder um eine Soda-Lösung. Die Natriumhydroxid-Lösung weist dabei bevorzugt eine NaOH-Konzentration von 20-100 g/l auf. Es kann auch ein Natriumhydroxid-Bad mit einer 3%-igen NaOH-Lösung verwendet werden. Als Soda-Lösung kann insbesondere eine 5%-ige Natriumcarbonat-Lösung (Na2CO3) verwendet werden. Die Badtemperaturen des Elektrolysebads werden zwischen 20 und 80°C gehalten.In the electrochemical treatment step, the black plate belt is passed through the belt speed through an electrolytic bath while being connected as an anode at a current density of 2-30 A / dm 2 . The electrolyte is either a sodium hydroxide solution or a soda solution. The sodium hydroxide solution preferably has a NaOH concentration of 20-100 g / l. A sodium hydroxide bath with a 3% NaOH solution may also be used. As soda solution, in particular a 5% sodium carbonate solution (Na 2 CO 3 ) can be used. The bath temperatures of the electrolysis bath are maintained between 20 and 80 ° C.
Nach der elektrochemischen Behandlung wird das Schwarzblech mit Wasser gespült. Das Spülen kann durch Eintauchen des Bands in einen Wassertank oder durch Abspritzen mit Wasser erfolgen. Bevorzugt wird dafür vollentsalztes (VE), deionisiertes Wasser, Osmosewasser oder destilliertes Wasser mit Temperaturen von 20 - 60 °C verwendet. Es können jedoch auch unbehandeltes Trinkwasser oder andere Spülflüssigkeiten verwendet werden. Nach dem Spülen wird das Schwarzblech getrocknet.After the electrochemical treatment, the black plate is rinsed with water. The rinsing can be done by immersing the tape in a water tank or by spraying with water. Preference is given to using demineralized (DI), deionized water, osmosis water or distilled water at temperatures of 20-60 ° C. However, untreated drinking water or other rinsing liquids can also be used. After rinsing, the black plate is dried.
Schließlich wird in einem abschließenden Schritt auf wenigstens eine Oberfläche des Schwarzblechs eine Konversionsschicht aufgetragen, indem eine wässrige chromfreie Behandlungslösung auf die zuvor in der elektrochemischen Behandlung inertisierte Oberfläche des Schwarzblechs appliziert wird.Finally, in a final step, a conversion layer is applied to at least one surface of the black plate by applying an aqueous chromium-free treatment solution to the surface of the black plate previously rendered inert in the electrochemical treatment.
Die Konversionsbeschichtung wird dabei in einem No-rinse-Verfahren aufgebracht, das heißt ein Spülen nach Erzeugen der Konversionsschicht unterbleibt. Die wässrige chromfreie Behandlungslösung, welche die Konversionsbeschichtung ausbildet, wird dabei bspw. mit einer Auftragsvorrichtung auf die Oberfläche des Schwarzblechs aufgebracht, welche einen Rollcoater, einen Rotationssprüher oder Sprühdüsen umfasst.The conversion coating is applied in a no-rinse process, that is, a rinsing after generating the conversion layer is omitted. The aqueous chromium-free treatment solution which forms the conversion coating is applied, for example, to the surface of the black plate with a coating device which comprises a roller coater, a rotary sprayer or spray nozzles.
Bevorzugt wird zur Applizierung der wässrigen Behandlungslösung eine Auftragsvorrichtung mit einem Rotationssprüher verwendet. Vor der Applikation der Behandlungslösung sollte die Oberfläche des Schwarzblechs, auf welche die Konversionsschicht aufgebracht werden soll, möglichst sauber und trocken sein. Deshalb wird zumindest die mit der Konversionsschicht zu beschichtende Oberfläche des Schwarzblechs mit einer Trocknungsvorrichtung, z.B. mit einem Air Knife, getrocknet. Mit diesem Air-Knife wird ein laminarer Heißluftstrom auf die Oberfläche des sich bewegenden Bands aufgeblasen, so dass störende Fremdpartikel von der Stahlbandoberfläche abgeblasen und die Stahlbandoberfläche getrocknet wird.For application of the aqueous treatment solution, it is preferable to use an application device with a rotary sprayer. Before application of the treatment solution, the surface of the black plate to which the conversion layer is to be applied should be as clean and dry as possible. Therefore, at least the surface of the black plate to be coated with the conversion layer is treated with a drying device, e.g. with an air knife, dried. With this Air-Knife a laminar hot air flow is inflated onto the surface of the moving belt, so that disturbing foreign particles are blown off the steel belt surface and the steel belt surface is dried.
Der Rotationssprüher weist mehrere quer zur Bandlaufrichtung nebeneinander angeordnete Sprührotoren auf, denen die wässrige Behandlungslösung zugeführt wird und welche von einem Antrieb in Rotation versetzt werden, um die wässrige Behandlungslösung zentrifugalkraftbedingt in Form eines feinen Sprühstrahls auf die oder jede Oberfläche des Bands zu sprühen und dort einen Nassfilm der wässrigen Lösung auszubilden. Nach dem Auftragen des Nassfilms der wässrigen Behandlungslösung wird diese mittels angetriebener Glättrollen auf der Oberfläche des Schwarzblechs vergleichmäßigt. Die Glättrollen sind dabei zweckmäßig in Bezug auf die Schwarzblechoberfläche(n) so angeordnet, dass sie nur wenig Druck auf den Nassfilm der wässrigen Behandlungslösung ausüben und keine oder allenfalls einen minimalen Anteil der applizierten Behandlungslösung von der Oberfläche abquetschen. Die Menge der mit dem Rotationssprüher aufgesprühten Behandlungslösung wird entsprechend so angepasst, dass kein Überschuß auf der Schwarzblechoberfläche entsteht. Dadurch entfällt eine sonst notwenige Entsorgung oder Aufbereitung des überschüssigen Anteils der Behandlungslösung. Nach der Vergleichmäßigung des aufgesprühten Nassfilms wird dieser getrocknet, so dass eine Trockenauflage der Behandlungssubstanz auf der oder den behandelten Schwarzblechoberflächen verbleibt. Zweckmäßig beträgt die Trockenauflage der Behandlungslösung nach dem Trocknen zwischen 1 und 50 mg/m2 und sie liegt bevorzugt im Bereich von 10 bis 30 mg/m2. Die den Sprührotoren des Rotationssprühers pro Zeiteinheit zugeführte Menge der wässrigen Behandlungslösung wird zweckmäßig an die Bandgeschwindigkeit angepasst. Dadurch kann gewährleistet werden, dass nur die genau benötigte Menge an frischer Behandlungslösung in der entsprechenden Konzentration mit dem Rotationssprüher als Nassfilm auf dem Schwarzblechband aufgebracht wird. So kann bspw. eine konstante Auflage des Nassfilms im Bereich von 2 ml/m2 bis 8 ml/m2 und bevorzugt von ca. 5 ml/m2 pro Bandseite unabhängig von der Bandgeschwindigkeit eingestellt werden.The rotary sprayer has a plurality of spray rotors juxtaposed transversely to the belt running direction to which the aqueous treatment solution is supplied and which are rotated by a drive to spray the aqueous treatment solution on the or each surface of the belt in the form of a fine spray jet due to centrifugal force Form wet film of the aqueous solution. After application of the wet film of the aqueous treatment solution, this is made uniform by means of powered smoothing rollers on the surface of the black plate. The smoothing rollers are included expediently with respect to the black plate surface (s) arranged so that they exert only little pressure on the wet film of the aqueous treatment solution and squeeze no or at most a minimum proportion of the applied treatment solution from the surface. The amount of treatment solution sprayed with the rotary sprayer is adjusted accordingly so that there is no excess on the blackplate surface. This eliminates the otherwise necessary disposal or treatment of the excess portion of the treatment solution. After the wetted wet film is evened out, it is dried so that a dry coating of the treatment substance remains on the treated black sheet surface (s). The dry coating of the treatment solution after drying is expediently between 1 and 50 mg / m 2 and is preferably in the range from 10 to 30 mg / m 2 . The amount of the aqueous treatment solution fed to the spray rotors of the rotary sprayer per unit time is expediently adapted to the belt speed. This can ensure that only the exact amount of fresh treatment solution is used in the appropriate concentration with the rotary sprayer as a wet film on the black plate tape is applied. Thus, for example, a constant circulation of the wet film in the range of 2 ml / m 2 to 8 ml / m 2 and preferably of about 5 ml / m 2 per band side can be set independently of the belt speed.
Nach dem Applizieren des Nassfilms der Behandlungslösung wird das Band durch einen Bandtrockner geführt, um den Nassfilm zu trocknen. Nach dem Trocknen verbleibt auf der Oberfläche des Schwarzblechs pro Seite eine Trockenauflage der so ausgebildeten Konversionsschicht von 2 mg/m2 bis 30 mg/m2. Die gewünschte Trockenauflage der Konversionsschicht lässt sich dabei durch die dem Rotationssprüher pro Zeiteinheit zugeführte Menge der Behandlungslösung einstellen.After applying the wet film of the processing solution, the belt is passed through a belt dryer to dry the wet film. After drying, a dry coating of the conversion layer formed in this way from 2 mg / m 2 to 30 mg / m 2 remains on the surface of the black plate per side. The desired dry coverage of the conversion layer can be adjusted by the amount of treatment solution fed to the rotary sprayer per unit of time.
Ein Vorteil dieser Art der Applikation besteht darin, dass immer nur frische Behandlungslösung verwendet wird und diese nicht durch Kontakt und Rezyklieren mit dem Stahlband durch Eisenablösung kontaminiert werden kann. Außerdem hat sich gezeigt, dass das Verfahren sehr wirtschaftlich ist, da nur die genau benötigte Menge appliziert wird und kein Überschuss benötigt wird, wodurch überschüssige Behandlungslösung nicht mehr aufgesammelt werden muss. Dadurch kann verhindert werden, dass nachzubehandelnde Abwässer entstehen.An advantage of this type of application is that only fresh treatment solution is used and that it can not be contaminated by iron separation by contact and recycling with the steel strip. In addition, it has been found that the process is very economical, since only the exact amount needed is applied and no excess is needed, so that excess treatment solution does not have to be collected. This can prevent that post-treated wastewater arise.
Alternativ dazu kann der Auftrag der Behandlungslösung auch über Rollcoater durch einen Walzenauftrag - ebenfalls auf eine vorher getrocknete Schwarzblechoberfläche - erfolgen. Rollcoater werden bevorzugt im unteren Geschwindigkeitsbereich der Bandgeschwindigkeit und insbesondere bei Geschwindigkeiten von weniger als 200 m/min eingesetzt. Alternativ kann die Applikation auch durch Aufsprühen der Behandlungslösung oder durch Eintauchen des Bands in einen Bad mit der Behandlungslösung erfolgen. Da dabei die Behandlungslösung im Überschuss auf das Schwarzblech aufgebracht wird, ist es zur Erzielung einer vorbestimmten gewünschten Auflage der Konversionsschicht erforderlich, den überschüssigen Anteil des Nassfilms bspw. mittels Quetschrollen abzuquetschen, wobei dies "nass in nass" erfolgen kann. Bei diesem Verfahren wird die Lösung allerdings nicht geschwindigkeitsunabhängig konstant gleich appliziert und die Behandlungslösung kann außerdem durch Eisen kontaminiert werden und muss dann erneuert und nach Überschreiten einer Kontaminationsschwelle entsorgt werden.Alternatively, the application of the treatment solution can also Rolling coater by a roller application - also on a previously dried black plate surface - done. Roll coaters are preferably used in the lower speed range of the belt speed and in particular at speeds of less than 200 m / min. Alternatively, the application can also be carried out by spraying the treatment solution or by immersing the tape in a bath with the treatment solution. In this case, since the treatment solution is applied in excess to the black plate, it is necessary to achieve a predetermined desired edition of the conversion layer, squeeze off the excess portion of the wet film, for example by means of squeezing rollers, which can be done "wet on wet". In this method, however, the solution is not applied the same constant regardless of the speed and the treatment solution can also be contaminated by iron and must then be renewed and disposed of after exceeding a contamination threshold.
Der mit den beschriebenen Applikationsverfahren aufgebrachte Nassfilm der Behandlungslösung wird schließlich zur Ausbildung einer trockenen Konversionsschicht getrocknet. Dies kann bspw. durch Durchführen des Schwarzblechs durch einen Trocknungsofen erfolgen, in dem Nassfilm mittels Heißluft oder IR-Strahlung getrocknet wird. Das Trocknen erfolgt bevorzugt bei Temperaturen von 50 - 250° C. Abschließend wird die Oberfläche der trockenen Konversionsschicht mit Dioctylsebacat (DOS), Acetyltributylcitrat (ATBC), Butylstearat (BSO) oder Polyalkylenglykol, insbesondere Polyethylenglykol (PEG, vorzugsweise mit einer Molmasse von 6000 g/mol), oder Kombinationen davon eingeölt bzw. nachbehandelt. Eine Nachbehandlung durch Einölung mit DOS, ATBC, BSO oder PEG erfolgt zweckmäßig elektrostatisch mit handelsüblichen Einölern wie bei ECCS oder Weißblech, oder auch mittels eines Rotationssprühers.The wet film of the treatment solution applied with the described application methods is finally dried to form a dry conversion layer. This can be done, for example, by passing the black plate through a drying oven in which wet film is dried by means of hot air or IR radiation. The drying is preferably carried out at temperatures of 50-250 ° C. Finally, the surface of the dry conversion layer with Dioctylsebacat (DOS), acetyltributylcitrate (ATBC), butyl stearate (BSO) or polyalkylene glycol, in particular polyethylene glycol (PEG, preferably having a molecular weight of 6000 g / mol), or combinations thereof oiled or post-treated. Aftertreatment by oiling with DOS, ATBC, BSO or PEG is advantageously carried out electrostatically with commercially available oilers as in ECCS or tinplate, or else by means of a rotary sprayer.
Die zur Konversionsbeschichtung verwendete wässrige Behandlungslösung beinhaltet mindestens die folgenden
- metallischen Bestandteile:
- a. Titan und Zirkonium,
- b. oder Titan, Zirkonium und Mangan,
- c. oder Titan, Zink und Phosphate,
- d. oder Titan, Zink, Mangan und Phosphate;
- Sie kann weiterhinorganische Bestandteile ausgewählt aus Polyacrylat, Polycarboxylatund Kombinationen davon enthalten.
- metallic components:
- a. Titanium and zirconium,
- b. or titanium, zirconium and manganese,
- c. or titanium, zinc and phosphates,
- d. or titanium, zinc, manganese and phosphates;
- It may further contain organic components selected from polyacrylate, polycarboxylate and combinations thereof.
Die Behandlungslösung kann weiterhin wenigstens einen Haftvermittler für Lacke oder organische Beschichtungsmaterialien enthalten, wobei der Haftvermittler insbesondere Bestandteile von Maleinsäure, Isophthalsäure und Cyclohexandimethanol (CHDM) oder Kombinationen davon enthält. Als besonders geeignete Haftvermittler haben sich Zusammensetzungen erwiesen, die Polyethylenterephthalat (PET) oder Polycyclohexylendimethylenterephthalat (PCT), enthalten, wie z.B. glykolmodifiziertes Polyethylenterephthalat (PET-G, welches weniger als ca. 30% CHDM enthält) oder PCTG (welches mehr als ca. 30% CHDM enthält).The treatment solution may further comprise at least one adhesion promoter for lacquers or organic coating materials, the adhesion promoter in particular containing constituents of maleic acid, isophthalic acid and cyclohexanedimethanol (CHDM) or combinations thereof. Especially suitable adhesion promoters have been found to be compositions containing polyethylene terephthalate (PET) or polycyclohexylenedimethylene terephthalate (PCT), e.g. glycol-modified polyethylene terephthalate (PET-G containing less than about 30% CHDM) or PCTG (containing more than about 30% CHDM).
Die Auflagen betragenbeispielsweise 1 bis 50 mg/m2 für die jeweiligen Substanzen.The requirements are for example 1 to 50 mg / m 2 for the respective substances.
Nachstehend sind einige ausgewählte im Handel befindliche Mittel angeführt, die zur Erzeugung von Konversionsbeschichtungen mit dem erfindungsgemäßen Verfahren geeignet sind.
Bevorzugte Behandlungslösungen zur Erzeugung der Konversionsschichten können beispielsweise wie folgt zusammengesetzt sein:
- a) eine wässrige Lösung, die Aluminiumfluorozirkonat mit einem Molverhältnis von A1 : Zr : F von (0,15 bis 0,67): 1: (5 bis 7) enthält, wobei die Gesamt-Konzentration von AI + Zr + F 0,1 bis 2,0 g/l beträgt und der pH-Wert auf weniger als 5, vorzugsweise 3 bis 5 eingestellt ist.
- b) eine wässrige Lösung, die im Wesentlichen enthält:
- 0,2 bis kleiner 10 g/l Zinkionen,
- 0,5 bis 25 g/l Manganionen und
- 2 bis 300 g/l Phosphationen, gerechnet als P2O5,
wobei das Zink : Mangan - Gewichtsverhältnis der Phosphatierungslösung im Bereich von 0,05 : 1 bis 1 : 1 gehalten wird.
- c) eine wässrige Lösung, die Zink und Mangan enthält, mit Zink im Bereich von 0,05 bis 5 g/l, Mangan im Bereich von 0,075 bis 5,2 g/l sowie Kupfer im Bereich von 0,008 bis 0,05 g/l und/oder insgesamt 0,002 bis 0,5 g/l an Hexafluoridkomplexen von Bor, Aluminium, Titan oder/und Zirkonium, berechnet als F6.
- d) eine wässrige Lösung mit mindestens einem Filmbildner, der mindestens ein wasserlösliches oder wasserdispergiertes Polymer mit einer Säurezahl im Bereich von 5 bis 200 enthält, und mindestens einer anorganischen Verbindung in Partikelform mit einem mittleren Partikeldurchmesser gemessen an einem Rasterelektronenmikroskop im Bereich von 0,005 bis 0,3 µm Durchmesser, wobei das Polymer aus mindestens einem Kunstharz auf der Basis von Acrylat, Ethylen, Polyester, Polyurethan, Siliconpolyester, Epoxid, Phenol, Styrol, Harnstoff-Formaldehyd, deren Derivate, Copolymere, Polymere, Mischungen oder/und Mischpolymerisate ausgewählt ist und die anorganische Verbindung in Partikelform aus mindestens einer Verbindung des Aluminiums, Siliciums, Titans, Zinks oder/und Zirkoniums ausgewählt ist. oder
- e) eine wässrige Lösung mit
- i) mindestens einem organischen Filmbildner, der mindestens ein wasserlösliches oder wasserdispergiertes Polymer enthält, das ein Kunstharz auf der Basis von Polyacrylsäure, Polyacrylat oder/und Polyethylen-Acryl-säure ist oder ein Kunstharzgemisch oder/und ein Mischpolymerisat mit einem Gehalt an Kunstharz auf der Basis von Acrylat bzw. Polyacryl, darstellt und
- ii) einem Gehalt an Kationen oder/und Hexa- oder Tetrafluorokomplexen von Kationen ausgewählt aus der Gruppe von Titan, Zirkonium, Silicium, Aluminium und Bor im Bereich von 0,2 bis 30 g/l bezogen auf den Gehalt des elementaren Metalls.
- a) an aqueous solution containing aluminum fluorozirconate having a molar ratio of A1: Zr: F of (0.15 to 0.67): 1: (5 to 7), the total concentration of Al + Zr + F 0, 1 to 2.0 g / l and the pH is adjusted to less than 5, preferably 3 to 5.
- b) an aqueous solution containing essentially:
- 0.2 to less than 10 g / l zinc ions,
- 0.5 to 25 g / l manganese ions and
- 2 to 300 g / l of phosphate ions, calculated as P 2 O 5 ,
wherein the zinc: manganese weight ratio of the phosphating solution is maintained in the range of 0.05: 1 to 1: 1.
- c) an aqueous solution containing zinc and manganese with zinc in the range of 0.05 to 5 g / l, manganese in the range of 0.075 to 5.2 g / l and copper in the range of 0.008 to 0.05 g / l and / or a total of 0.002 to 0.5 g / l of hexafluoride complexes of boron, aluminum, titanium or / and zirconium, calculated as F 6 .
- d) an aqueous solution comprising at least one film former containing at least one water-soluble or water-dispersed polymer having an acid number in the range from 5 to 200, and at least one inorganic compound in particle form having a mean particle diameter measured on a scanning electron microscope in the range from 0.005 to 0, 3 μm in diameter, the polymer being selected from at least one synthetic resin based on acrylate, ethylene, polyester, polyurethane, silicone polyester, epoxide, phenol, styrene, urea-formaldehyde, their derivatives, copolymers, polymers, mixtures or / and copolymers and the inorganic compound is selected in particulate form from at least one compound of aluminum, silicon, titanium, zinc or / and zirconium. or
- e) an aqueous solution with
- i) at least one organic film former containing at least one water-soluble or water-dispersed polymer which is a synthetic resin based on Polyacrylic acid, polyacrylate and / or polyethylene-acrylic acid or a synthetic resin mixture and / or a copolymer containing acrylate or acrylic based synthetic resin, and
- ii) a content of cations and / or hexa- or tetrafluoro complexes of cations selected from the group consisting of titanium, zirconium, silicon, aluminum and boron in the range from 0.2 to 30 g / l based on the content of the elemental metal.
Das erfindungsgemäße Verfahren kann ohne größeren Installationsaufwand in eine vorhandene Beschichtungsanlage, z.B. in eine Bandbeschichtungsanlage zur Herstellung von ECCS (bzw. TFS) integriert werden. Die Bandgeschwindigkeit beträgt in solchen Bandbeschichtungsanlagen typischerweise 80 - 600 m/min.The process according to the invention can be carried out without major installation effort into an existing coating installation, e.g. be integrated into a coil coating plant for the production of ECCS (or TFS). The belt speed in such belt coating systems is typically 80-600 m / min.
Das erfindungsgemäße Verfahren besitzt die Vorteile einer chromfreien und damit umweltschonenden und nicht gesundheitsgefährdenden sowie kostengünstigen Beschichtung auf herkömmlichem Schwarzblech, insbesondere im Fein- und Feinstblech-Dickenbereich. Zudem wird durch das gewählte Applikationsverfahren (No-Rinse-Verfahren) zum Auftragen der Konversionsschicht durch Wegfall der Schlussspülung eine wirksame Kosten- und Energieersparnis erzielt werden. Insbesondere durch die Kombination von anorganischer Passivierung und polymerhaltiger Dünnfilmbeschichtung werden zusätzlich Vorteile erzielt. Die mit dem erfindungsgemäßen Verfahren behandelten Schwarzbleche eignen sich hervorragend zur Herstellung von Verpackungen, insbesondere von Dosen, und können daher die herkömmlich als Verpackungsstahl verwendeten Weißbleche und zinnfreien Stahlbleche (TFS bzw. ECCS) ersetzen. Diese Schwarzbleche sind hinsichtlich ihrer Korrosionsbeständigkeit vergleichbar mit Weißblech und weisen ähnlich gute Hafteigenschaften für Lacke und Kunststoffbeschichtungen, bspw. aus PP oder PET, auf wie zinnfreie Stahlbleche (TFS bzw. ECCS).The inventive method has the advantages of a chromium-free and thus environmentally friendly and not harmful to health and cost-effective coating on conventional black plate, especially in the fine and Feinstblech thickness range. In addition, by the selected application method (no-rinse method) for applying the conversion layer by eliminating the final rinse effective cost and energy savings can be achieved. In particular, advantages are achieved by the combination of inorganic passivation and polymer-containing thin-film coating. The black sheets treated by the process of the invention are eminently suitable for the production of packaging, in particular cans, and can therefore replace the tinplates and tin-free steel sheets (TFS or ECCS) conventionally used as packaging steel. These black sheets are comparable in their corrosion resistance with tinplate and have similarly good adhesion properties for paints and plastic coatings, for example of PP or PET, on as tin-free steel sheets (TFS or ECCS).
Claims (11)
- Method for passivating black sheet in strip form, with the following steps which are carried out sequentially.- provision of a cold-rolled, annealed and rerolled steel strip with a carbon content of from 20 to 1000 ppm related to the weight and passing of the steel strip through a strip coating installation with a strip speed of at least 200 m/min,- cleaning and degreasing of the steel strip by passing the steel strip at the strip speed through a cleaning tank with an alkaline solution of sodium hydroxide or potassium hydroxide and then rinsing it,- electrochemical treatment of the black sheet by passing the steel strip at the strip speed through an alkaline electrolyte with current densities of from 2 to 30 A/dm2 with the steel strip connected as the anode, to form an inert steel surface, wherein the electrolyte is a solution of sodium hydroxide or soda which is maintained at temperatures of between 20 and 80°C,- rinsing and drying of the steel strip,- application of an aqueous chromium-free treatment solution to at least one surface of the steel strip to form a conversion layer protecting against corrosion and an adhesive layer for paints and organic coating materials by applying the aqueous treatment solution to the steel strip moving at the strip speed in a no-rinse process, wherein the treatment solution contains as essential chemical constituent:a. titanium and zirconium,b. or titanium, zirconium and manganese,c. or titanium, zinc and phosphates,d. or titanium, zinc, manganese and phosphates.
- Method according to claim 1, wherein after the degreasing and before the electrochemical treatment the steel strip is additionally pickled and rinsed again.
- Method according to claim 1 or 2, wherein after the application of the treatment solution the steel strip is dried, preferably at temperatures of between 50°C and 250°C, in order to form a dry coating of treatment solution on the surface of the steel strip.
- Method according to claim 3, wherein the aqueous treatment solution is applied to the steel strip either without an excess with a rotation sprayer or applied with an excess with a roll coater or spraying nozzles and then the excess treatment solution is squeezed off with squeezing rollers.
- Method according to one of claims 3 or 4, wherein after the drying the dry coating of the treatment solution is treated again with dioctyl sebacate (DOS), acetyl tributyl citrate (ATBC), butyl stearate (BSO) or a polyalkylene glycol, in particular polyethylene glycol (PEG).
- Method according to one of claims 3 to 5, wherein the dry coating of the treatment solution is between 1 mg/m2 and 50 mg/m2.
- Method according to one of the preceding claims, wherein the steel strip is a ferritic or multiphase steel sheet.
- Method according to one of the preceding claims, wherein the temperature of the electrolyte during the electrochemical treatment of the steel strip is between 20 and 50°C.
- Method according to one of the preceding claims, wherein the current density during the electrochemical treatment of the black sheet is between 2 and 10 A/dm2.
- Method according to one of the preceding claims, wherein the aqueous treatment solution also contains organic constituents selected from polyacrylate, polycarboxylate and combinations thereof.
- Method according to claim 1, characterised in that the treatment solution contains at least one adhesion-promoter for paints or organic coating materials, wherein the adhesion-promoter has in particular constituents of maleic acid, isophthalic acid and cyclohexane dimethanol (CHDM) or combinations thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RS20170926A RS56351B1 (en) | 2013-07-16 | 2014-07-03 | Method for passivating strip black iron plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE201310107506 DE102013107506A1 (en) | 2013-07-16 | 2013-07-16 | Method for passivation of band-shaped black plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2826569A1 EP2826569A1 (en) | 2015-01-21 |
| EP2826569B1 true EP2826569B1 (en) | 2017-06-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14175621.3A Active EP2826569B1 (en) | 2013-07-16 | 2014-07-03 | Method for passivating strip black iron plate |
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| Country | Link |
|---|---|
| US (1) | US20150024222A1 (en) |
| EP (1) | EP2826569B1 (en) |
| JP (1) | JP2015028210A (en) |
| CN (1) | CN104294348B (en) |
| BR (1) | BR102014017368B1 (en) |
| CA (1) | CA2855673C (en) |
| DE (1) | DE102013107506A1 (en) |
| ES (1) | ES2634870T3 (en) |
| RS (1) | RS56351B1 (en) |
| RU (1) | RU2663232C2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102015113878B4 (en) * | 2015-08-21 | 2023-03-16 | Thyssenkrupp Ag | Process for the thermal treatment of a black plate coated with a conversion layer |
| CN105695698A (en) * | 2015-12-31 | 2016-06-22 | 芜湖市金宇石化设备有限公司 | Preparing method for heat treating agent for heat treatment of speed changing box shell |
| CN105567920A (en) * | 2015-12-31 | 2016-05-11 | 芜湖市金宇石化设备有限公司 | Heat treatment agent for heat treatment of transmission shell |
| DE102017117080A1 (en) * | 2017-07-28 | 2019-01-31 | Thyssenkrupp Ag | Steel sheet with a conversion layer, process for producing a conversion-coated steel sheet and treating agent for applying a conversion layer to a steel sheet |
| JP6573042B1 (en) * | 2017-11-28 | 2019-09-11 | Ｊｆｅスチール株式会社 | Oriented electrical steel sheet and manufacturing method thereof |
| 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 |
| DE202020100524U1 (en) * | 2020-01-31 | 2021-05-04 | Thyssenkrupp Rasselstein Gmbh | Sheet metal packaging product, in particular tinplate or electrolytically chrome-plated sheet steel |
| KR102204664B1 (en) * | 2020-12-15 | 2021-01-19 | 우리하이피 주식회사 | Nano passivation treatment method of reel-to-reel metal plate and processed products, and metal plate and processed products manufactured accordingly |
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| JPS5989776A (en) * | 1982-11-13 | 1984-05-24 | Sumitomo Metal Ind Ltd | Production of cold rolled steel sheet having excellent characteristic for chemical conversion |
| FR2730942B1 (en) * | 1995-02-24 | 1997-05-16 | Lorraine Laminage | PROCESS FOR THE PREPARATION OF A SHEET OR A STEEL STRIP FOR THE PRODUCTION OF A BOX AND SHEET OR STEEL STRIP OBTAINED BY THIS PROCESS |
| DE19615664A1 (en) | 1996-04-19 | 1997-10-23 | Surtec Produkte Und Systeme Fu | Chromium (VI) free chromate layer and process for its production |
| DE19635560A1 (en) * | 1996-09-02 | 1998-03-05 | Basf Lacke & Farben | Non-porous coating of metal containers |
| GB2334906A (en) * | 1998-03-02 | 1999-09-08 | British Steel Plc | Laminated metal strip |
| ES2265445T3 (en) * | 2000-10-11 | 2007-02-16 | Chemetall Gmbh | PROCEDURE FOR THE COATING OF METAL SURFACES WITH AN AQUOUS COMPOSITION, AQUOUS COMPOSITION AND USE OF COATED SUBSTRATES. |
| JP4054539B2 (en) * | 2001-03-07 | 2008-02-27 | 日本パーカライジング株式会社 | Method for producing metal material for plastic working having inclined two-layer lubricating film |
| JP4110750B2 (en) * | 2001-06-07 | 2008-07-02 | Ｊｆｅスチール株式会社 | Organic coated steel sheet with excellent corrosion resistance and conductivity |
| WO2004067802A1 (en) * | 2003-01-31 | 2004-08-12 | Jfe Steel Corporation | Black zinc-plated steel sheet |
| JP2005272972A (en) * | 2004-03-26 | 2005-10-06 | Nisshin Steel Co Ltd | Method of pretreatment for coating of bright annealing-treated stainless steel sheet and bright annealing-treated stainless steel sheet for coating |
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- 2014-06-26 JP JP2014131073A patent/JP2015028210A/en active Pending
- 2014-07-03 EP EP14175621.3A patent/EP2826569B1/en active Active
- 2014-07-03 ES ES14175621.3T patent/ES2634870T3/en active Active
- 2014-07-03 RS RS20170926A patent/RS56351B1/en unknown
- 2014-07-03 CA CA2855673A patent/CA2855673C/en active Active
- 2014-07-10 RU RU2014128191A patent/RU2663232C2/en not_active IP Right Cessation
- 2014-07-15 BR BR102014017368-4A patent/BR102014017368B1/en not_active IP Right Cessation
- 2014-07-15 CN CN201410337358.3A patent/CN104294348B/en active Active
- 2014-07-16 US US14/332,490 patent/US20150024222A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| CN104294348A (en) | 2015-01-21 |
| BR102014017368A2 (en) | 2015-10-06 |
| JP2015028210A (en) | 2015-02-12 |
| EP2826569A1 (en) | 2015-01-21 |
| CA2855673C (en) | 2016-09-27 |
| ES2634870T3 (en) | 2017-09-29 |
| RU2663232C2 (en) | 2018-08-02 |
| CA2855673A1 (en) | 2015-01-16 |
| US20150024222A1 (en) | 2015-01-22 |
| BR102014017368B1 (en) | 2021-06-29 |
| DE102013107506A1 (en) | 2015-01-22 |
| CN104294348B (en) | 2017-12-12 |
| RU2014128191A (en) | 2016-01-27 |
| RS56351B1 (en) | 2017-12-29 |
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