GB2071699A - Production of tin plated steel sheet - Google Patents
Production of tin plated steel sheet Download PDFInfo
- Publication number
- GB2071699A GB2071699A GB8104043A GB8104043A GB2071699A GB 2071699 A GB2071699 A GB 2071699A GB 8104043 A GB8104043 A GB 8104043A GB 8104043 A GB8104043 A GB 8104043A GB 2071699 A GB2071699 A GB 2071699A
- Authority
- GB
- United Kingdom
- Prior art keywords
- tin
- steel sheet
- compound
- electrolyte
- chromium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 63
- 239000010959 steel Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 36
- 238000011282 treatment Methods 0.000 claims abstract description 22
- 238000007654 immersion Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 229910001430 chromium ion Inorganic materials 0.000 claims description 19
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052804 chromium Inorganic materials 0.000 claims description 18
- 239000011651 chromium Substances 0.000 claims description 18
- 238000007747 plating Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 150000002222 fluorine compounds Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 150000003464 sulfur compounds Chemical class 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000001845 chromium compounds Chemical class 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- -1 phosphorus compound Chemical class 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 5
- 229940079864 sodium stannate Drugs 0.000 claims description 5
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 5
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- LCALOJSQZMSPHJ-QMMMGPOBSA-N (2s)-2-amino-3-cyclohexa-1,5-dien-1-ylpropanoic acid Chemical compound OC(=O)[C@@H](N)CC1=CCCC=C1 LCALOJSQZMSPHJ-QMMMGPOBSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 2
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229940048084 pyrophosphate Drugs 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 229940044652 phenolsulfonate Drugs 0.000 claims 2
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 claims 1
- XXAXVMUWHZHZMJ-UHFFFAOYSA-L 4,5-dihydroxybenzene-1,3-disulfonate Chemical compound OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-L 0.000 claims 1
- JXBUOZMYKQDZFY-UHFFFAOYSA-N 4-hydroxybenzene-1,3-disulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1S(O)(=O)=O JXBUOZMYKQDZFY-UHFFFAOYSA-N 0.000 claims 1
- 229910003638 H2SiF6 Inorganic materials 0.000 claims 1
- 229910004039 HBF4 Inorganic materials 0.000 claims 1
- 229910020440 K2SiF6 Inorganic materials 0.000 claims 1
- 229910020261 KBF4 Inorganic materials 0.000 claims 1
- 229910017665 NH4HF2 Inorganic materials 0.000 claims 1
- 229910004883 Na2SiF6 Inorganic materials 0.000 claims 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims 1
- RAGLTCMTCZHYEJ-UHFFFAOYSA-K azanium;chromium(3+);disulfate Chemical compound [NH4+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RAGLTCMTCZHYEJ-UHFFFAOYSA-K 0.000 claims 1
- HLVXFWDLRHCZEI-UHFFFAOYSA-N chromotropic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 HLVXFWDLRHCZEI-UHFFFAOYSA-N 0.000 claims 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 claims 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims 1
- 239000004922 lacquer Substances 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000003466 welding Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000005029 tin-free steel Substances 0.000 description 7
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004826 seaming Methods 0.000 description 6
- 239000005028 tinplate Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000009928 pasteurization Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- 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
- C25D11/38—Chromatising
-
- 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
- C23C22/24—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 hexavalent chromium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—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 hexavalent chromium compounds
- C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
-
- 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/33—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 hexavalent chromium compounds containing also phosphates
-
- 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
- C23C22/37—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 containing also hexavalent chromium compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electrochemical Coating By Surface Reaction (AREA)
Abstract
Steel sheet is first electrolytically plated with 0.05-1.12 g/m<2> tin and an upper layer of 0.5-5 mg/m<2> hydrated chromium oxide is then formed by immersion or electrolytic treatment. The steel sheet produced has excellent weldability, corrosion resistance and lacquer adhesion.
Description
SPECIFICATION
Production of tin plated steel sheet
The present invention relates to a method for the production of an extremely thin tin plated steel sheet possessing excellent weldability characteristics. In detail, the invention relates to a method for the production of a steel sheet having an upper layer of a thin hydrated chromium oxide and a lower thin layer of tin.
DESCRIPTION OF THE PRIOR ART
Recently the change from expensive electrotinplates to cheaper tin free steel (TFS) consisting of a metallic chromium and hydrated chromium oxide as well as a decrease in the weight of the tin coating in electrotinplates have rapidly taken place in the field of food cans. This is because the tin used for the production of tinplates is very expensive, and there is concern over the exhaustion of tin resources in the world.
An ordinary metal can consists of two can ends and a single can body. In the case of TFS, the seaming of the can body is generally carried out with nylon adhesives by using the Toyo Seam and Mira
Seam methods.
Nowadays, a TFS can body seamed by a nylon adhesive is not only used for beer and carbonated beverages, but also used for foods, such as fruit juices (which are immediately placed after pasteurization at a temperature of 90-1 000C), or coffee, meat and fish (which are pasteurized by hot steam at a temperature above 1000C in a retort after being packed in the can at 90-1 000C). This is because of the progress in the TFS manufacturing techniques and improvements of TFS films as exemplified in Laid-Open Japanese Patent Application No. Sho 53-58442, No. Sho 54-64034 and
No. Sho 54-89946.
Another method of seaming a TFS can body by electric welding is also well known. In such electric welding process, however, the seaming process is intricate because the metallic chromium layer and the hydrated chromium oxide layer must be mechanicaily or chemically removed from the TFS surface.
On the other hand, the seaming of a tinplate can body is generally carried out by soldering. In this soldering process, however, it is impossible to decrease the weight of the tin coating on the tinplate to under 2.8 g/m2, because it is difficult to stabilize the soldering process when the weight of the coating is under 2.8 g/m2.
A method of seaming the tinplate can body employing organic adhesives has been also proposed, for instance in Laid-Open Japanese Patent Application No. Sho 49-37829 and Japanese Patent
Publication No. Sho 48-18929. However, after a few months, the tinplate can body seamed by an organic adhesive may be broken, because the bonding strength in the seam becomes remarkably low.
In view of the above, a lap seam welding, for instance, the Soudronic Process has been recently proposed as a new method of seaming the tinplate can body. This Soudronic process is used for manufacturing an aerosol can body or a dry fill can body. In this field, it is also desirable to decrease the tin coating weight, but the weldability of tinplate becomes poor with a decrease of the tin coating weight.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method for the production of an extremely thin tin plated steel sheet having excellent weldability as well as excellent lacquer adhesion and corrosion resistance after lacquering and forming.
This object can be accomplished by the formation of a uniform hydrated chromium oxide layer containing from 0.5 to 5 mg/m2 calculated as chromium, on a steel sheet which has been covered with a dense and thin layer of tin in which the tin coating weight is 0.05-1.12 g/m2.
As a result of investigations on the weldability of extremely thin tin plated steel sheets having a hydrated chromium oxide layer formed by treatment of the tin coated steel sheet in a solution containing mainly hexavalent chromium ions, it has been determined that the weldability of said tin plated steel sheet by the Soudronic Process depends on the amount of hydrated chromium oxide, calculated as chromium, on said thin tin plated steel sheet. The weldability is improved with a decrease of the amount of hydrated chromium oxide, as chromium, particularly in the case of a thin tin plated steel sheet.
Although the reason is not obvious, it is assumed that the effect of the amount of hydrated chromium oxide, based on the amount of chromium, can be neglected in the case when the tin coating weight is increased, because a large amount of tin which is present under the hydrated chromium oxide layer is melted during welding, and in the case of tin coating weight decreased, the amount of hydrated chromium oxide as chromium affects the weldability, because the thin tin layer is converted immediately into an iron-tin alloy layer.
As described above, by simply decreasing the amount of hydrated chromium oxide, as chromium, on the thin tin plated steel sheet, the weldability is improved, but the desired excellent lacquer adhesion and corrosion resistance, after lacquering, and forming, are not maintained. So, it is also important in the present invention to subject the steel sheet to a dense and thin tin plating step, which is necessary for the formation of an uniform and thin hydrated chromium oxide layer on said thin tin plated steel.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a method for the production of thin tin plated steel sheet comprises, as the only essential steps, electrolytically tin plating a substantially clean steel sheet and subjecting the resultant steel sheet to chromic acid treatment to form a hydrated chromium oxide layer on the exposed surface of tin. From an industrial point of view, the present invention can be carried out according to the following process: degreasing with an alkali and pickling with an acid < water rinsing - < very thin electrolytic tin plating r+ water rinsing < chromic acid treatment < water rinsing < drying.
In some cases, the heating of the very thin tin plated steel sheet at a temperature below or above the melting point of the tin and the subsequent quenching operations are carried out after the thin tin plating step.
To carry out the electrolytic tin plating in the present invention, a known tinplating electrolyte may be employed, for sample, an acidic electrolyte, such as stannous sulfate, a stannous aromatic sulfonate, stannous fluoborate and stannous chloride, or an alkaline electrolyte may be used such as sodium stannate and potassium stannate, or a neutral electrolyte such as stannous sulfate containing a carboxylic acid additive may be employed. It is preferable for the formation of a dense tin layer in the present invention to use the known alkaline electrolytes or the weakly acidic electrolytes having a low concentration of stannous ions (described in Japanese Patent Application No. Sho. 46-25603, Laid
Open Japanese Patent Application No.Sho 55-73887), especially an improved alkaline electrolyte (described in Laid-Open Japanese Patent Application No. Sho 54-11 7332, in which a considerable amount of hydrogen gas is generated.
In the present invention, the following electrolytic tin plating conditions are employed when an acidic electrolyte is used:
Concentration of stannous ions: 1.5-1 5 g/l Concentration of free acid (as H2SO4): 1.0-15 g/l
Concentration of organic addition agents, such as
Ethoxylated ez-naphthol sulfonic acid or
cresol sulfonic acid: 1-6 g/l
Temperature of the electrolyte: 25-600C Current density: 5-50 A/dm2
Generally, a lower current density is applied for the formation of a dense tin layer at lower electrolyte temperatures, for a lower concentration of the stannous ions and finally lower current densities are used for higher concentrations of the free acid.On the contrary, when higher temperatures are employed and a higher concentrations of the stannous ions as wel! as lower concentrations of free acid is used, a higher current density must be applied. Furthermore, when the concentration of the stannous ions and the free acid are below 1.5 and 1.0 girl, respectively, the electric resistance of the electrolyte increases and the current efficiency in the tin plating operation becomes very low, and therefore, such low concentrations are not suitable for the industrial production of thin tin plated steel sheets.
It is preferred in the present invention that the electrotinplating be carried out in a current efficiency of 20-70 percent in respect to the tin deposition.
In the present invention, the following electrolytic conditions are employed, when alkaline electrolytes are used:
Concentration of stannic ions: 30--70 g/l Concentration of base (as NaOH or KOH); 10-25 g/l Temperature of the electrolyte: 70-900C Current density: 1 --10 A/dm2 Generally, in an alkaline electrolyte, as compared with an acidic electrolyte, a more dense tin layer is obtained but the current efficiency of the tin plating step is lower. Especially, the current efficiency for tin plating decreases remarkably with an increase in the current density and a decrease in the temperature of the electrolyte.
In the present invention, the optimum range for the amount of plated tin is from 0.05 to 1.12 g/m2, preferably from 0.22 to 1.12 g/m2. if the amount of tin is less than 0.05 g/m2, the corrosion resistance becomes remarkably poor. An increase in the amount to above 1.12 g/m2 is not economical because of the high price of tin, although the weldability would not be affected.
In some cases, the thin tin plated steel sheet is heated at a temperature above or below the melting temperature of the tin and the thus-heated plate is quenched. In this case, heating is carried out by known methods such as resistance heating as is generally used in the electrotinplating.
The hydrated chromium oxide layer is formed on the thin tin plated steel sheet, according to a cathodic treatment or an immersion treatment in a known solution containing hexavalent chromium ions, such as a sodium dichromate solution or a chromic acid solution.
In the present invention, the hexavalent chromium compound is selected from the group consisting of chromic acid, ammonium chromate, ammonium dichromate, and the chromate or dichromate of an alkali metal. It is also possible in some cases to call at least one compound selected from trivalent chromium compounds, sulfur compounds, fluorine compounds and phosphorus compounds to the hexavalent chromium ion-containing solution.
Trivalent chromium ions are formed by the addition of a trivalent chromium compound, such as chromium sulfate, chromium hydroxide, by the addition of a reducing agent such as an alcohol and hydrogen peroxide or by an electrolyte reduction of the hexavalent chromium ions. The sulfur compounds are selected from the group consisting of sulfuric acid, an aromatic disulfonic acid, a sulfate, a sulfite, a thiocyanate, or an aromatic disulfonate of ammonium and alkali metals and thiourea. The fluorine compound is selected from the group consisting of hydrofuloric acid, a hydrofluoboric acid, a hydrofluosilicic acid, a fluoride, a borofluoride, or a silicofluoride of ammonium and alkali metals. The phosphorus compound is selected from the group of phosphoric acid, pyro-phosphoric acid, a phosphate, or a pyrophosphate of ammonium and alkali metals.
In the case of an immersion treatment of the thin tin plated steel sheet, it is desirable to control the pH of the solution below 6, and for an immersion time of about 0.1-10 seconds.
In the case of an electrolytic treatment, the thin tin plated steel sheet is generally subjected to a cathodic treatment using an acqueous solution containing hexavalent chromium ions.
However, in the present invention, an anodic treatment, an anodic treatment after a cathodic treatment or a cathodic treatment after an anodic treatment is also applied for the treatment of the thin tin plated steel sheet. Furthermore, it is possible to repeat these treatments several times. In the point of practical application, a quantity of electricity below 10 coulombs/dm2 is sufficient for the formation of the hydrated chromium oxide having less than 5 mg/m2 as chromium on the thin tin plated steel sheet, although the quantity of electricity depends on the composition of the electrolyte, the pH of the electrolyte, the temperature of the electrolyte and the surface conditions of the tin plated steel sheet.
The conditions for the formation of the hydrated chromium oxide are summarized as follows:
Concentration of hexavalent chromium ions: 5-50 g/l
pH of solution: 1-6 Temperature of solution: 3 5-600C Current density (in case of electrolytic treatment): 5-50 A/dm2
Treating time or immersion time: 0.1-10 sec.
Concentration of additives such as sulfur compound, fluorine compound and phosphorus compound in some cases: 1/1 0--l/l 50 of the hexavalent chromium ions
The optimum range for the amount of hydrated chromium oxide formed under the conditions described above is 0.5-5 mglm2, preferably 0.5-3 mg/m2, calculated as chromium. If the amount of the hydrated chromium oxide calculated as chromium, is above 5 mg/m2, the weldability is decreased.
Generally, the weldability is improved when the amount of hydrated chromium oxide is decreased because the surface resistance is decreased, but if the amount of hydrated chromium oxide falls below 0.5 mg/m2, based upon the calculated chromium content, the corrosion resistance and the lacquer adhesion is remarkably decreased.
It is very important in the present invention that a thin and uniform hydrated chromium oxide layer is formed on the thin tin plated steel sheet in order that all the properties, excellent weldability, and corrosion resistance after lacquering and forming is achieved as well as excellent lacquer adhesion. It has been found that the uniformity of the formed hydrated chromium oxide layer depends on the uniformity and denseness of the tin layer to be treated, although it is also affected by the conditions used in the formation of the hydrated chromium oxide. That is to say, in the case that the plated tin layer does not sufficiently cover the surface of the steel sheet, the hydrated chromium oxide layer formed on tin plated steel sheet is not uniform and shows a net-work like structure.
Therefore, it is very important in the present invention that the steel sheet be suhjected to a dense and uniform tin plating by using the known alkaline electrolytes or the weakly acidic electrolytes having a low concentration of stannous ions in order to form a uniform hydrated chromium oxide layer on the thin tin plated steel sheet.
This invention is illustrated by the following examples.
EXAMPLE 1
A cold reduced steel sheet having a thickness of 0.23 mm was electrolytically degreased in a solution of sodium hydroxide and then pickled in dilute sulfuric acid. The steel sheet, after being rinsed with water, was electroplated with tin under the following plating conditions and then rinsed with water and dried.
Composition of electrolyte:
Stannous sulfate:5 g/l
Phenolsulfonic acid (60% aqueous solution): 20 g/l
Ethoxylated cr-naphthol sulfonic acid: 5 g/l
Bath temperature: 400C
Cathodic current density: 10 A/dm2 Tin coating weight: 0.51 g/m2 After that, the tin on the steel sheet was melted by using resistance heating, and then was treated by an immersion into the following solution:
Composition of solution:
Chromic acid: g/l Sodium hydroxide: 10 g/l
Bath temperature: 400C
Chromium weight in hydrated chromium oxide: 1.4 mg/m2 EXAMPLE 2
A steel sheet pre-treated as in Example 1 was electroplated with tin under the following plating conditions and then rinsed with water and dried:
Composition of electrolyte:
Sodium stannate: 80 g/l
Sodium hydroxide: 20 gIl Bath temperature: 850C
Cathodic current density: 1 5 A/dm2 Tin coating weight: 0.39 g/m2 After that, the tin coated steel sheet was heated at 21000, and then was treated by an immersion into the following solution:
Composition of solution:
Chromic acid: 30 g/l Sodium fluoride: 0.5 g/l
Bath temperature: 500C
Chromium weight in hydrated chromium oxide: 0.7 mg/m2 EXAMPLE 3
A steel sheet pre-treated as in Example 1 was electroplated with tin under the following plating conditions and then rinsed with water and dried:
Composition of electrolyte:
Sodium stannate: 70 g/l Sodium hydroxide: 15 g/l
Sodium aluminate: 40 g/l
Bath temperature: 850C
Cathodic current density: 5 A/dm2 After that, tin on the steel sheet was melted by using resistance heating, and then was cathodically treated under the following conditions and then rinsed with water and dried: Composiiion of electrolyte:
Sodium dichromate: 30 g/l Bath temperature: 400C
Cathodic current density: 5 A/dm2 Chromium weight in hydrated chromium oxide: 2.3 mg/m2 COMPARATIVE EXAMPLE 1
A steel sheet pre-treated as in Example 1 was electroplated with tin of 0.25 g/m2 under the same conditions as in Example 1.After rinsing with water, and drying, the tin on the coated steel sheet was reflowed by using resistance heating and then was cathodically treated under the same conditions as in
Example 1 for the formation of hydrated chromium oxide on the tin coated steel sheet in an amount of 6.1 mg!m2, calculated as chromium. After that, the treated steel sheet was rinsed with water and dried.
COMPARATIVE EXAMPLE 2
A steel sheet pre-treated, as in Example 1, was electroplated with tin in an amount of 0.56 g/m2 under the same conditions as in Example 1. After rinsing with water, the tin coated steel sheet was cathodically treated, under the same conditions as in Example 1 for the formation of hydrated chromium oxide on the tin layer in an amount of 8.2 mg/m2. After that, the treated steel sheet was rinsed with water and dried.
The weldability, corrosion resistance and lacquer adhesion of thus treated steel sheet in the above described Examples and Comparative Examples were evaluated by the following testing methods, the results of which are shown in the attached Table.
(1) Weldability The weldability was evaiuated by using a welding test machine which is similar to that of
Soudronic type having a copper wire as an intermediate electrode, under the following welding conditions:
Welding conditions:
Power supply frequency: 60 Hz
Welding speed: 8.4 m/min.
Overlap of sheet: 0.4 mm
Added pressure: 45 kg
The weldability was shown as an available range of secondary current in welding. The upper limit in the available secondary current range corresponds to the welding conditions in which some defect,
such as splash, is found and the lower limit corresponds to the welding conditions in which the
breakage occurs in the parent metal or welded part by tearing tests.
This weldability is judged by the method of Williams, that is to say, the wider the secondary
current range in welding, the better the weldability.
(2) Corrosion Resistance After Lacquering and Forming
The sample was based at 21 00C for 12 minutes after coating with 50 mg/dm2 of an epoxy
phenolic type of lacquer. The coated sample was cut to a size of 1 5 mm x 100 mm. The test piece was
bent to 1 80 by the drop of a 3 kg weight from a height of 1 50 mm, after placing a steel sheet having a
thickness of 0.25 mm between the pre-bent test piece. The bent test piece was sealed by paraffin,
except for the formed part, and was put in 300 ml of a 0.01 mole/l phosphoric acid solution at room temperature for one week.
The same procedure was repeated for another test piece, except, a 0.01 mole/l citric acid solution containing 0.3 percent by weight of sodium chloride, was used. The iron pick-up in each solution was
measured.
(3) LacquerAdhesion Two pieces of the sample were pretreated. One piece of the sample was based at 21 OOC for 1 2 minutes after coating with 60 mg/dm2 of an epoxy-phenolic type of lacquer and the other piece was baked under the same conditions as described above after coating with 25 mg/dm2 of the same lacquer.
the two pieces of the differential coated sample which were each cut to a size of 5 mm x 100 mm, were bonded together by using a 100 um nylon film at 2000C for 30 seconds under 3 kg/cm2 of pressure by using a hot press after preheating at 2000C for 1 20 seconds.
The peel strength (kg/5 mm) of the assembly was measured by a conventional tensile testing machine.
The weldability, corrosion resistance after lacquering and forming and lacquer adhesion of the steel sheet obtained by the Examples and the Comparative Examples were evaluated by the tests described above, the results of which are shown in the Table.
As apparent from the Table, the treated steel sheet of the present invention has excellent weldability, corrosion resistance after lacquering and forming, and excellent lacquer adhesion.
This treated steel sheet is therefore quite suitable for use as a material for making welded cans. TABLE
Characteristics of Treated Steel Sheet
Comparative Comparative Example 1 Example 2 Example 3 Example 1 Example 2 Available secondary current range for welding (Ampere) 210 250 180 0 50 0.01 mole/l Corrosion H3PO4 0.15 0.22 0.23 0.71 0.46 resistance (ppm) 0.01 mole/l citric acid 0.18 0.20 0.22 0.65 0.42 Lacquer adhesion (kg/5 mm) 6.4 6.1 7.3 0.8 0.5 Total evaluation as a material for welded cans Excellent Excellent Excellent Poor Fair
Claims (14)
1. A process for producing a steel sheet having a lower layer of tin and an upper layer of hydrated chromium oxide having excellent weldability which comprises electrolytically tin plating a substantially clean steel sheet in an electrolyte containing stannous sulfate, stannous phenolsulfonate, stannous chloride, stannous fluoborate, sodium stannate or potassium stannate, to obtain a tin plated steel sheet in which the amount of the plated tin is 0.05-1.12 g/m2;; and subjecting the resultant steel sheet to an immersion treatment or an electrolytic treatment in a solution containing hexavalent chromium ions or hexavalent chromium ions and at least one member selected from the group consisting of a trivalent chromium compound, a sulfur compound, a fluorine compound and a phosphorus compound to form an upper layer consisting essentially of hydrated chromium oxide in an amount of 0.5-5 mg/m2, calculated as chromium.
2. A process for producing a steel sheet having a lower layer of tin and iron-tin alloy and an upper layer of hydrated chromium oxide having excellent weldability which comprises electrolytically tin plating a substantially clean steel sheet in an electrolyte containing stannous sulfate, stannous phenolsulfonate, stannous chloride, stannous fluoborate, sodium stannate or potassium stannate to obtain a tin plated steel sheet in which the amount of plated tin is 0.05-1.1 2 g/m2; heating said tin plated steel sheet at a temperature above or below the melting point of tin for a short time; and
subjecting the resultant steel sheet to an immersion treatment or an electrolytic treatment in a solution containing hexavalent chromium ions or hexavalent chromium ions and at least one member selected from the group consisting of a trivalent chromium compound, a sulfur compound, a fluorine compound and a phosphorous compound to form an upper layer consisting essentially of hydrated chromium oxide in an amount of 0.5-5 mg/2, calculated as chromium.
3. A process according to claims 1 or 2, wherein the electrolytic tin plating is carried out in an acidic electrolyte at a temperature of 25-600C and a current density of 5-50 A/dm2; the concentration of the stannous ion in the electrolyte is 1.5-1 5 g/l; the concentration of acid, calculated as sulfuric acid, in the electrolyte being 1.5-1 5 g/l; and wherein the electrolyte contains ethoxylated a- naphtholsulfonic acid in a concentration of 1-6 g/l.
4. A process according to claims 1 or 2, wherein the electrolytic tin plating is carried out in an alkaline electrolyte at a temperature of 70-900C and a current density of 1-10 A/dm2; the concentration of the stannic ions in the electrolyte is 30-70 gIl; and wherein the concentration of alkaline material in the electrolyte is 10-25 g/l.
5. A process according to claim 2, wherein the heating of said tin plated steel sheet is carried out at a temperature of 1 50-3000C for 0.5-1 0 seconds.
6. A process according to claim 1 or 2, wherein the upper layer is formed by an immersion carried out at a temperature of 35-600C and an immersion time of 0.1-10 seconds in an aqueous containing 5-50 g/l of hexavalent chromium ions, said aqueous solution having a pH of 1-6.
7. A process according to claims 1 or 2, wherein the upper layer is formed by an immersion treatment carried out at a temperature of 35-600C and at an immersion time of 0.1-10 seconds in an aqueous solution having a pH of 1-6 and containing 5-50 g/l of hexavalent chromium ions and at least one additive selected from the group consisting of a trivalent chromium compound, a sulfur compound, a fluorine compound and a phosphor compound, said additive being present in an amount of 1/10--1/1 50 based on the amount of hexavalent chromium ions in the aqueous solution.
8. A process according to claims 1 or 2, wherein the upper layer is formed by an electrolytic treatment carried out at a temperature of 35-600C and at a quantity of electricity below 10 coulombs/dm2, under a current density of 5-50 Aids2 and in an aqueous solution having a pH of 1-6 and containing 5-50 g/l of hexavalent chromium ions.
9. A process according to claims 1 or 2, wherein the upper layer is formed by an electrolytic treatment carried out at a temperature of 35-600C and at a quantity of electricity below 10 coulombs/dm2, under a current density of 5-50 A/dm2 and in an aqueous solution having a pH of 1-6 and containing 5-50 g/l of hexavalent chromium ions and at least one additive selected from the group consisting of a trivalent chromium compound, a sulfur compound, a fluorine compound and a phosphorous compound which additive is present in an amount of 1/1 0--l/l 50 based on the amount of hexavalent chromium ions in the aqueous solutions.
10. A process according to claims 1 or 2, wherein said trivalent chromium compound is selected from the group consisting of chromium sulfate, chromium ammonium sulfate, chromium hydroxide and a product formed by the electrolytic reduction of hexavalent chromium ions or by the addition of alcohol or hydrogen peroxide.
11. A process according to claims 1 or 2, wherein said sulfur compound is selected from the group consisting of sulfuric acid, 2,4-disulfophenol, 3,5-disulfocatechol, 3,6-disulfonaphtho-2-0 1, 3,6-disulfo- 1, 8-dihydroxynaphthalene, and ammonium, or alkali metal salts thereof, and a sulfite or a thiocyanate of an ammonium or alkali metal.
12. A process according to claims 1 or 2, wherein said fluorine compound is selected from the group consisting of HF, NaF, KF, NH4F, H2SiF6, Na2SiF6, K2SiF6, (NH4)2SiF6, HBF4, NaBF4, KBF4, NaHF2,
KHF2, NH4HF2 and Na3AIF6.
13. A process according to claims 1 or 2, wherein said phosphorus compound is selected from the group consisting of phosphoric acid, pyrophosphoric acid, and a phosphate, or a pyrophosphate of ammonium or alkali metals.
14. A steel sheet having a lower layer of tin and an upper layer of a hydrated chromium oxide produced according to the process of any one of the preceding claims, and cans made therefrom.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3343380A JPS56130487A (en) | 1980-03-18 | 1980-03-18 | After-treatment for extra-thin tin-plated steel sheet for welding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2071699A true GB2071699A (en) | 1981-09-23 |
| GB2071699B GB2071699B (en) | 1983-04-13 |
Family
ID=12386398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8104043A Expired GB2071699B (en) | 1980-03-18 | 1981-02-10 | Production of tin plated steel sheet |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS56130487A (en) |
| CA (1) | CA1179628A (en) |
| DE (1) | DE3106014C2 (en) |
| FR (1) | FR2478680A1 (en) |
| GB (1) | GB2071699B (en) |
| IT (1) | IT1143523B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102308026B (en) * | 2009-02-04 | 2015-02-18 | 新日铁住金株式会社 | Method for producing tin-plated steel sheet |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4511631A (en) * | 1984-04-13 | 1985-04-16 | Toyo Kohan Co., Ltd. | Metallic chromium-nickel-hydrated chromium oxide-coated tin free steel and process for the production thereof |
| NL189310C (en) * | 1984-05-18 | 1993-03-01 | Toyo Kohan Co Ltd | COATED STEEL SHEET WITH IMPROVED WELDABILITY AND METHOD FOR MANUFACTURING. |
| JPS62124296A (en) * | 1985-11-25 | 1987-06-05 | Toyo Kohan Co Ltd | Surface treated steel sheet having excellent seam weldability and paint adhesiveness and its production |
| JPS6376896A (en) * | 1986-09-18 | 1988-04-07 | Nippon Steel Corp | Production of surface-treated steel sheet having excellent seam weldability and corrosion resistance |
| FR2687693B1 (en) * | 1992-02-25 | 1994-05-27 | Lorraine Laminage | METHOD OF SURFACE TREATMENT OF A PRODUCT FORMED OF A METAL SUBSTRATE COMPRISING A MULTILAYERED METAL COATING AND AN ORGANIC COATING AND PRODUCTS OBTAINED BY THIS PROCESS. |
| CN104099646B (en) * | 2014-06-25 | 2016-08-17 | 武汉钢铁(集团)公司 | Electroplating additive for stannous fluoboric acid system |
| CN104099649B (en) * | 2014-06-25 | 2016-08-24 | 武汉钢铁(集团)公司 | Passivator for electrolytic tinplate |
| EP3933075A4 (en) * | 2019-03-01 | 2022-10-19 | Schaeffler Technologies AG & Co. KG | Method for processing surface of steel member, and steel member |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB535570A (en) * | 1939-02-23 | 1941-04-15 | Spirito Mario Viale | Improved breach mechanism for guns |
| BE487191A (en) * | 1948-10-27 | |||
| GB819305A (en) * | 1955-11-07 | 1959-09-02 | Ekco Products Company | Improvements in or relating to anodic treatment of tin and tin alloys |
| NL288587A (en) * | 1962-02-05 | |||
| US3282744A (en) * | 1963-05-08 | 1966-11-01 | Lubrizol Corp | Chromate conversion coating |
| BE752901A (en) * | 1969-07-09 | 1971-01-04 | Uss Eng & Consult | IRON-WHITE WITH DIFFERENTIAL PROTECTION |
| US3755018A (en) * | 1971-04-26 | 1973-08-28 | Eltzroth & Ass J M | Composition and process for inhibiting corrosion of non-ferrous metal surfaced articles and providing receptive surface for synthetic resin coating compositions |
| US3890164A (en) * | 1973-07-09 | 1975-06-17 | Kawasaki Steel Co | Surface treatment of tinplate for improving sulfur resistance |
| JPS5323833A (en) * | 1976-08-18 | 1978-03-04 | Toyo Kohan Co Ltd | Surface treated steel sheet for coating |
| JPS5326236A (en) * | 1976-08-25 | 1978-03-10 | Toyo Kohan Co Ltd | Surface treated steel sheet for coating |
| LU77061A1 (en) * | 1977-04-01 | 1979-01-18 | ||
| JPS54142135A (en) * | 1978-04-28 | 1979-11-06 | Nippon Kokan Kk <Nkk> | Tin-plated steel plate and its manufacture |
| JPS55131198A (en) * | 1979-03-30 | 1980-10-11 | Toyo Kohan Co Ltd | Electrolytic chromic acid treating steel sheet for adhesion can |
| JPS55134197A (en) * | 1979-04-05 | 1980-10-18 | Toyo Kohan Co Ltd | Electrolytic chromic acid treating steel sheet for adhesion can |
-
1980
- 1980-03-18 JP JP3343380A patent/JPS56130487A/en active Pending
-
1981
- 1981-02-10 GB GB8104043A patent/GB2071699B/en not_active Expired
- 1981-02-16 FR FR8103042A patent/FR2478680A1/en active Granted
- 1981-02-18 DE DE3106014A patent/DE3106014C2/en not_active Expired
- 1981-02-20 IT IT67239/81A patent/IT1143523B/en active
- 1981-03-11 CA CA000372719A patent/CA1179628A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102308026B (en) * | 2009-02-04 | 2015-02-18 | 新日铁住金株式会社 | Method for producing tin-plated steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3106014C2 (en) | 1985-06-20 |
| DE3106014A1 (en) | 1981-12-24 |
| CA1179628A (en) | 1984-12-18 |
| GB2071699B (en) | 1983-04-13 |
| IT8167239A0 (en) | 1981-02-20 |
| FR2478680B1 (en) | 1984-06-22 |
| IT1143523B (en) | 1986-10-22 |
| FR2478680A1 (en) | 1981-09-25 |
| JPS56130487A (en) | 1981-10-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960210 |