CA1179628A - Steel sheet with thin tin electroplate and hydrated chromium oxide - Google Patents
Steel sheet with thin tin electroplate and hydrated chromium oxideInfo
- Publication number
- CA1179628A CA1179628A CA000372719A CA372719A CA1179628A CA 1179628 A CA1179628 A CA 1179628A CA 000372719 A CA000372719 A CA 000372719A CA 372719 A CA372719 A CA 372719A CA 1179628 A CA1179628 A CA 1179628A
- Authority
- CA
- Canada
- Prior art keywords
- tin
- steel sheet
- compound
- chromium
- process according
- 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.)
- Expired
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 81
- 239000010959 steel Substances 0.000 title claims abstract description 81
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910000423 chromium oxide Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 238000007747 plating Methods 0.000 claims abstract description 28
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 24
- 239000011651 chromium Substances 0.000 claims abstract description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 23
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 21
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 10
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 10
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 9
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 phosphorus compound Chemical class 0.000 claims abstract description 7
- 229940079864 sodium stannate Drugs 0.000 claims abstract description 7
- 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 abstract description 5
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 5
- 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 abstract description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 4
- 229940044652 phenolsulfonate Drugs 0.000 claims abstract description 4
- 239000001119 stannous chloride Substances 0.000 claims abstract description 4
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000011282 treatment Methods 0.000 claims description 27
- 229940107218 chromium Drugs 0.000 claims description 23
- 235000012721 chromium Nutrition 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 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
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 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
- 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
- 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
- 239000000463 material Substances 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
- 229940035427 chromium oxide Drugs 0.000 claims 5
- 229940032330 sulfuric acid 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 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
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-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
- 229910001610 cryolite Inorganic materials 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
- 239000004922 lacquer Substances 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000003466 welding Methods 0.000 description 12
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 11
- 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 11
- 239000005029 tin-free steel Substances 0.000 description 10
- 239000005028 tinplate Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000004826 seaming Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 229940037395 electrolytes Drugs 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 4
- 229940065278 sulfur compound Drugs 0.000 description 4
- 241001600451 Chromis Species 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 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 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 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
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000005554 pickling Methods 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 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
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 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
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 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
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 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
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 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
Abstract
ABSTRACT OF THE DISCLOSURE
The disclosure describes a process for producing a steel sheet having a lower layer of tin and an upper layer of hydrated chromium oxide having excellent weldability. The process comprises electrolytically tin plating a substantially clean steel sheet in an electrolyte containing stannous sul-fate, stannous phenolsulfonate, stannous chloride, stannous fluoborate, sodium stannate or potassium stannate, to obtain a tin plated steel sheet having an amount of plated tin of 0.05 - 1.12 g/m2. Then the resultant steel is immersed 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. This steel sheet also has excellent lacquer adhesion and corrosion resist-ance after lacquering and forming.
The disclosure describes a process for producing a steel sheet having a lower layer of tin and an upper layer of hydrated chromium oxide having excellent weldability. The process comprises electrolytically tin plating a substantially clean steel sheet in an electrolyte containing stannous sul-fate, stannous phenolsulfonate, stannous chloride, stannous fluoborate, sodium stannate or potassium stannate, to obtain a tin plated steel sheet having an amount of plated tin of 0.05 - 1.12 g/m2. Then the resultant steel is immersed 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. This steel sheet also has excellent lacquer adhesion and corrosion resist-ance after lacquering and forming.
Description
9~
The present invention relates to a method for the production of an extremely thin tin plated steel sheet possess-ing excellent weldability charac-teristics. More particularly, 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.
Recently, in the field of food cans, a change has rapidly taken place from expensive electro-tin plates to cheaper tin free steel (TFS) consisting of a metallic chromium and hydrated chromium oxide. It has also been observed that there is a rapid decrease in the weight of the tin coating in electro-tin plates used to manufacture food cans. This is because the tin used for the production of tin plates is very expensive, and there is some 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 I'FS, the seaming of the can body is generally carried out with nylon adhesives by using the Toyo Seam and Mira Seam rnethods.
Nowaclays, a ~FS can body seamed by a nylon adhesive is not only used for beer and carbonated beverages, but is also used for foods, such as fruit juices (which are immediately placed after pasteurization at a temperature of 90 - 100C), or coffee, meat and fish ~which are pasteurized by hot steam at a temperature above 100C in a retort after being packed in the can at 90 - 100C)~ This is the result of the progress in the TFS manufacturing techniques and improvements of TFS films as exemplified in Laid-Open Japanese Patent Applications No.
Sho 53-58442, No. Sho 54-64034 and No. ShO 54-89946.
Laid-Open Japanese Patent Application No. Sho 53-58442, inventors: T. Nishimura, J. Morita, K. Yoshida, Y. Tsukahara and K. Koyama, entitled "Process of Producing ,~ - 1 -~7~
Electrolytic Chromic Acid Trea~ed Steel Sheet", Applicant:
Japan Steel Corporation, Date of Application: 6th November, 1976, relates to the electrolyte used in producing tin free steel having a lower layer of metallic chromium and an upper layer of hydrated chromium oxlde. After metallic chromium plating, the steel sheet is electrolysed in a chromic acid solution in which the concentration of SO4 is 0.01 ~ 0.7%
of CrO3. By the above-mentioned process, one can obtain tin free steel for cemented can body having small reduction of peel strength of adhered part aged in hot water.
Laid-Open Japanese Patent Application No. Sho 54-64034, lnventors: T. Inui, H. Kuroda, K. Hizuka and ~.
Hamano, Applicant: Toyo Kohan Co., Ltd., entitled "Pretreatment of Electrolytic Chromic Acid Treated Steel Sheet", Date of Application: 31st October 1977, relates to the pretreating of tin free steel. Prior to the cathodic electrolysis, steel sheet is subjected to an anodic electrolysis followed by cathodic electrolysis in solu~ion consisting of one or more than two kinds of chromic acid, alkaline metal, chromate or dichromate, ammonium chromate and ammonium dichromate after degreasing and pickling~ This process enable~ to obtain tin free steel for cemented can body having small reduction of peel strength of adhered part after aging in hot water.
Laid-Open Japanese Patent Application No. Sho 54-89946, inventors: M. Kamata, M. Higuchi, Y. Tsukamoto and K.
Tano, Applicant: Japan Steel Corporation, entitled "Process of Producing Electrolytically Chromated Steel Sheet Having Small Reduction of Peel Strength After Aging", Date of Application: 28th December, 1977, relates to the post treating process of electrolytically chromated steel sheet having a lower layer of metallic chromium and an upper layer of hydrated chromium oxide produced by cathodic e:Lectrolysis in ~lt~
chromic acid, chromate and dichromate solution. Af~er metallic chromium plating and rinsing, the s~eel sheet is treated in hot water at 65 ~100C, a pFI more than 4 during 0.5~,15 seconds. One can obtain tin free steel for cemented can body having small reduction of peel strength of adhered part after aging in hot water.
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 chromiurn layer and the hydrated chromium oxide layer must be mechanically or chemically removed from the TFS surface.
On the other hand, the seaming of a tin plate 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 tin plate 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/m .
A method oî seaming the tin plate can body employing organic adhesives has been also proposed, for in~stance in Laid-Open ~apanese Patent Application No. Sho 49~3782 9 and Japanese Patent Publiaation No. 5ho 48-18929, Laid-Open Japanese Patent ~pplication No. Sho 49-3782 9, inventors: H. Eotta and T. Mori, Applicant: K. Yoshizaki, entitled "Tin Plated Steel Sheet Having Excellent Adhesive Strength", Date of Application: 11th August, 1972, relates to tin plated steel sheet for cemented can body having high ad-hesive strength, The surface of tin plated steel consists of metallic tin and iron-tin alloy of which the area of exposed iron-tin alloy is more than 30% of the total surface area. One can obtain tin plated steel sheet for cemented can having high adhesive strength using the above-mentioned tin plated steel sheet.
11'7~
` Japanese Patent Publication No. Sho 48-18929, inventor: H. ~Io-tta, AppLicant. K. Yoshizaki, entitled "Process for Adhering Tin Plated Steel Sheet with Organic Adhesive", Date of Application: 4th December, 1969, relates to a process for producing a cemented can body using a tin plated steel sheet and a linear polyamide having a lower melting point than that of tin after base coating and curing.
The tin plate used has a hydrated chromium oxide layex of 3 ~20 ~g/dm2 and a tin oxide layer of 160 ~640 mc/dm2 equi-valent to the amount of electricity required for the reduct-ion of tin oxide to tin, and a base coating lacquer made of 20 ~40 parts of resol type phenolic resin and 80~ 60 parts of epoxy resin. This process enables to obtain a cemented can body having high peel strength more than 20 kg/cm.
However, after a few months, the tin plate can body seamed by an organic adhesive may be broken, because the b~nd-ing strength in the seam becomes quite low.
In view of t'he above, a lap seam welding, for in-stance, one obtained by the SoudronicrM process 'has recently been proposed as a new met'hod of seaming the tin plate can body.
The Soudronic process involves the continuous production of cans by means of electrically resistant seam welding. After rounding the blank sheet, the overlapping ends are joined by electrical heating using alternating current between two copper wires serving as electrodes. 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 with a decrease of the tin coating weight, the weld-ability of the tin plate becomes poor.
It is an object of the present invention to provide a method for the production of an extremely thin tin plated ~teel sheet having excellent weldab:ility as well as excellent _ a, ~t7~ 8 lacquer adhesion and corrosion resistance after lac~uering and forming.
This object can be accomplished by the formation of a uniform hydrated chromium oxide layer containing from 0.5 to 5 mg/m , calculated as chromiurn, 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/m .
It is another objec~ of the present invention to provide a process for producing a stee1 sheet having a lower layer of tin and an upper layer of hydrated chromium oxide, said steel sheet having excellent weldability, which comprises electrolytically tin plating a substantially clean steel sheet in an electrolyte containing a compound selected from the group consisting of stannsus sulfate, stannous phenolsulfonate, stannous chloride, stannous fluoborate, sodium stannate and potassium stannate, to obtain a tin plated steel sheet having an amount of plated tin of 0.05 - 1.12 g/m2, and subjecting the resultant steel sheet to a treatment in a solution con-taining hexavalent chromium ions, or hexavalent chromium ions and at l.east one member selected from the g:roup consisting of a trivalent chromium compound, a sul-fur compound, a fluorine compound and a pho~phorus compound to form an upper layer - consisting essentially of hydrated chromium oxide in an amount of 0.5 - 5 mg/m , calculated as chromium.
As a result of investigations on the weldability of extrernely thin tin plated steel sheets having a hydrated chromium oxide layer fonned by treatment of the tin coated steel sheet in a solution containing mainly hexavalent chromi~un ions, it has been determined that the ~eldability of said tin .plated steel sheet by the Soudronic process depends on the amount of hydrated chromi~m oxide, calculated as chromiuml on said thin tin plated steel sheet. The weldability is improved ~7'3~
with a decrease of the amount o~ hydrated chromium oxide, as chromiu~, particularly in the case of a thin tin plated steel -- sheet.
It is assumed that the effect of the arnount of hydrated chromium oxide, based on the amount of chromium, can be neglected in the case when the tin coating weight is in-creased, because a large amount of tin which is present under - the hydrated chromium oxide layer is melted during welding, and in the case of a weight decrease of the tin coating, the amount of hydrated chromium oxide as-chromium affects the weldability, because the thin tin layer is immediately converted 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 w~ldability 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 khin tin plating step, which is necessary for the format:ion of a uniform and thin hydrated chromium oxide layer on said thin tin plated steel sheet.
In the present invention, a method for the production of a thin tin plated steel sheet comprises, as the only essen-tial 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 inve~tion can be carried out according to the follow-ing process: degreasing with an alkali and pickling with an acid -~ water rlnsing ~ very thin electrolytic tin plating --~water rinsing --~ chromic acid treatment ~ water rinsing_-~drying.
~; - 5a -~1~7~
In some cas~s, the heating of the very thin tin plated steel sheet at a temperature below or abo~e the meltiny 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 according to the present invention, a known tin plating electrolyte may be e~ployed, for exarnple, an acidic electrolyte, such as - stannous sulfate, a stannous aromatic sulfonate, stannous fluoborate~and stannous chIoride, an alkaline electrolyte, such as sodium stannate and potassium stannate; or a neutral electrolyte such as stannous sul~ate containing a carboxylic acid additive'may be employed. For the formation of a dense tin layer according to the present invention it is preferable to use the known alkaline electrolytes or the weakly acidic electrolytes having a low concentration of stannous ions (described in Japanese Patent Application ~o. Sho 46-25603, Laid-Open Japane~e Patenk Application ~. Sho 55-73887), especially an improved alkaline electrolyte (describ~d in Laid-Open Japanese Patent Application No~ Sho 54-117332), in which a considerable arnount of hydrogen gas is generated.
Japanese Patent Publication ~o. Sho 46-25603, .inventors: T. O~ama, A. Miyachi and T~ Kikuta, Applicant:
Toyo Kohan Co., Ltd., entitled "Acidic Tin Preplating Process", Date of Application: l9th April, 1967, relates to a process of preplating tin in acidic solution. Prior to tin plating in acidic solution, preplaking is carried out in acidic solution containing stannous ion of 1.6 ~ 15 g~l and acid equivalent to sulfuric acid of 1 ~ 9.5 g/l. Thi.s process enables to obtain a tin plat~ having excellent corrosion resistance.
Laid-Open Japanese Patent Application Nc. Sho 55-73887, inventors: T. Inui, H. Kuroda, T. Hanafusa and K.
Yazaki, Applicant: Toyo Kohan Co., Ltd~, entitled "Acidic - 5b -~ 17 ~.3~ ~
Tin Plating Bath, Dake of Application: 27th November, 1978, relates to a tin plating bath consisting of surface or phenolic sul~onate bath containing 1.5~50 g/l of stannous ion' the bath contains one or more than two kinds of sulfate of alkaline metal, aluminum, ammonium, manganese and chrom-ium in the range of 5 ~150 g/l. This acidic bath enables to obtain fine and dense deposition of tin.
Laid-Open Japanese Patent Application No. Sho 54-117332, inventors: T. Inui, H. Kuroda, F. Kunishige and K. Hakota, Applicant: Toyo Kohan Co., Ltd.r entitled "Alkaline Tin Plating Bath, Date of Application: 6th March, 1978, relates to a tin plating bath consisting of stannate and hydroxide of alkaline metal; the bath contains one or more than two kinds of aluminate, borate, molybdate, tungstate, chromate, dichromate of alkaline metal or ammoniu~. With the above~mentioned alkaline bath, one can obtain fine and dense depositîon of tin and also fine and dense iron-tin alloy a~ter heating. The lacquer adhesion and corrosion resistance of the tin plate using the bath described in this invention are higher than that o~ tin plate without additives.
According to the present invention, the following electrolytic tin plating conditions are employed when an acidic electrolyte is used:
Concentration of stannous ions: 1~5 - 15 g/l Concentration o~ free acid (as ~ H2SO4): 1.0 - 15 g/l Concentration o~ organic addition agents, such as ethoxylated ~-naphthol sulfonic acid or cresol sulfonic acid: 1 - 6 g/l Temperature o~ the electrolyte: 25 60C
Current density: 5 - 50 A~dm _ 5c -1~7~3~2~
Generally, a lower current density is used ~or the formation of a dense tin layer at lower electrolyte temperatures, and for a lower concentration of the stannous ions. Finally, lower current densities are also used for higher concentrations of the free acid. On the contrary, when higher temperatures are employed and if there is a higher concentration of the stannous ions as well as lower concentrations of free acid, a - higher current density must be applied. Furthermore, when the concentration of the stannous ions and of the free acid are below 1.5 and 1.0 g/l, respectively, the electrical resistance of the electrolyte increases and the current efficiency during - 5d -the tin plating operation becomes very low, and therefore, such low concentrations are not suitable for the industrial produc-tion of thin tin plated steel sheets.
According to the present invention the electro-tin plating is preferably carried out at a current efficiency of 20 - 70 percent in respect to the tin deposition.
According to the present invention, the following electrolytic conditions are employedl when alkaline electro-lytes are used:
Concentration of stannic ions: 30 ~ 70 g/l Concentration of base (as NaOH or KOH): 10 - 25 g/1 Temperature of the electrolyte: 70 - 90C
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 e~ficiency of the tin plating step is lower.
Especially, the current efficiency for tin platiny decreases remarkably with an increase in the current density and a de-crease in the ternperatur~ of the electrolyte.
In the present invention, the optimurn range for the amount of plated tin is from 0.05 to 1~12 g/rn2, 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 quite poor. An increase in the amount of tin 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 o~ the tin and the thus heated plate is quenched. In this case, heating is carried out by kno~l methods such as resistance heating as is generally used in the electro-tin plating.
The hydrated chrorni~n oxide layer is forrned on the 9~
~hin tin pla-ted steel sheet, according to a cathodic treatmént or an i~nersion treatment in a known solution containing hexa-valent 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 add 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, chrom-ium hydroxide, by the addition of a reducing agent such as an alcohol and hydrogen peroxide or by an electrolytic 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 sul~ite, a thiocyanate, or an aromatic disulfonate of a~nonium and alkali metals and thiourea.
The fluorine compound is selected from the group consisting of hydrofluoric acid, a hydrofluoboric acid, a hydrofluosilicic acid, a fluoride, a borofluoride, or a silicofluoride of ammonium and alkali metals. The phosphorus compound is select-ed from the group o~ phosphoric acid, pyro-phosphoric acid, a phosphate, or a pyrophosphate of ammonium and alkali metals.
In the case of an immersion treatmen-t of the thin tin plated steel sheet, it is desirable to control the pH of the solution below 6, and to provide for an irnmerslon 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 ~7~28 treatment using an aqueous solution containing hexavalent chromium ions.
However, according to the present inven~ion, an anod ic treatment, an anodic treatment after a cathodlc treatment or a cathodic treatment after an anodic treatment is also applied for the treatment of the thin tin plated st,eel sheet.
Furthermore, it is poss.ible to repeat these treatments several times. As a matter of practical application, a quantity of electricity below 10 coulombs/dm2 is sufficient for the forma-tion of the hydrated chromium oxide having less then 5 mg/m2 as chromium on the thin tin plated steel sheet, although the quantity of electricity depends on the composition of the elec-trolyte, the pH of the electrolyte, the temperature of the electrolyte and the sur-face conditions of the tin plated steel sheet.
The conditions for the formation of the hydrated chromiurn oxide are surnmarized as f~llows:
Concentration of hexavalent chromium .ion~: 5 - 50 g/l pH of solution: 1 - 6 Temperature of ~olution: 35 - 60C
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 phosphorous compound in some cases: 1/10 - 1jl50 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 mg/m2, preferably 0.5 - 3 rng/m2, calculated as chromium. If the amount of hydrated chromium oxide calculated as chromium, is above 5 mg/m2, the weldability is decreased.
~1'7~
Generally, the weldabllity is i~proved when the amount of hydrated chromium oxide is decreased because the sur-face 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 substantially decreased.
It is very important according to the present inven-tion that a thln and uniform hydrated chromium oxide layer be formed on the thin tin plated steel sheet in order to achieve all the properties including excellent weldability, corrosion resistance after lacquering, forming as well as excellent lacquer adhesion. It has been found that the uniformity of the formed hydrated chromium oxide layer depends on the uni-formity and denseness of the tin layer to be trea-ted, although it is also affected by the conditions used in the formation of the hydrated chromium oxide. I~lat is to say, in the case when the plated tin layer does not sufficiently cover the sur-face of the steel sheet, the hydrated chromium oxide layer formed on tin plated steel sheet is not uniform and shows a network like structure~
Therefore, it is very :important according to the present invention that the steel sheet be subjected to a dense and uniform tin plating by using the known alkaline electro lytes or the weakly acidic electrolytes having a low concentra-tion 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.
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 ~ ~'f'~3 ~ ~ ~
sheet, after beiny rinsed with water, was electroplated with tin under the ~ollowing plating conditions and then rinsed with water and dried.
Composition of electrolyte:
Stannous sulfate: 5 g/l Phenolsulfonic acid (60% a~ueous solution): 20 g/l Ethoxylated ~-naphthol sulfonic acid: 5 g/l Bath temperature: 40C
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 the steel sheet was treated by immersiny it into the following solution:
Composition of solution:
Chromic acid: 25 g/l Sodiwm hydroxide: 10 g/l Bath temperature: 40~C
Chromium weight in hydrated chromium oxide: 1.4 mg/m2 A steel sheet pre treated as in Example 1 was elec-troplated with tin under the following plating conditions after which it was rinsed with water and dried:
Composition of electrolyte:
Sodium stannate: 80 g/l Sodium hydroxide: 20 g/l Bath temperature: 85~C
Cathodic current density: 15 A/dm2 Tin coating weight: 0.39 y/m2 After that, the tin coated steel sheet w~s heated at 210C, and then was treated by immersing it into the following solution:
3~
Composition of solution:
Chromic acid: 30 g/l Sodium fluoride: 0.5 g/l Bath temperature: 50C
Chromium weight in hydrated chromi~n oxide: 0.7 mg/m2 EXAMPLE_3 A steel sheet pre~treated as in Example l was elec-troplated with tin under the following plating conditions after which it was rinsed with water and dried:
lOComposition of electrolyte:
, Sodium stannate: 70 g/l Sodium hydroxide: 15 g/l Sodium aluminate: 40 g/l Bath temperature: 85C
; ~athodic current density: 5 A/dm2 ~in coating weight: ~-24 g/m2 Af-~er that, tin on the steel sheet was melted by using resistance heating, and khen the steel sheet was cathod ically treated under the following conditions, and rinsed with water and dried:
Composikion of electrolyte:
Sodium dichromate: 30 g/l Bath temperature~ 40~C
Cathodic current density: 5 A/drn Chromium weight in hydrated chromium oxide: 2.3 mg/m2 COMPARATIVE ExAMæLE 1 A steel sheet pre-treated as in Example 1 was elec-troplated with tin of 0.25 g/m2 under the same conditions as in Example l. After rinsing with water, and drying, the tin on the coated steel sheet was reflowed by using resi.stance heating and then was cathodically treated under the same conditions as in Exarn~le 1 for the formation of hydrated chromium oxide on the tin coated steel sheet in an arnount of 6.1 mg/m2, calculat-ed as chromium. After that, the treated steel sheet was rinsed , - -~
~ ~9~
with water and dried.
COMRARATIVE EXAMP~E 2 A steel sheet pre-treated as in Exarnple 1, was electroplated with tin in an amount of 0~56 g/m2 under the same conditions as in Example 1. After rinsing with waterl the tin coated steel sheet was cathodically treated, undsr 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/m~.
After that, the treated steel sheet was rinsed with water and dried.
The weldability, corrosion resistance and lacquer adhesion of the thus treaked steel sheet in the above described Examples and Comparative E~arnples were evaluated by the follow-ing testing methods, the results of which are shown in the attached Table.
(1) Weldability The weldability was evaluated by using a welding test machine which is similar to the 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 ranye 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 rnetal or welded part by tearing tests.
This weldability is judged by the method of Williams, - 1~
that is to say, the wider the secondary current range in wel~-ing, the better the weldability.
The present invention relates to a method for the production of an extremely thin tin plated steel sheet possess-ing excellent weldability charac-teristics. More particularly, 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.
Recently, in the field of food cans, a change has rapidly taken place from expensive electro-tin plates to cheaper tin free steel (TFS) consisting of a metallic chromium and hydrated chromium oxide. It has also been observed that there is a rapid decrease in the weight of the tin coating in electro-tin plates used to manufacture food cans. This is because the tin used for the production of tin plates is very expensive, and there is some 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 I'FS, the seaming of the can body is generally carried out with nylon adhesives by using the Toyo Seam and Mira Seam rnethods.
Nowaclays, a ~FS can body seamed by a nylon adhesive is not only used for beer and carbonated beverages, but is also used for foods, such as fruit juices (which are immediately placed after pasteurization at a temperature of 90 - 100C), or coffee, meat and fish ~which are pasteurized by hot steam at a temperature above 100C in a retort after being packed in the can at 90 - 100C)~ This is the result of the progress in the TFS manufacturing techniques and improvements of TFS films as exemplified in Laid-Open Japanese Patent Applications No.
Sho 53-58442, No. Sho 54-64034 and No. ShO 54-89946.
Laid-Open Japanese Patent Application No. Sho 53-58442, inventors: T. Nishimura, J. Morita, K. Yoshida, Y. Tsukahara and K. Koyama, entitled "Process of Producing ,~ - 1 -~7~
Electrolytic Chromic Acid Trea~ed Steel Sheet", Applicant:
Japan Steel Corporation, Date of Application: 6th November, 1976, relates to the electrolyte used in producing tin free steel having a lower layer of metallic chromium and an upper layer of hydrated chromium oxlde. After metallic chromium plating, the steel sheet is electrolysed in a chromic acid solution in which the concentration of SO4 is 0.01 ~ 0.7%
of CrO3. By the above-mentioned process, one can obtain tin free steel for cemented can body having small reduction of peel strength of adhered part aged in hot water.
Laid-Open Japanese Patent Application No. Sho 54-64034, lnventors: T. Inui, H. Kuroda, K. Hizuka and ~.
Hamano, Applicant: Toyo Kohan Co., Ltd., entitled "Pretreatment of Electrolytic Chromic Acid Treated Steel Sheet", Date of Application: 31st October 1977, relates to the pretreating of tin free steel. Prior to the cathodic electrolysis, steel sheet is subjected to an anodic electrolysis followed by cathodic electrolysis in solu~ion consisting of one or more than two kinds of chromic acid, alkaline metal, chromate or dichromate, ammonium chromate and ammonium dichromate after degreasing and pickling~ This process enable~ to obtain tin free steel for cemented can body having small reduction of peel strength of adhered part after aging in hot water.
Laid-Open Japanese Patent Application No. Sho 54-89946, inventors: M. Kamata, M. Higuchi, Y. Tsukamoto and K.
Tano, Applicant: Japan Steel Corporation, entitled "Process of Producing Electrolytically Chromated Steel Sheet Having Small Reduction of Peel Strength After Aging", Date of Application: 28th December, 1977, relates to the post treating process of electrolytically chromated steel sheet having a lower layer of metallic chromium and an upper layer of hydrated chromium oxide produced by cathodic e:Lectrolysis in ~lt~
chromic acid, chromate and dichromate solution. Af~er metallic chromium plating and rinsing, the s~eel sheet is treated in hot water at 65 ~100C, a pFI more than 4 during 0.5~,15 seconds. One can obtain tin free steel for cemented can body having small reduction of peel strength of adhered part after aging in hot water.
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 chromiurn layer and the hydrated chromium oxide layer must be mechanically or chemically removed from the TFS surface.
On the other hand, the seaming of a tin plate 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 tin plate 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/m .
A method oî seaming the tin plate can body employing organic adhesives has been also proposed, for in~stance in Laid-Open ~apanese Patent Application No. Sho 49~3782 9 and Japanese Patent Publiaation No. 5ho 48-18929, Laid-Open Japanese Patent ~pplication No. Sho 49-3782 9, inventors: H. Eotta and T. Mori, Applicant: K. Yoshizaki, entitled "Tin Plated Steel Sheet Having Excellent Adhesive Strength", Date of Application: 11th August, 1972, relates to tin plated steel sheet for cemented can body having high ad-hesive strength, The surface of tin plated steel consists of metallic tin and iron-tin alloy of which the area of exposed iron-tin alloy is more than 30% of the total surface area. One can obtain tin plated steel sheet for cemented can having high adhesive strength using the above-mentioned tin plated steel sheet.
11'7~
` Japanese Patent Publication No. Sho 48-18929, inventor: H. ~Io-tta, AppLicant. K. Yoshizaki, entitled "Process for Adhering Tin Plated Steel Sheet with Organic Adhesive", Date of Application: 4th December, 1969, relates to a process for producing a cemented can body using a tin plated steel sheet and a linear polyamide having a lower melting point than that of tin after base coating and curing.
The tin plate used has a hydrated chromium oxide layex of 3 ~20 ~g/dm2 and a tin oxide layer of 160 ~640 mc/dm2 equi-valent to the amount of electricity required for the reduct-ion of tin oxide to tin, and a base coating lacquer made of 20 ~40 parts of resol type phenolic resin and 80~ 60 parts of epoxy resin. This process enables to obtain a cemented can body having high peel strength more than 20 kg/cm.
However, after a few months, the tin plate can body seamed by an organic adhesive may be broken, because the b~nd-ing strength in the seam becomes quite low.
In view of t'he above, a lap seam welding, for in-stance, one obtained by the SoudronicrM process 'has recently been proposed as a new met'hod of seaming the tin plate can body.
The Soudronic process involves the continuous production of cans by means of electrically resistant seam welding. After rounding the blank sheet, the overlapping ends are joined by electrical heating using alternating current between two copper wires serving as electrodes. 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 with a decrease of the tin coating weight, the weld-ability of the tin plate becomes poor.
It is an object of the present invention to provide a method for the production of an extremely thin tin plated ~teel sheet having excellent weldab:ility as well as excellent _ a, ~t7~ 8 lacquer adhesion and corrosion resistance after lac~uering and forming.
This object can be accomplished by the formation of a uniform hydrated chromium oxide layer containing from 0.5 to 5 mg/m , calculated as chromiurn, 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/m .
It is another objec~ of the present invention to provide a process for producing a stee1 sheet having a lower layer of tin and an upper layer of hydrated chromium oxide, said steel sheet having excellent weldability, which comprises electrolytically tin plating a substantially clean steel sheet in an electrolyte containing a compound selected from the group consisting of stannsus sulfate, stannous phenolsulfonate, stannous chloride, stannous fluoborate, sodium stannate and potassium stannate, to obtain a tin plated steel sheet having an amount of plated tin of 0.05 - 1.12 g/m2, and subjecting the resultant steel sheet to a treatment in a solution con-taining hexavalent chromium ions, or hexavalent chromium ions and at l.east one member selected from the g:roup consisting of a trivalent chromium compound, a sul-fur compound, a fluorine compound and a pho~phorus compound to form an upper layer - consisting essentially of hydrated chromium oxide in an amount of 0.5 - 5 mg/m , calculated as chromium.
As a result of investigations on the weldability of extrernely thin tin plated steel sheets having a hydrated chromium oxide layer fonned by treatment of the tin coated steel sheet in a solution containing mainly hexavalent chromi~un ions, it has been determined that the ~eldability of said tin .plated steel sheet by the Soudronic process depends on the amount of hydrated chromi~m oxide, calculated as chromiuml on said thin tin plated steel sheet. The weldability is improved ~7'3~
with a decrease of the amount o~ hydrated chromium oxide, as chromiu~, particularly in the case of a thin tin plated steel -- sheet.
It is assumed that the effect of the arnount of hydrated chromium oxide, based on the amount of chromium, can be neglected in the case when the tin coating weight is in-creased, because a large amount of tin which is present under - the hydrated chromium oxide layer is melted during welding, and in the case of a weight decrease of the tin coating, the amount of hydrated chromium oxide as-chromium affects the weldability, because the thin tin layer is immediately converted 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 w~ldability 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 khin tin plating step, which is necessary for the format:ion of a uniform and thin hydrated chromium oxide layer on said thin tin plated steel sheet.
In the present invention, a method for the production of a thin tin plated steel sheet comprises, as the only essen-tial 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 inve~tion can be carried out according to the follow-ing process: degreasing with an alkali and pickling with an acid -~ water rlnsing ~ very thin electrolytic tin plating --~water rinsing --~ chromic acid treatment ~ water rinsing_-~drying.
~; - 5a -~1~7~
In some cas~s, the heating of the very thin tin plated steel sheet at a temperature below or abo~e the meltiny 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 according to the present invention, a known tin plating electrolyte may be e~ployed, for exarnple, an acidic electrolyte, such as - stannous sulfate, a stannous aromatic sulfonate, stannous fluoborate~and stannous chIoride, an alkaline electrolyte, such as sodium stannate and potassium stannate; or a neutral electrolyte such as stannous sul~ate containing a carboxylic acid additive'may be employed. For the formation of a dense tin layer according to the present invention it is preferable to use the known alkaline electrolytes or the weakly acidic electrolytes having a low concentration of stannous ions (described in Japanese Patent Application ~o. Sho 46-25603, Laid-Open Japane~e Patenk Application ~. Sho 55-73887), especially an improved alkaline electrolyte (describ~d in Laid-Open Japanese Patent Application No~ Sho 54-117332), in which a considerable arnount of hydrogen gas is generated.
Japanese Patent Publication ~o. Sho 46-25603, .inventors: T. O~ama, A. Miyachi and T~ Kikuta, Applicant:
Toyo Kohan Co., Ltd., entitled "Acidic Tin Preplating Process", Date of Application: l9th April, 1967, relates to a process of preplating tin in acidic solution. Prior to tin plating in acidic solution, preplaking is carried out in acidic solution containing stannous ion of 1.6 ~ 15 g~l and acid equivalent to sulfuric acid of 1 ~ 9.5 g/l. Thi.s process enables to obtain a tin plat~ having excellent corrosion resistance.
Laid-Open Japanese Patent Application Nc. Sho 55-73887, inventors: T. Inui, H. Kuroda, T. Hanafusa and K.
Yazaki, Applicant: Toyo Kohan Co., Ltd~, entitled "Acidic - 5b -~ 17 ~.3~ ~
Tin Plating Bath, Dake of Application: 27th November, 1978, relates to a tin plating bath consisting of surface or phenolic sul~onate bath containing 1.5~50 g/l of stannous ion' the bath contains one or more than two kinds of sulfate of alkaline metal, aluminum, ammonium, manganese and chrom-ium in the range of 5 ~150 g/l. This acidic bath enables to obtain fine and dense deposition of tin.
Laid-Open Japanese Patent Application No. Sho 54-117332, inventors: T. Inui, H. Kuroda, F. Kunishige and K. Hakota, Applicant: Toyo Kohan Co., Ltd.r entitled "Alkaline Tin Plating Bath, Date of Application: 6th March, 1978, relates to a tin plating bath consisting of stannate and hydroxide of alkaline metal; the bath contains one or more than two kinds of aluminate, borate, molybdate, tungstate, chromate, dichromate of alkaline metal or ammoniu~. With the above~mentioned alkaline bath, one can obtain fine and dense depositîon of tin and also fine and dense iron-tin alloy a~ter heating. The lacquer adhesion and corrosion resistance of the tin plate using the bath described in this invention are higher than that o~ tin plate without additives.
According to the present invention, the following electrolytic tin plating conditions are employed when an acidic electrolyte is used:
Concentration of stannous ions: 1~5 - 15 g/l Concentration o~ free acid (as ~ H2SO4): 1.0 - 15 g/l Concentration o~ organic addition agents, such as ethoxylated ~-naphthol sulfonic acid or cresol sulfonic acid: 1 - 6 g/l Temperature o~ the electrolyte: 25 60C
Current density: 5 - 50 A~dm _ 5c -1~7~3~2~
Generally, a lower current density is used ~or the formation of a dense tin layer at lower electrolyte temperatures, and for a lower concentration of the stannous ions. Finally, lower current densities are also used for higher concentrations of the free acid. On the contrary, when higher temperatures are employed and if there is a higher concentration of the stannous ions as well as lower concentrations of free acid, a - higher current density must be applied. Furthermore, when the concentration of the stannous ions and of the free acid are below 1.5 and 1.0 g/l, respectively, the electrical resistance of the electrolyte increases and the current efficiency during - 5d -the tin plating operation becomes very low, and therefore, such low concentrations are not suitable for the industrial produc-tion of thin tin plated steel sheets.
According to the present invention the electro-tin plating is preferably carried out at a current efficiency of 20 - 70 percent in respect to the tin deposition.
According to the present invention, the following electrolytic conditions are employedl when alkaline electro-lytes are used:
Concentration of stannic ions: 30 ~ 70 g/l Concentration of base (as NaOH or KOH): 10 - 25 g/1 Temperature of the electrolyte: 70 - 90C
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 e~ficiency of the tin plating step is lower.
Especially, the current efficiency for tin platiny decreases remarkably with an increase in the current density and a de-crease in the ternperatur~ of the electrolyte.
In the present invention, the optimurn range for the amount of plated tin is from 0.05 to 1~12 g/rn2, 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 quite poor. An increase in the amount of tin 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 o~ the tin and the thus heated plate is quenched. In this case, heating is carried out by kno~l methods such as resistance heating as is generally used in the electro-tin plating.
The hydrated chrorni~n oxide layer is forrned on the 9~
~hin tin pla-ted steel sheet, according to a cathodic treatmént or an i~nersion treatment in a known solution containing hexa-valent 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 add 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, chrom-ium hydroxide, by the addition of a reducing agent such as an alcohol and hydrogen peroxide or by an electrolytic 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 sul~ite, a thiocyanate, or an aromatic disulfonate of a~nonium and alkali metals and thiourea.
The fluorine compound is selected from the group consisting of hydrofluoric acid, a hydrofluoboric acid, a hydrofluosilicic acid, a fluoride, a borofluoride, or a silicofluoride of ammonium and alkali metals. The phosphorus compound is select-ed from the group o~ phosphoric acid, pyro-phosphoric acid, a phosphate, or a pyrophosphate of ammonium and alkali metals.
In the case of an immersion treatmen-t of the thin tin plated steel sheet, it is desirable to control the pH of the solution below 6, and to provide for an irnmerslon 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 ~7~28 treatment using an aqueous solution containing hexavalent chromium ions.
However, according to the present inven~ion, an anod ic treatment, an anodic treatment after a cathodlc treatment or a cathodic treatment after an anodic treatment is also applied for the treatment of the thin tin plated st,eel sheet.
Furthermore, it is poss.ible to repeat these treatments several times. As a matter of practical application, a quantity of electricity below 10 coulombs/dm2 is sufficient for the forma-tion of the hydrated chromium oxide having less then 5 mg/m2 as chromium on the thin tin plated steel sheet, although the quantity of electricity depends on the composition of the elec-trolyte, the pH of the electrolyte, the temperature of the electrolyte and the sur-face conditions of the tin plated steel sheet.
The conditions for the formation of the hydrated chromiurn oxide are surnmarized as f~llows:
Concentration of hexavalent chromium .ion~: 5 - 50 g/l pH of solution: 1 - 6 Temperature of ~olution: 35 - 60C
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 phosphorous compound in some cases: 1/10 - 1jl50 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 mg/m2, preferably 0.5 - 3 rng/m2, calculated as chromium. If the amount of hydrated chromium oxide calculated as chromium, is above 5 mg/m2, the weldability is decreased.
~1'7~
Generally, the weldabllity is i~proved when the amount of hydrated chromium oxide is decreased because the sur-face 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 substantially decreased.
It is very important according to the present inven-tion that a thln and uniform hydrated chromium oxide layer be formed on the thin tin plated steel sheet in order to achieve all the properties including excellent weldability, corrosion resistance after lacquering, forming as well as excellent lacquer adhesion. It has been found that the uniformity of the formed hydrated chromium oxide layer depends on the uni-formity and denseness of the tin layer to be trea-ted, although it is also affected by the conditions used in the formation of the hydrated chromium oxide. I~lat is to say, in the case when the plated tin layer does not sufficiently cover the sur-face of the steel sheet, the hydrated chromium oxide layer formed on tin plated steel sheet is not uniform and shows a network like structure~
Therefore, it is very :important according to the present invention that the steel sheet be subjected to a dense and uniform tin plating by using the known alkaline electro lytes or the weakly acidic electrolytes having a low concentra-tion 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.
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 ~ ~'f'~3 ~ ~ ~
sheet, after beiny rinsed with water, was electroplated with tin under the ~ollowing plating conditions and then rinsed with water and dried.
Composition of electrolyte:
Stannous sulfate: 5 g/l Phenolsulfonic acid (60% a~ueous solution): 20 g/l Ethoxylated ~-naphthol sulfonic acid: 5 g/l Bath temperature: 40C
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 the steel sheet was treated by immersiny it into the following solution:
Composition of solution:
Chromic acid: 25 g/l Sodiwm hydroxide: 10 g/l Bath temperature: 40~C
Chromium weight in hydrated chromium oxide: 1.4 mg/m2 A steel sheet pre treated as in Example 1 was elec-troplated with tin under the following plating conditions after which it was rinsed with water and dried:
Composition of electrolyte:
Sodium stannate: 80 g/l Sodium hydroxide: 20 g/l Bath temperature: 85~C
Cathodic current density: 15 A/dm2 Tin coating weight: 0.39 y/m2 After that, the tin coated steel sheet w~s heated at 210C, and then was treated by immersing it into the following solution:
3~
Composition of solution:
Chromic acid: 30 g/l Sodium fluoride: 0.5 g/l Bath temperature: 50C
Chromium weight in hydrated chromi~n oxide: 0.7 mg/m2 EXAMPLE_3 A steel sheet pre~treated as in Example l was elec-troplated with tin under the following plating conditions after which it was rinsed with water and dried:
lOComposition of electrolyte:
, Sodium stannate: 70 g/l Sodium hydroxide: 15 g/l Sodium aluminate: 40 g/l Bath temperature: 85C
; ~athodic current density: 5 A/dm2 ~in coating weight: ~-24 g/m2 Af-~er that, tin on the steel sheet was melted by using resistance heating, and khen the steel sheet was cathod ically treated under the following conditions, and rinsed with water and dried:
Composikion of electrolyte:
Sodium dichromate: 30 g/l Bath temperature~ 40~C
Cathodic current density: 5 A/drn Chromium weight in hydrated chromium oxide: 2.3 mg/m2 COMPARATIVE ExAMæLE 1 A steel sheet pre-treated as in Example 1 was elec-troplated with tin of 0.25 g/m2 under the same conditions as in Example l. After rinsing with water, and drying, the tin on the coated steel sheet was reflowed by using resi.stance heating and then was cathodically treated under the same conditions as in Exarn~le 1 for the formation of hydrated chromium oxide on the tin coated steel sheet in an arnount of 6.1 mg/m2, calculat-ed as chromium. After that, the treated steel sheet was rinsed , - -~
~ ~9~
with water and dried.
COMRARATIVE EXAMP~E 2 A steel sheet pre-treated as in Exarnple 1, was electroplated with tin in an amount of 0~56 g/m2 under the same conditions as in Example 1. After rinsing with waterl the tin coated steel sheet was cathodically treated, undsr 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/m~.
After that, the treated steel sheet was rinsed with water and dried.
The weldability, corrosion resistance and lacquer adhesion of the thus treaked steel sheet in the above described Examples and Comparative E~arnples were evaluated by the follow-ing testing methods, the results of which are shown in the attached Table.
(1) Weldability The weldability was evaluated by using a welding test machine which is similar to the 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 ranye 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 rnetal or welded part by tearing tests.
This weldability is judged by the method of Williams, - 1~
that is to say, the wider the secondary current range in wel~-ing, the better the weldability.
(2) Corrosion Resistance After Lacquerin~ and Forminq The sample was based at 210~C far 12 minutes af-ter coating with 50 mg/drn2 of an epoxy-phenolic type of lacquer.
The coated sar~ple was cut to a size of 15 mm x 100 mm. The test piece was bent to 180 by the drop of a 3 kg weight from a height o 150 mm, after placing a steel sheet having a thick-ness of 0.25 mm between the pre-bent test piece. The bent test piece was sealed with 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 that a 0.01 mole/l citric acid solution contain-ing 0.3 percent by weight of sodium chloride, was used. The iron pick-up in each solution was measured.
The coated sar~ple was cut to a size of 15 mm x 100 mm. The test piece was bent to 180 by the drop of a 3 kg weight from a height o 150 mm, after placing a steel sheet having a thick-ness of 0.25 mm between the pre-bent test piece. The bent test piece was sealed with 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 that a 0.01 mole/l citric acid solution contain-ing 0.3 percent by weight of sodium chloride, was used. The iron pick-up in each solution was measured.
(3) Lacquer Adhesion Two pieces of the sample were pretreated. One piece of the sample was baked at 210C for 12 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 sarne lacquer. The two pieces having a different coating, were each cut to a size of 5 mm x 100 mm, were bonded together by using a 100 ~n nylon film at 200C for 30 seconds under 3 kg/cm2 of pressure by using a hot press after preheating at 200C for 120 seconds.
The peel strength (kg/5 rMn) of the assembly was measured by a conventional tensile testing machine.
The weldability, corrosion resistance after lacquer-ing and forming and lacquer adhesion of the steel sheet obtainedby the Examples and the Comparative Exarnples were evaluated by the tests described above, the results of which are shown in the Table.
1~'7~
As it is apparent from the Table, the treated steel sheet of the present invention has excellent weldability, corrosion resistance after lacquering and forming, and excel-lent lac~uer adhesion, This treated steel sheet is therefore quite suitable for use as a material for making welded cans.
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The peel strength (kg/5 rMn) of the assembly was measured by a conventional tensile testing machine.
The weldability, corrosion resistance after lacquer-ing and forming and lacquer adhesion of the steel sheet obtainedby the Examples and the Comparative Exarnples were evaluated by the tests described above, the results of which are shown in the Table.
1~'7~
As it is apparent from the Table, the treated steel sheet of the present invention has excellent weldability, corrosion resistance after lacquering and forming, and excel-lent lac~uer adhesion, This treated steel sheet is therefore quite suitable for use as a material for making welded cans.
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Claims (18)
1. A process for producing a steel sheet having a lower layer of tin and an upper layer of hydrated chromium oxide, said steel sheet having excellent weldability, which comprises electrolytically tin plating a substantially clean steel sheet in an electrolyte containing a compound selected from the group consisting of stannous sulfate, stannous phenolsulfonate, stannous chloride, stannous fluoborate, sodium stannate and potassium stannate, to obtain a tin plated steel sheet having an amount of plated tin of 0.05 - 1.12 g/m2; and subjecting the resultant steel sheet to a treatment in a solution contain-ing 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 according to claim 1, wherein said treat-ment comprises an immersion treatment.
3. A process according to claim 1, wherein said treat-ment comprises an electrolytic treatment.
4. A process for producing a steel sheet having a lower layer of iron-tin alloy, an intermediate layer of tin and an upper layer of hydrated chromium oxide, said steel sheet having excellent weldability, which comprises electrolytically tin plating a substantially clean steel sheet in an electrolyte contianing a compound selected from the group consisting of stannous sulfate, stannous phenolsulfonate, stannous chloride, stannous fluoborate, sodium stannate and potassium stannate to obtain a tin plated steel sheet having an amount of plated tin of 0.05 - 1.12 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 treatment in a solution containing hexavalent chromium ions or hexa-valent 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 chrom-ium oxide in an amount of 0.5 - 5 mg/m2, calculated as chromium.
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 treatment in a solution containing hexavalent chromium ions or hexa-valent 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 chrom-ium oxide in an amount of 0.5 - 5 mg/m2, calculated as chromium.
5. A process according to claim 4, wherein said treat-ment comprises an immersion treatment.
6. A process according to claim 4, wherein said treat-ment comprises an electrolytic treatment.
7. A process according to claims 1 to 4, wherein the electrolytic tin plating is carried out in an acidic electro-lyte at a temperature of 25 - 60°C and a current density of 5 -50 A/dm2; the concentration of the stannous ion in the electro-lyte is 1.5 - 15 g/l; the concentration of acid, calculated as sulfuric acid, in the electrolyte being 1.5 - 15 g/1; and wherein the electrolyte contains ethoxylated ?-naphtholsulfonic acid at a concentration of 1 - 6 g/l.
8. A process according to claims 1 or 4, wherein the electrolytic tin plating is carried out in an alkaline electro-lyte at a temperature of 70 - 90°C and a current density of 1 - 10 A/dm2; the concentration of the stannic ions in the electrolyte is 30 - 70 g/l; and wherein the concentration of alkaline material in the electrolyte is 10 - 25 g/1.
9. A process according to claim 4, wherein heating of said tin plated steel sheet is carried out at a temperature 150 - 300°C for 0.5 - 10 seconds.
10. A process according to claims 1 or 4, wherein the upper layer is formed by an immersion treatment carried out at a temperature of 35 - 60°C and an immersion time of 0.1 - 10 seconds in an aqueous solution containing 5 - 50 g/1 of hexa-valent chromium ions, said aqueous solution having a pH of 1 -6.
11. A process according to claims 1 or 4, wherein the upper layer is formed by an immersion treatment carried out at a temperature of 35 - 60°C 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/1 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 phosphorus compound, said additive being present in an amount of 1/10 - 1/150 based on the amount of hexavalent chromium ions in the aqueous solution.
12. A process according to claims 1 or 4, wherein the upper layer is formed by an electrolytic treatment carried out at a temperature of 35 - 60°C 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.
13. A process according to claims 1 or 4, wherein the upper layer is formed by an electrolytic treatment carried out at a temperature of 35 - 60°C 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 addi-tive selected from the group consisting of a trivalent chromium compound, a sulfur compound, a fluorine compound and a phosphor-us compound which additive is present in an amount of 1/10-1/150 based on the amount of hexavalent chromium ions in the aqueous solutions.
14. A process according to claims 1 or 4, wherein said trivalent chromium compound is selected from the group consist-ing 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.
15. A process according to claims 1 or 4, wherein said sulfur compound is selected from the group consisting of sul-furic acid, 2,4-disulfophenol, 3,5-disulfocatechol, 3,6-disul-fonaphtho-2-ol, 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.
16. A process according to claims 1 or 4, wherein said fluorine compound is selected from the group consisting of NaF, KF, NH4F, H2SiF6, Na2SiF6, K2SiF6, (NH4)2SiF6, HBF4, NaBF4, KBF4, NaHF2, KHF2, NH4HF2 and Na3AlF6.
17. A process according to claims 1 or 4, 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.
18. A steel sheet having a lower layer of tin in which the tin coating weight is 0.05 - 1.12 g/m2 and an upper layer of a hydrated chromium oxide containing 5 mg/m2 calculated as chrom-ium.
Applications Claiming Priority (2)
| 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 |
| JP33433/80 | 1980-03-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1179628A true CA1179628A (en) | 1984-12-18 |
Family
ID=12386398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000372719A Expired CA1179628A (en) | 1980-03-18 | 1981-03-11 | Steel sheet with thin tin electroplate and hydrated chromium oxide |
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 |
|---|---|---|---|---|
| CN104099646A (en) * | 2014-06-25 | 2014-10-15 | 武汉钢铁(集团)公司 | Electroplating additive for stannous fluoborate system |
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. |
| KR101310598B1 (en) * | 2009-02-04 | 2013-09-23 | 신닛테츠스미킨 카부시키카이샤 | Tin-plated steel sheet and method for producing the same |
| 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 |
Family Cites Families (14)
| 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 |
| BE627962A (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 |
|---|---|---|---|---|
| CN104099646A (en) * | 2014-06-25 | 2014-10-15 | 武汉钢铁(集团)公司 | Electroplating additive for stannous fluoborate system |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2478680A1 (en) | 1981-09-25 |
| IT1143523B (en) | 1986-10-22 |
| GB2071699A (en) | 1981-09-23 |
| DE3106014C2 (en) | 1985-06-20 |
| GB2071699B (en) | 1983-04-13 |
| FR2478680B1 (en) | 1984-06-22 |
| DE3106014A1 (en) | 1981-12-24 |
| JPS56130487A (en) | 1981-10-13 |
| IT8167239A0 (en) | 1981-02-20 |
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