TWI316974B - Phosphate treated zinc-coated steel sheet having excellent corrosion resistance and blackening resistance - Google Patents
Phosphate treated zinc-coated steel sheet having excellent corrosion resistance and blackening resistance Download PDFInfo
- Publication number
- TWI316974B TWI316974B TW095105383A TW95105383A TWI316974B TW I316974 B TWI316974 B TW I316974B TW 095105383 A TW095105383 A TW 095105383A TW 95105383 A TW95105383 A TW 95105383A TW I316974 B TWI316974 B TW I316974B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- treatment
- zinc
- phosphate
- steel sheet
- Prior art date
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims description 51
- 239000010452 phosphate Substances 0.000 title claims description 51
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 50
- 229910000831 Steel Inorganic materials 0.000 title claims description 46
- 239000010959 steel Substances 0.000 title claims description 46
- 239000011701 zinc Substances 0.000 title claims description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 37
- 229910052725 zinc Inorganic materials 0.000 title claims description 36
- 238000005260 corrosion Methods 0.000 title description 9
- 230000007797 corrosion Effects 0.000 title description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 17
- 239000013589 supplement Substances 0.000 claims description 14
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 10
- 239000008397 galvanized steel Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 94
- 238000012360 testing method Methods 0.000 description 26
- 239000007788 liquid Substances 0.000 description 21
- 235000002639 sodium chloride Nutrition 0.000 description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 235000010755 mineral Nutrition 0.000 description 18
- 239000011707 mineral Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000005868 electrolysis reaction Methods 0.000 description 11
- 229910001425 magnesium ion Inorganic materials 0.000 description 11
- 238000007747 plating Methods 0.000 description 11
- 229910021653 sulphate ion Inorganic materials 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005246 galvanizing Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 phosphate compound Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 206010036790 Productive cough Diseases 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000020637 scallop Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 210000003802 sputum Anatomy 0.000 description 2
- 208000024794 sputum Diseases 0.000 description 2
- 229910052917 strontium silicate Inorganic materials 0.000 description 2
- QSQXISIULMTHLV-UHFFFAOYSA-N strontium;dioxido(oxo)silane Chemical compound [Sr+2].[O-][Si]([O-])=O QSQXISIULMTHLV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- UJZQBMQZMKFSRV-RGKBJLTCSA-N (2s,3s)-4-[(e)-3-[(1r)-1-carboxy-2-(3,4-dihydroxyphenyl)ethoxy]-3-oxoprop-1-enyl]-2-(3,4-dihydroxyphenyl)-7-hydroxy-2,3-dihydro-1-benzofuran-3-carboxylic acid Chemical compound C([C@H](C(=O)O)OC(=O)\C=C\C=1C=2[C@H](C(O)=O)[C@H](OC=2C(O)=CC=1)C=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 UJZQBMQZMKFSRV-RGKBJLTCSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- XAGHZOOCNNEKAP-UHFFFAOYSA-K C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Zn+2].[Bi+3] Chemical compound C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Zn+2].[Bi+3] XAGHZOOCNNEKAP-UHFFFAOYSA-K 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UJZQBMQZMKFSRV-PHQFMFTGSA-N Lithospermic acid Natural products O([C@@H](C(=O)O)Cc1cc(O)c(O)cc1)C(=O)/C=C/c1c2[C@@H](C(=O)O)[C@H](c3cc(O)c(O)cc3)Oc2c(O)cc1 UJZQBMQZMKFSRV-PHQFMFTGSA-N 0.000 description 1
- NFOCYHUCMXEHDG-UHFFFAOYSA-N Monomethyl lithospermate Natural products COC(=O)C1C(C=2C=C(O)C(O)=CC=2)OC(C(=CC=2)O)=C1C=2C=CC(=O)OC(C(O)=O)CC1=CC=C(O)C(O)=C1 NFOCYHUCMXEHDG-UHFFFAOYSA-N 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 241000238413 Octopus Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000237509 Patinopecten sp. Species 0.000 description 1
- 241000237503 Pectinidae Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 229940125368 controlled substance Drugs 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- STCJJTBMWHMRCD-UHFFFAOYSA-N salvianolic acid B Natural products OC(=O)C(Cc1ccc(O)c(O)c1)OC(=O)C=Cc2cc(O)c(O)c3OC(C(C(=O)OC(Cc4ccc(O)c(O)c4)C(=O)O)c23)c5ccc(O)c(O)c5 STCJJTBMWHMRCD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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Description
1316974 九、發明說明: 【發明所屬之技術領域】 本發明係關於適合於建材用或家電用等之表面處理鋼 板尤其疋適合作為塗裝用底材鋼板之鱗酸鹽處理鍍辞 …板。 .·、【先前技術】 •於建材、家電製品等用途中要求对餘性的部位,係使用 施仃鑛鋅或鑛鋅合金等表面處理的鑛鋅系鋼板。此等錄辞 系:鋼板很:直接使用’通常係施以塗裝而使用。施行塗裝 吟作為刖處理,通常係施行磷酸鹽處理、鉻酸鹽處理蓉 化成處理。 寻 ' 滅鹽處理係使含有墙酸離子之酸性溶液與鐘鋅系鋼 .板接觸而使其反應,在鑛層表面形成以峨酸辞作為主成分 之結晶性皮膜的處理,具有使其提高與塗膜之密合性且對 於各種塗裝安定的塗裝底層性能。因此,施有構酸鹽處理 春之錢鋅系鋼板,廣泛地被使用作為建材用、家電用等之塗 裝用底材鋼板。 然而,若單獨以磷酸鹽處理’其耐蝕性不足,因此,通 .2於磷酸鹽處理後施行稱為「密封處理」之封孔處理。此 •雄、封處理係以喷霧、浸潰等方法使含有6價絡之水溶液盘 •鋼板接觸,然後在不水洗下進行乾燥之處理,藉由此處理 而提高耐钕性。然而,由於6價鉻為環保管制物質,故代 替此使用含6價鉻之水溶液的「密封處理」之填酸鹽處理 皮膜之耐蝕性提高方法受到企盼。 312XP/發明說明書(補件)/95-05/95105383 5 1316974 祕=於此止盼’例如於日本專利特開2刪-⑽抓號公報 β出在鍵鋅系層面上具有結晶質之碟酸鹽系化成處理 進—步於其上具有非晶質餐系皮膜的義性優里 的表面處理鋼板。又,於日本專利特開·4_丨4期號 艮中曰提出在鑛鋅系鋼板表面具有碟酸辞處理皮膜,在豆 具有:塗佈含有銅化合物;選自鈦化合物及錯化合物 之至41種金屬化合物;或更進—步含有雙、胺類 聚縮合樹脂化合物;以及水的液狀組成物,使其 L丈木而得到之始、封處理皮膜的耐餘性及塗料密合性昱 的非鉻系鱗酸鋅處理鋼板。此等技術均為完全不使 密封處理。 m技術皆須於形成最上層皮膜的步驟中塗佈水溶 液’並進—步加熱烘烤,於既有_酸鹽處理鑛辞鋼 ^造设備之外’必須有額外的用以塗佈此等藥液之塗佈 设備及供烤設備’殘存有導致製造成本高寐之經濟面問 題。 • v + 另一方面,於無密封處理下設法提高磷酸鹽處理皮膜 身的耐蝕性之技術亦被嘗試。 、 . 例如,於日本專利特開平卜312081號公報中曾提出一 種表面處理鋼板’係在金屬材料表面形成Zn系鑛層,並 、於該鐘層上形成由含有〇.】重量%以上、5重量㈣下為佳 的Mg之磷酸系化合物所構成的皮膜。於此技術中,係土 由在填酸鹽皮膜中含有重量%以上的Mg而使•性^ 312XP/發明說明書(補件)/9M)5/95〗053 83 6 1316974 ':而,此技術中,由於在上層皮膜 在尚溫多濕環产T 、 有·,於曝露 是其問題。A P兄’表面可能會變黑,耐發黑性差 再者’於日本專利特開·2_285346號公 種耐钱性及色調優異的鱗酸辞處理鑛中4出- 膜含有2%以μ夕Μ 又f糸鋼板,磷酸辞 3有⑽上之%及〇. 0卜1%之選自Νι、 子皮 種以上的兀素’附著量為0. 7g/m2以上。 之1 二:技術中,由於在磷酸鋅皮膜中含有大量的 耐多濕環境下之情況,表面可能會變里, C0:CU且由於碟酸辞皮臈中含有高濃度的Nl’’’: C〇、Cu,導致磷酸鋅皮膜的色調變暗,是其問題。 有鑑於切技術之問題,本發明之目的在於提供不 L用絡之t封處理,具有與以往的密封處理之同等耐钱丁 且耐發黑性優異的磷酸鹽處理鍍鋅鋼板。 【發明内容】 亦即,本發明為-種耐歸及财發黑性優異之鱗酸 理鑛鋅鋼板,係於鋼板之至少一面具有链鋅層及在該^鋅 層上具有石舞酸鹽處理層者;其特徵在於,在前述錄鋅層與 磷酸鹽處理層中間形成有的鎳(Ni)附著 部。又,此鋼板以前述磷酸鹽處理層中含 層之附著量以lg/m2以上且i〇〇g/m2以下為佳。又,本發 明中,前述磷酸鹽處理層之附著量以〇2g/m1以上且3§/\2 以下為佳。 1 】2XW發明說明書(補件)/95-〇5/95丨〇5383 1316974 又,本發明之磷酸鹽處理鍍 施行下述步驟者,其為:在鋼板之至少:::=依序 錄鋅處理步驟;以及在該鑛鋅處理步驟中:: :有’:上形成鱗酸鹽處理層之鱗酸鹽處佳: 為^有附著部形成處理步驟 叙彳土者 戰後且前述碟酸趟處理牛p f 别述鑛鋅處理步 板盘含有Ϊ :: 使形成有前轉 析二者=溶液接觸’在鍍辞層表面使Nl取代 極而於含有成有前述鍵辞層的鋼板作為陰 『卢、有離子的水溶液中電解’在鑛鋅層表面折屮 I,在前述鍍鋅層表面形成微量的^ 面析出 鹽處理步驟係使用Mg離子濃度盘 °)則述崎酸 VZn、過0. 〇5之鱗:::-度的比滿足 荽邦w ^ 處 將施行過前述Ni附 物/ W 乂驟的鋼板浸潰於該磷酸鹽處理液中,或對 亀以該磷酸鹽處理液施行噴霧,在前述N : 形成作為前述_層的上層之含有Q1 f量%以上且L 2.0質量%的Mg之磷酸鹽處理層之步驟。 " j ’於本發明之魏鹽處理輯鋼板之製造方 離子以藉由硝酸%之添加者為佳,又,於本發明中, 辞處理步驟以鋅健處理步驟或炫融鑛鋅處理步 碰,X ’於本發明中,前述鑛鋅 以上且,下為佳’又,本發明中,前述N: 时均W附著量以〇.卜5〇〇mg/m2為佳,又,於本㈣卜 則述磷酸鹽處理層的附著量以〇. 2g/m2以上且3^以下 為佳。 312XP/發明說明書(補件)/95-05/951053 83 16974 【實施方式】 鋼板之Hi 4達成上述課題,針對影㈣酸鹽處理鐘鋅 作二::!、:耐發黑性的要因進… 特願2_月…果題之磷酸鹽處理鍍鋅鋼板,以曰本專利 有目單相所構成的錄鋅層、在其上具有含 此鱗酸鹽里的鱗酸鹽處理鑛辞鋼板。 惟, ,X> 兼八么/、之耐蝕性及耐發黑性, 必須在鋼板表面形成由含有 二兄’於鍍液中添加適當量的以離子可容易地形 易,Π其:晴辞來形成的情況則並不是那麼容 =此,本發明者#更進—步針對影響魏鹽處理鍵辞 板的耐錄及耐發黑性的各種要因進行深入檢討。 到在鑛鋅層與鱗酸鹽處理層的中間介人微量的W附著 之技術。因而有如下之新發現:在鋼板表面形成鑛辞層之 後,在鑛鋅層表面形成微量的Ni附著部,在該Η附著部 上再形成含有既定量的Mg之磷酸鹽處理層,藉由作成此 種表面處理層構造’提高而寸钱性及而寸發黑性,不須密封成 理,亦不須於鑛辞層中含有Ni,即可製得耐純及耐發处 黑性皆優異的鱗酸鹽處理經鋅鋼板。 本發明為基於上述之新發現再加以檢討而完成者。本發 明之磷酸鹽處理鍍鋅鋼板係在作為基板的鋼板之至少— 312XP/發明說明書(補件)/95_05/95105383 1316974 :_鋅層與該鍍鋅層上之碟 f f酸鹽處理層的"彻著‘著::二在鑛鋅層 基板的鋼板,口 I B n 才者4而作成者。作為 其種類並無特別限定^。二::為鍍辞系鋼板的鋼板皆可, 本發明t,在作適當地選擇。 辞電鑛處理』的鋼板上形成之鑛鋅層,可藉由 量,可依用途而處理來處理。又,鑛辞層的附著 以上為佳Γ而選擇’就铜生的觀點考量以 性降低。又鑛層之耐剝離
〇g/m以下為更佳。 二二於鍍鋅層表面形…1附著部,介在於其與 ^ 2 酸鹽處理層的MU /明中’介在於鑛辞層與碟酸鹽處理層的中間之 鋅?::的Nl平均附著量定為°,1〜5_多設置於鍍 = 部’只要滿足上述平均附著量的範 以均Μ的形式存在,亦可以微觀上不連續之 又’此處’「平均附著量」為如後述般,依據 01-1999中規定之附著試驗所定量的值,測定面 積為HS Η麵-1999中規定之面積的附著量之平均值。 I附著部之平均附著量若未滿〇. lmg/m2,於在上層形成 含有Mg之磷酸鹽處理層的情況,尤其無法防止在高溫多 濕環境下發生之發黑。X,Ni附著量愈多,防止發黑效 果愈確實,故Ni平均附著量以lmg/m2以上為佳,5mg/m2 以上為更佳。另一方面,Ni平均附著量若超過5〇〇mg/m2, 耐蝕性會變差,故以500mg/m2作為上限。又,以1〇〇mg/m2 312XP/發明說明書(補件)/95-05/95105383 1316974 以下為佳,以20rag/in2以下為更佳。 又,本發明之填酸鹽處理鑛鋅鋼板係在上述W附 之上具有磷酸鹽處理層作為鍍鋅層的上層。於本發明。来 酸鹽處理鍍辞鋼板中,磷酸鹽處理層含有〇. 1質量t ^ 且未滿2. 0質量%的Mg。藉由在碟酸鹽處理層中含有μ上 可延緩於鹽水喷霧試驗中發生白鐵鏽(whi te⑽士)的^ 間,可於未施行密封處理下提高石舞酸鹽處理鑛鋅鋼板之^ 餘性。藉由使磷酸鹽處理層中的%含有量成^ 」 以上’上述效果可更顯著,於未施行密封處理下,可確里0 達到與習知之施行密封處理的石舞酸鹽處理鑛辞鋼板。 蝕性大致同等的耐姓性。另一方面,即使含有2 〇質 以上的Mg,提高耐钱性的效果已達飽和,而且,鱗酸= 處理層中的Mg含有量之增加不易,且耐發黑性有變差: 傾向。因此,磷酸鹽處理層中的Mg含有量以未滿^質 夏%作為上限。又,就耐發黑性的觀點考量,以立 質量%以下為佳,尤以〇.5〜1.0質量%為更佳。. 又’於鱗酸鹽處理層中’侧處理液中所含有以他 ::子(例如Nl、Mn、c〇等)以〇.〇1〜0.4質細程度作 為無法避免的雜質而含有,亦無問題。 又’輕鹽處理層之附著量,為了销耐錄及 塗料密合性’以定為0.2g/n]2以上為佳,以"g/m2以上 為佳’以以上為更佳。又,因於 =果’於以上即達到飽和,故以3仏2定為上限 為佳。 312XP/發明說明書(補件)/95_〇5/95】〇53 83 1316974 作=’。就本發明之碌酸鹽處理鍵辞鋼板之較佳製造方法 板板依序進行下述步驟:在鋼 層表面形成微量的Ni附著部之 ^ f 以及在該N1附著部上形成石粦酸鹽處7/形成處理步驟; 上層之磷酸鹽處理步驟。 Θ卞為该鍍鋅層的 又’作為前處理’當然可視雲 _ 空蒸,::鑛;Γ及;的:=:,可例示如真 驟中,較佳者為使用電鑛法或 =之鍍鋅處理步 驟或炫融鑛鋅處理步驟。以下,作為辞電鑛處理步 進行說明。 吏用電鍵法的情況為例 於本發明之鍍鋅處理步驟中, 鍍浴組成的電鑛法之任意方法。車乂仏者可利用使用通常的 锻鋅浴為通常用以形成 液、氯化鋅溶液等,任—者皆適浴之硫酸鋅溶 又,當然可依鍍鋅層的附著 敕;特別限定之必要。 件。又,鍵辞層之附著量電流密度等之通電條 點考量,以卜100g/ffl2的範圍為佳。耐錢層制離性的觀 本:明中’於繼理步驟後且鱗 附著部形成處理步驟 ;= 步驟之前, 中’較佳者為將藉由鑛鋅處 ::蝴理步驟 3,2ΧΡ/*««)/95-05/95105383 4㈣表面形成鑛鋅層的 22 1316974 鋼板’與含有Ni離子的水溶液接 鋅層表面,或者,更積極地以形成有析出於锻 為陰極,於合古Μ. # 有則述鍍鋅層的鋼板作 3有Nl離子的水溶液中電解,在鲈锌 取代析出Ni ,萨&报旦& λ1. 隹鍍鋅層表面 θ _成心的Nl附著部 處理步驟中所❹之含有Nl離子的水溶液,可使= 鎳或硫酸鎳等之水溶液。又二 对錄々、、六、、产丄 傲琢N1附者I而適當地 二K # Nl濃度、液溫、接觸時間或電解條件等 馬佳。
施行過Ni附著部形成處理步驟的鋼板,接著再施行麟 酸鹽處理步驟。於磷酸鹽處理步驟中,在W 成含有0」質她上且未滿2·〇質量%之此的石粦酸鹽處 理層。鱗酸鹽處理層較佳者為使施行過Ni附著部形成處 理步驟的鋼板與磷酸鹽處理液,藉由噴霧或浸潰等之通常 方法使其接觸而形成。為了使磷酸鹽處理層中含有Mg, 於^發明中,係使用Mg離子濃度與Zn離子濃度之重量比 (Mg2+/Zn2+)超過〇. 〇5(以5以下為佳)之磷酸鹽處理液。 又,方;鱗酸鹽處理液中含入之Mg的量,於處理液中之
Mg2+/Zn2+比之外’處理液中之Zn濃度、液溫、pH等亦有 影響。前述Mg2+/Zn2+的範圍,於進行通常的化成處理之條 件下,特佳者為例如Zn濃度:〇. 5〜5g/L、液溫:30〜70 °C、pH : 1. 0〜2. 5 的範圍。
Mg2+/Zn2+若為〇. 05以下,會有無法作成含有〇. 1質量% 以上之Mg的磷酸鹽處理層之情況。又Mg2+/Zn2+若超過5 而變得太高’則磷酸鹽處理層中之Mg量會有偏離適當範 312XP/發明說明書(補件)/95-05/95105383 13 1316974 圍之情況。為了使磷酸鹽處理液中之Mg2+/Zn: 的程度中,必須使Mg鹽以適當的濃度溶解。因此,與 配對之陰離子的選擇非常重要。於使用氫氧化Mg、石炭、/
Mg二硫酸Mg等作· Mg離子源的情況,會有無法得到人二 的〉谷解度之傾向。氯化Mg雖有充分的溶解度,惟,高二 度的氯離子會與Mg離子同時混入到麟酸鹽處理液中3 辱牛駄鹽皮膜的形成造成不良影響。基於此,哋離子· 石肖酸Mg為佳。 '、 本發明中使用之磷酸鹽處理液,較佳者可利用於含 離子、碟酸離子,並進-步含有促進劑等之市售的處理液 (例如日本Parkerizing (股)製之商品名「PB3312M」)等 中再添加既定量的上述Mg離子源所成者。又,碟酸越户 理層之附著量,藉由控制鋼板與_鹽處理液的接觸^ 之通常方法而調整於〇·2〜3. 〇g/m2的範圍為佳。 /又’以於進行«鹽處理步驟之前,對施行Νι附著部 形成處理步驟之鋼板表面作表面調整處理為佳。經施行 Ni附著部形成處理步驟之鋼板表面的表面調整,以使用 鈦膠體⑴恤⑶山⑷系活性處理劑進行喷霧為佳。欽 私體糸活性處理劑可例示如日本ParkeHzing⑻製之 普雷巴連ZN(商品名)。接著’依據實施例 細地加以說明。 又干 (實施例) 自板厚的冷軋鋼板裁取大小為2ig χ刚_之言式 驗板。對此試驗板I先施行前處理。前處理係於添加石夕酸 312χρ/發明說明書(補件)/95-〇5/95105383 14 1316974 鈉(60g/L)之鹼脫脂液(液溫·· 70t)中,以不鎸鋼為對電 極,於電流密度:5A/dm2下施行30秒間的電解脫脂與電 角午脫知後水洗,再於3 0g/L的硫酸水溶液(液溫:3 〇 ) 中浸潰5秒進行酸洗,之後再水洗的處理。於施行此前處 理後,對試驗板實行鋅電鍍處理,在試驗板的單面形成附 著量·· 5〜40g/m2的鑛鋅層。 電鍍鋅處理如下述。
使用添加有440g/L的硫酸鋅7水合物之鍍鋅液作為鍍 鋅浴。於鍍鋅液添加硫酸,調整pH為15。又,鍍鋅浴" 的浴溫設定為5(TC。於上述鍍辞浴中,以被覆氧化銥: Ti板電極作為對f極,將該對電極與試驗板以極間距離 ίο麵平行地配置,一邊於極間以流速15m/s使鍍液循 環’一邊以電流密度7〇A/dm2通電。 如此般,於試驗板表面形成輯層後,在韻鋅層表面
施2 Ni附著職之⑽附著形成處理,錢鋅層上形成 附著量為0. 1〜500mg/in2之Ni附著部。
Ni附著形成處理係如下述。 面形成有鑛鋅層之試驗片浸潰於叫几的硫酸 鎳水洛液(40。〇中1〜10秒,或以被覆氡 作為對電極,使該對電極與試驗片平行地配置,^電、^ ^ 5A^通電進^電解,使既^量的Ni析出形成^著 二。1附者量可藉由改變浸潰時間或電解時間而調 進行水洗,接著 如此,在鍍鋅層上形成Ni附著部後 3_發明說明書(補件)/95卿9簡如 1316974 再施行磷酸鹽處理。又,磷酸鹽處理之前處理,係對在铲 鋅層上形成有Ni附著部的鋼板,施行藉由表面調整劑(日" 本Parkerizing (股)製··商品名「普連帕連z」)進"行之 表面調整處理。 磷酸鹽處理係使在鍍鋅層上形成有Ni附著部的鋼板以 石粦酸鋅處理液(於曰本Parker izing (股)製:商品名 「PB3312M」中添加有硝酸Mg者;Zn濃度:3 5g/L、液 溫:60°C、pH : 2. 2)噴霧使其接觸,再水洗、乾燥,形成 石粦酸鹽處理層,作成在鍍鋅層與碟酸鹽處理層中間介在著 Ni附著部而構成之磷酸鹽處理鍍鋅鋼板(試驗板)。又, 藉由改變添加於磷酸鹽處理液中之Mg源的添加量,可改 變磷酸鹽處理層中的Mg量。又,磷酸鹽處理層的附著量 可藉由改變與磷酸鹽處理液的接觸時間而改變。 又,在比較之目的下,使用通常的鍍鋅浴形成純鋅鍍 層用通#的礙酸鹽處理液形成不含有Mg之鱗酸鹽處理 層’再用以鉻(VI)酸酐為主成分的水溶液(曰本 Parkerizing (股)製:商品名rLN62」)施行密封處理, 作成磷酸鹽處理鍍鋅鋼板(試驗板)(試驗板N〇. 26)。亦 製作未施行密封處理的磷酸鹽處理鍍鋅鋼板(試驗板)(試 驗板 N 〇. 2 4 )。 對得到的試驗板,就鍍鋅層、Ni附著部及磷酸鹽處理 層的附著量、耐蝕性及耐發黑性進行調查。又,係以得到 的試驗板之形成有鍍鋅層及磷酸鹽處理層的面作為進行 調查的面。調查方法如下。 16 312XP/發明說明書(補件)/9105/95】05383 1316974 ⑴鑛鋅層、Ni附著部及魏鹽處理層的附著量 鑛鋅層中之Μ相著量及形成賊鋅層上的 量,係如下求出:對鍍辞處理細析出附:: 形成Nl附著部的鑛鋅層,依據JISH_h999 2見疋㈣者钱驗方法,使其溶解於 I,將溶解鑛層的独JISK012卜刪中規定土的H …方式原子吸光分析裝置進行 ;: 的附英旦在丨、/击Μ * 析而求出。磷酸鹽處理層 水溶液溶解,以重量法求出。又, 磷酸鹽處理層中之M合右旦 ^ 人 重鉻酸銨水溶液中,龄錢伽鹽處理層溶解於 電裝發光分㈣行分料⑽分析(感應結合 (2 )耐Ί虫性 自得到之試驗片裁切出試驗 試驗片的端部及背面以膠帶密 ,將 的規定實施鹽水喷霧試驗。試驗中定= JISZ 237卜2000 面,觀察至白鐵鐵產生面積相、也規察試驗片表 成為咖時間(白鐵鏽產生時驗片之全部評估面積 白鐵鏽產生時間為24 λ!、時以上的棒/丁耐钱性之評估。 時以上且未滿24小時的情況判定定為「◎」,8小 未滿8小時的情況判定為「△, 」,4小時以上且 為「X」。 」,未滿4小時的情況判定 (3)耐發黑性 自得到之試驗片裁切出試驗片(尺 分光式色差計SQ2000(日本電辛制、寸:100 χ 50麵),用 之 衣)’首先測定試驗片 312ΧΡ/發明說明書(補件)/95-〇5/95105383 17 1316974 初』L值(明度,1 ightness)。然後,脸 声8 π。广 e- …、後’將试驗片放置於溫 度㈣、濕度95%RH的恆溫㈣ 置於/皿 同樣地測定試驗片的“直,求 卞。放置後’ 而未滿-1的情況判定為「〇 疋”、、〇」,—2以上 定為「△」,来、$ 4 ^ 4以上未滿-2的情況判 之,… 的情況判定為「X」,依此作耐發里性 之汗估。得到之結果示於表丨。 ‘、、、『生 本發明例之任一者皆在未施 具有與習知之磷酸鴎處理鈿 山、 卩可侍到 芬门々“ 處里鋼板之同等或其以上的耐飯性 ^專的耐發黑性之_鹽處理㈣鋼板。另— 本發明範圍外之比較例,於耐純、㈣黑性 = 會變差。 仕者
312ΧΡ/發明說明書(補件)/95-05/95 ] 053 83 18 1316974 〔5
〇i 泰發明例 \ X 比較例 襟註i 4 5 容 4 本發明例 丨 本發明例 本發明例 本發明例 1 冬發明例 1 -4 本發明例 本發明例 本發明例 1 本發明例 1 珈 4 本發明例 本發明例 本發明例 本發明例 本發明例 本發明例 1 本發明例 〇 泰發明例 军 ϋ 比較例 % 試驗結果 j ◎ 〇 〇 〇 <1 <] ◎ ◎ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 <1 〇 〇 X 〇 X 〇 <3 <3 〇 ◎ ◎ ◎ <3 <3 ◎ ◎ <] <3 〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇 <1 <1 〇 X 磷酸鹽處理層 LT5 οα ο CS] 卜 〇► (>α —— CO CO oa 〇〇 oi CO 一 § 〇〇 r-H 〇〇 1—1 C? »—Η οα CO i 1 LO 1 t (Nl 1 in ο ΙΟ ο 〇 1- i LO »—1 C? cm' 〇 CO 03 1 (NI 03 r-H CN r—^ 1 Mg含量 C質量» »-»-Η CD ίΝΙ 〇> LO Ο ο 寸 03 r-1 · <=3 (Nl <Z> CO -丨Η γ· Ή 〇 CO c=> LO Ο »—Η r-H oo CO οο r«< C3 LO 03 C5 CM C3 C<I 1 LO C? Ni附著部 w附著量 (ms/πι2)丨 C3 τ-Η Ο 〇> Ξ ο s § 〇 〇 ο s Ο S ΙΛ LO to in L〇 r-H ! 1 τ—Η τ—Η 1 1 1 1 鍍鋅層 附著量1 (g/m2) LO Ο m ! LO LO 另 § s S s § 密封處理 碟 碟 碡 碟 m 碡 碟 媒 礫 碟 碱 碟 碟 碟 碟 碟 碟 磲 碟 碟 杯 蛾酸鹽處理 處理液中 MgVZif ◦ οα ο s ο § 1—< g CO s g ο LO cs] g 寸 〇 c^a ο S <=> § 1—( g s § § 03 C<1 g i 0.60 1 Ni附著部 形成處理 效S 1! 電解 電解 浸潰 遂 丨電解 電解 1 電解 電解 電解 電解 黎 電解 電解 電解 1 電解 電解 浸潰 浸潰 電解 杳解 1 1 1 1 試驗 板No. »—ί <Μ CO L〇 CO 卜 οο σϊ Ο CN (X L〇 ς〇 c— 00 σ> C< CO CvJ (Nl L〇 CNI CD 61 S£S2 56/so-s6/ff}5i)修器鑑Ka 微/dxcsI ε 1316974 (產業上之可利用性) 依據本發明,不須施行密封處理,容易且廉價地製造可 具有與習知之磷酸鹽處理鍍鋅鋼板同等以上的耐蝕性且 具有同等之耐發黑性的磷酸鹽處理鍍鋅鋼板,於產業上可 發揮特別的效果。又,依據本發明,可於防止對環境造成 不良影響下製造磷酸鹽處理鍍鋅鋼板。
312XP/發明說明書(補件)/95-05/95105383 20
Claims (1)
1316974 十、申請專利範圍: 1 ·—種耐録及耐發黑性優異之 板’係於鋼板之至少一面具有錢❹/;處理鑛鋅鋼 •鹽處理層者.料彳/^ 該料層上具有 層中H 述料層㈣酸鹽處理 T間形成有0·卜500mg/m2的鎳(Ni)附著部。 2.如申請專利範圍第丨項之磷酸鹽處理鍍鋅鋼板,其 旦,上述磷酸鹽處理層含有〇1質量%以上且未滿2 ^質 量%之Mg。 ·、 312XP/發明說明書(補件)/95-〇5/951 〇5383 21
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